KR20190055759A - Antifouling coating composition - Google Patents

Abstract

The present invention relates to a novel binder for an antifouling coating composition comprising an acidic comonomer-containing (meth)acrylate copolymer and having a low glass transition temperature (Tg). The binder can prepare an antifouling coating having low fresh water absorption and a coating having an optimal viscosity such that a coating process may be allowed without the need for an excessive amount of solvent. A binder for an antifouling coating composition of the present invention comprises: a (meth)acrylate copolymer (A) having a Tg of 0 °C or less and including as a comonomer, i) at least one (meth)acrylate of formula (I), in which R^1 is H or CH_3, and R^2 is a C1-C20 hydrocarbyl substituent, and ii) 0.70 to 8.6 wt% of at least one carboxylic acid-containing comonomer based on the total weight of the copolymer (A), a combination of the monomers (i) and (ii) representing at least 80 wt% of the monomers existing in the copolymer (A); and a cyclic monocarboxylic acid, e.g., rosin or derivatives thereof (B).

Description

ANTIFOULING COATING COMPOSITION [0001]

The present invention relates to a novel binder for antifouling coating compositions comprising a (meth) acrylate copolymer containing an acidic comonomer and having a low Tg. The binder can produce anti-fouling coatings with low fresh water absorption and coatings with optimal viscosity to allow application without the need for excessive amounts of solvent.

Surfacing surfaces are subject to contamination by marine organisms such as green and brown algae, barnacles, mussels, western ponds and other similar species. Such contaminants in offshore structures such as ships, oil platforms, buoys, etc. have undesirable economic consequences. Contamination can lead to biological degradation of the surface, increased load and accelerated corrosion. Contamination at the vessel will increase the frictional resistance which will result in reduced speed and / or increased fuel consumption. It can also lead to reduced maneuverability.

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

An important parameter is water absorption in fresh water, given the antifouling coating for locked surfaces. These parameters are important in the coatings to be used in seawater. Many sailing vessels will sail through fresh water for some periods, such as those that run through the Panama Canal. Freshwater absorption is also an important parameter in certain areas of China where, for example, new buildings are replenished from rivers in freshwater rivers. In these cases, high water uptake may lead to excessive swelling and, in the case of weakness, breakage of the coating film. This property is an important indicator of seawater performance because coatings with long term stability in fresh water have good performance in seawater. In seawater, the coating absorbs water, but the rate and amount are reduced due to lower osmotic pressure compared to fresh water.

The antifouling coating is designed to operate for up to 7.5 years during operation. The maintenance of minimum water absorption during this period is an important factor in controlling release of the active ingredient from the coating. Within any given type of pollution prevention technology there is a clear relationship between long-term reliable performance and moisture absorption. Excessive water uptake may lead to a lower performance of the active ingredient than desired and a deterioration in performance over the lifetime of the coating. Depending on the type of binder system used, increased water uptake can lead to faster hydrolysis of the active ingredient and excessive erosion or accelerated leaching, resulting in a thickened layer (a leached layer) against the surface of the coating . Control of moisture uptake in all cases is a key parameter in the design of high performance antifouling coatings such as new structures and dry docking coatings.

The inventors have surprisingly found that a composition comprising a (meth) acrylate copolymer binder ideally having a Tg of 0 DEG C or less and comprising a specified amount of an acidic comonomer, To provide excellent results on freshwater absorption. Below the optimum range of the acidic comonomer content, undesirably high fresh water absorption is observed, while above the optimum range, a high viscosity is obtained, which means that a higher amount of solvent is required for the application of the paint It turned out. Finding paint with low VOC content is clearly undesirable because there are many countries with limited levels of VOCs allowed.

This document includes a number of disclosures of binder polymers for antifouling coatings. Silyl ester copolymers and acrylate polymers are particularly well known. However, there is little disclosure of binders comprising (meth) acrylic acid comonomers as required in the present invention.

In EP 1288234, antifouling coating compositions are prepared based on hydrophilic monomers and N-vinyl lactam. The above exemplified polymers include functionalized copolymers of methacrylic acid, methyl methacrylate, butyl acrylate, and vinyl pyrrolidone. Polymer Example 3 contains MAA: vinylpyrrolidone: MMA: MA: BA (0.9: 18.6: 23.2: 49.3: 8 mol%), indicating that vinylpyrrolidone is present in an amount of 21 wt% it means.

WO 9744401 discusses the use of rosin, fiber and polymer softeners in antifouling coatings. In the above examples, Zn-Resinate is used with polymers based on various monomers. As it is used throughout the trade name, the nature of the polymer used is not disclosed.

WO2008105122 discloses antifouling coating compositions comprising polymeric softeners, silyl copolymers and antifouling agents. The above examples use various forms of rosin with polymers based on silyl esters and acrylate comonomers. Acrylic acid or methacrylic acid is not mentioned as possible monomer.

WO2005005516 describes a silyl stearic copolymer having a low molecular weight. An example is the combination of an acrylate polymer and rosin, but clearly no acrylic acid monomer.

WO2011131721 discloses coating compositions produced by the addition of different ingredients in a particular order. In the examples, rosin is used with Neocryl B725 (acrylate-based copolymer). Neocryl B725 has a very high Tg value.

WO2014175140 describes silyl copolymers having specific end groups. TISA and TISMA copolymers are used in the practice. Rosin, hydrogenated rosin and zinc rosinate are used in paint embodiments. There is no indication of the presence of acrylic acid monomers.

EP 3078715 discloses a coating composition comprising a silyl ester copolymer, a tralopyril and a stabilizer. In embodiments, TISMA copolymers, gum rosins, and acrylic polymers are used.

CN105295630 and CN105001358 Copper / zinc acrylate contamination-preventing resin. Resins are prepared by reacting an acid-functional acrylic prepolymer with metal hydroxides and monocarboxylic acid compounds. In embodiments, the ratio between the acrylic prepolymer and the monocarboxylic acid compound is from about 11: 1 to 4: 1.

WO2003 / 027194 or JP2003246962 relates to an antifouling coating composition comprising a non-aqueous dispersion resin having a core-shell structure composed of (a) a hydrophilic core component and (b) a shell component. The hydrophilic polymer in the core comprises 5-75% by weight of monomer having an acidic group. A non-aqueous dispersion (NAD) is a system wherein discrete polymer particles are dispersed in a solvent. The non-aqueous dispersion of the document forms an opaque white dispersion. The copolymer of the present invention forms a clear solution, i.e. the polymer is soluble in the solvent and is not a separate phase from the solvent. The acid-containing core material has an estimated Tg of 60-75 占 폚.

KR20160081540 describes the preparation of zinc acrylate resins in which acid-functional acrylic is reacted with metal oxides, half-esters and monocarboxylic acid compounds.

GB 2204046 relates to antifouling paints comprising a copolymer based on cyclic tertiary amides or imides such as N-vinyl pyrrolidone.

The ingredients claimed in the claims provide novel and outstanding results.

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

(A) a (meth) acrylate copolymer having a Tg of 0 占 폚 or less as a comonomer and comprising:

i) at least one (meth) acrylate of formula (I):

(Wherein R ¹ is H or CH ₃ and R ² is a C ¹ -C 20 hydrocarbyl substituent); And

ii) at least one carboxylic acid-containing comonomer of from 0.70 to 8.6 wt%, based on the total weight of said copolymer (A), said combined comonomers (i) and (ii) being present in copolymer (A) Said carboxylic acid-containing comonomer exhibiting at least 80 wt% comonomer; And

(B) cyclic monocarboxylic acids such as rosin or derivatives thereof such as salts thereof.

The present invention also provides an antifouling coating composition comprising a combination as described herein, preferably dissolved in a solvent. The antifouling coating may further comprise antifouling agents, preferably copper oxide and / or copper pyrithione and / or zinc ethylene bis (dithiocarbamate). The binder and said antifouling coating may also comprise a hydrolyzable copolymer component (C) and / or a non-hydrolyzable component (D) as defined herein.

The present invention also provides a method of protecting an object from contamination, the method comprising coating at least a portion of the object to be contaminated with an anti-fouling coating composition as defined herein.

The present invention also relates to the use of the antifouling compositions of the present invention for protecting marine surfaces from contaminated objects or contamination with antifouling coating compositions as defined herein.

Justice

The term "marine antifouling coating composition", "antifouling coating composition" or simply "coating composition" refers to compositions suitable for use in marine environments. The antifouling coating composition preferably contains antifouling agents, such as biocides.

The term hydrocarbyl group refers to any group containing only C and H atoms and thus includes alkyl, alkenyl, aryl, cycloalkyl, arylalkyl, and the like.

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

The term " rosin " used in the following context is used to include " rosin or a derivative thereof ".

The term " binder " defines a portion of a composition comprising a copolymer and a cyclic monocarboxylic acid, and any other components that together form a matrix that imparts the substratum and strength to the composition. The term " binder " as used herein includes binder (A) and cyclic monocarboxylic acid binder (B) and optional components (C) and (D).

The term " Tg " means the glass transition temperature.

Given the wt% of a given comonomer, wt% is relative to the total weight of each comonomer present in the copolymer.

Detailed description of the baldness

The present invention relates to novel binders for marine antifouling coating compositions that exhibit significantly lower water uptake in fresh water. These compositions can therefore provide protection against contamination during prolonged service intervals. The binder comprises a (meth) acrylate copolymer (hereinafter referred to as a '(meth) acrylate copolymer (A)' or a 'binder component (A)'), which contains 0.70-8.6 wt% It contains monomers and has a Tg of less than 0 ° C. The binder also comprises a second binder component (B) which is a cyclic monocarboxylic acid such as a rosin or rosin derivative.

Copolymer A

(Meth) acrylate copolymer (A) comprises as comonomer:

i) at least one (meth) acrylate of formula (I):

(Wherein R ¹ is H or CH ₃ and R ² is a C ¹ -C 20 hydrocarbyl substituent); And

ii) from 0.70 to 8.6 wt%, based on the total weight of said copolymer (A), of at least one carboxylic acid-containing comonomer.

(Meth) acrylate copolymer (A) has a glass transition temperature (Tg) of 0 ° C or less, such as -1 ° C or less, -2 ° C or less, or -4 ° C or less, . Particularly, the (meth) acrylate copolymer (A) has a melting point of from 0 to -60 占 폚, for example from -1 to -60 占 폚 or from, for example, -5 to -55 占 폚, preferably from -10 to -50 占 폚, Lt; RTI ID = 0.0 > 45 C. < / RTI > It is contemplated that the use of a (meth) acrylate copolymer (A) having a glass transition temperature (Tg) of 0 DEG C or less will reduce the viscosity of the final antifouling coating composition and thus reduce the required solvent content.

The combination of comonomers as defined under i) and ii) comprises at least 80 wt%, such as at least 85 wt%, preferably at least 90 wt%, more preferably at least 95 wt%, or at least 96 wt% (A). In another specific embodiment, the combination of comonomers as defined under ii) and ii) represents up to 95 wt% of copolymer (A), such as up to 96 wt% or up to 99 wt% of copolymer (A).

Certainly, combinations of comonomers defined under " i) and ii) " include two or more comonomers of formula (I) or functional groups having two or more carboxylic acid-containing comonomers. The copolymer (A) preferably comprises less than 10 wt%, preferably less than 5 wt%, of the comonomer and the carboxylic acid-containing comonomer of formula (I) as described in i) and ii) Contains less than 4 wt%, preferably less than 2 wt%, of any comonomer. In certain embodiments, components (i) and (ii) comprise a comonomer component transfer of copolymer (A). Configure

In certain embodiments, the copolymer (A) does not include a hydrolysable comonomer, such as a silyl ester comonomer. Preferably, the copolymer (A) is non-hydrolyzable.

Preferably, the copolymer (A) has a weight average molecular weight (Mw) of 10,000 to 50,000 g / mol, preferably 15,000 to 45,000 such as 15,000 to 43,000 or 15,000 to 40,000 g / mol. The viscosity of the polymer solution increases with the increased average molecular weight (Mw). The preferred molecular weight of these ranges is to reduce the viscosity of the polymer and thereby reduce the amount of solvent required in the antifouling coating composition and volatile organic compound (VOCs) content. The copolymer (A) may have a PDI of 2 to 6.

When measured according to the acid value test described in the Example section, it may have an acid value of 2 to 12 mg KOH / g of polymer. In a further embodiment, the copolymer (A) has an acid number of 8.0-50.0 mg KOH / g dry polymer, such as 8.0-30.0 mg KOH / g dry polymer, such as 8.0-20.0 mg KOH / g dry polymer.

(Meth) acrylate comonomer (i)

The (meth) acrylate comonomer to be used in copolymer (A) is of formula (I)

Wherein R ¹ is H or CH ₃ and R ² is a C ¹ -C 20 hydrocarbyl, preferably a C 1-8 alkyl substituent, most preferably methyl, ethyl, n-propyl, n-butyl or 2- Ethylhexyl. Particularly preferred R < ² > groups are methyl, butyl, and 2-ethylhexyl.

Comonomers according to formula (I) are referred to herein as " non-hydrophilic " comonomers.

In certain embodiments, the (meth) acrylate copolymer (A) is selected from the group consisting of methyl methacrylate (MMA), n-butyl acrylate (n-BA), 2- ethylhexyl methacrylate (Meth) acrylate comonomer of formula (I) selected from ethylhexyl acrylate (2-EHA), and n-butyl methacrylate (n-BMA). In certain embodiments, the (meth) acrylate copolymer comprises at least two different comonomers of formula (I).

In certain embodiments, the (meth) acrylate copolymer (A) comprises methyl methacrylate (MMA) as one comonomer of formula (I) and at least one other comonomer. In a further specific embodiment, the (meth) acrylate polymer (A) comprises at least methyl methacrylate and butyl (meth) acrylate. When at least one (meth) acrylate comonomer of formula (I) is present, the sum weight percentage of these (meth) acrylate comonomers in the (meth) acrylate copolymer is preferably at most 99.30 wt% wt%, such as up to 99.0 wt%, such as up to 98.7 wt%, such as 98.6 wt%.

In addition, when at least one (meth) acrylate comonomer of formula (I) is present, the percentage of the sum of these (meth) acrylate comonomers in the weight methacrylate copolymer is such that (meth) acrylate copolymer (A) Preferably at least 80 wt%, such as at least 85 wt%, such as at least 90 wt%, such as at least 91.4 wt%, based on the total weight of the composition.

When present, methyl methacrylate is preferably present in an amount of from 1.5 to 50 wt% copolymer (A), preferably from 1.5 to 30 wt%, preferably from 1.5 to 25 wt%.

 When present, n-butyl acrylate is preferably present in an amount of from 50 to 99 wt%, preferably from 55 to 99 wt%, preferably from 65 to 99 wt%, such as from 70 to 99 wt%.

The carboxylic acid-containing comonomer (ii)

The carboxylic acid-containing comonomer (s) to be used in the (meth) acrylate copolymer (A) provide coatings with excellent results on fresh water absorption. The carboxylic acid-containing comonomer (s) are interchangeably referred to herein as the acidic comonomer (s). Below the optimum range of acidic comonomer content, undesirably high fresh water uptake is observed, whereas above the optimum range of acidic comonomer content, a high viscosity is obtained, which means that a higher amount of solvent is required for the paint application It was found that it means to do.

Preferably, therefore, the acidic comonomer is present in an amount of from 0.70 to 8.6 wt%, based on the weight of the (meth) acrylate copolymer (A). In a further specific embodiment, the carboxylic acid-containing comonomer is present in an amount of from 0.8 to 8.6 wt%, such as from 1.0 to 7.5 wt%, such as from 1.2 to 7.0 wt%, such as from 1.30 to 1.9 wt%, based on the weight of the (meth) 6.5 wt%, such as 1.4-6.0 wt%.

Preferably, the carboxylic acid-containing comonomer is acrylic acid (AA) or methacrylic acid (MAA), more preferably methacrylic acid. A combination of acrylic acid and methacrylic acid may be used. The carboxylic acid-containing comonomer is preferably free of any N-vinyl lactam comonomer. In particular, the absence of N-vinylpyrrolidone is preferred.

The binder preferably comprises 10 to 50 wt%, preferably 15 to 30 wt% (dry solid) of component (A).

In the present invention, the antifouling composition preferably contains 0.5 to 25 wt.%, Preferably 1 to 22 wt.%, Preferably 2 to 20 wt.%, Preferably 5 to 18 wt.% (Dry solid) ).

The amount of copolymer (A) in the binder is preferably limited to avoid too soft antifouling coating films. The hardness of the coating film is determined by the binder mixture. Too soft antifouling coating films are prone to block marks on the shipyard yard, fender damage and scratches during operation and, in extreme cases, low temperature flow of the coating film.

The cyclic monocarboxylic acid component (B)

The binder of the present invention comprises at least one cyclic monocarboxylic acid (B). Cyclic monocarboxylic acids may contain one ring or multiple cyclic rings. In particular, such rings may be fused rings. The cyclic monocarboxylic acid is preferably selected from resin acids, derivatives of resin acids, C6-20 cyclic carboxylic acids, and mixtures thereof. Suitable monocarboxylic acids include, but are not limited to, those derived from resin acids such as abietic acid, neoabietic acid, dehydroabietic acid, dihydroabietic acid, tetrahydroabietic acid, palustric acid, levopimaric acid, Acid, sandalacopimaric acid, comonic acid; (4-methyl-3-pentenyl) -3-cyclohexene-1-yl-carboxylic acid, 1-methyl- Methyl-3-pentenyl) -4-cyclohexen-1-yl-carboxylic acid, trimethylisobutylcyclohexene carboxylic acid such as 1,4,5-trimethyl- 2- Hexene-1-yl-carboxylic acid and 1,5,6-trimethyl-3- (2-methyl-1-propenyl) -4-cyclohexen-1-yl-carboxylic acid and mixtures thereof. Ideally, the cyclic monocarboxylic acid comprises rosin or a derivative thereof.

The monocarboxylic acid may be used to adjust the self-polishing and mechanical properties of the antifouling coating film.

The rosin used in the present invention may be rosin or a derivative thereof, such as a salt thereof, for example, as described below. Examples of rosin materials are wood rosin, tall oil rosin and gum rosin; Rosin derivatives such as hydrogenated and partially hydrogenated rosins, unsaturated rosins, maleic acid-modified rosins, fumaric acid-modified rosins; Metal salts of rosin and rosin derivatives such as copper recite, zinc recinate, calcium recite, magnesium reciteate and others as described in WO 97/44401. Preferred are derivatives of gum rosins and gum rosins.

In the present invention, the antifouling composition preferably contains from 0.5 to 25 wt.%, Preferably from 1 to 22 wt.%, Preferably from 2 to 20 wt.%, Preferably from 5 to 18 wt.% (Dry solids) ).

The binder preferably comprises 10 to 70 wt%, preferably 20 to 50 wt% (dry solid) of component (B).

Preferably, in the binder of the present invention, the copolymer (A) and component (B) are used in a ratio of from 1: 1 to 1:30, such as from 1: 1 to 1:20, such as from 1: 1 to 1:10, 1 to 1: 5. Typically, therefore, there are more components (B) than the polymer (A) by weight in the binder of the present invention.

The ratio between the copolymer (A) and the cyclic carboxylic acid compound (B) is important for the hardness of the coating film. Antifouling coatings with more component (A) than component (B) can have damage due to coatings which are too soft and easy to block marks at the shipyard, operating penter or scratches. In extreme cases, low temperature flow of the coating film may occur.

Further preferably, components (A) and (B) together make at least 50 wt%, such as at least 60 wt% of the binder of the antifouling coating composition of the present invention.

In one embodiment, the binder comprises 10 to 50 wt%, preferably 15 to 30 wt% (dry solid) of component (A) and 10 to 70 wt%, preferably 20 to 50 wt% And component (B).

The additional hydrolyzable copolymer (C)

The binder compositions of the present invention may comprise additional components. These may be non-hydrolyzable (meth) acrylates or hydrolyzable copolymers such as silyl ester copolymers.

The compositions of the present invention may thus comprise a hydrolysable binder component such as a silyl ester (meth) acrylate copolymer. Hereinafter, the terms 'hydrolyzable copolymer', or 'hydrolyzable silyl ester copolymer' are used interchangeably and refer to an optional silyl ester (meth) acrylate, which may be present in the binder and anti- ≪ / RTI > These copolymers contain side chains that are hydrolyzed in natural seawater. Non-hydrolyzable (meth) acrylates do not contain side chains that are hydrolyzed in natural seawater (for example, methyl methacrylate and n-butyl methacrylate).

Suitable silyl (meth) acrylate comonomers used in such hydrolyzable silyl ester (meth) acrylate copolymers are preferably represented by formula (II): < EMI ID =

Wherein,

R ³ is H or CH ₃ ;

Each R ⁴ is independently selected from a linear or branched C _1-4 alkyl group;

Each R < ⁵ > is a linear or branched C1-C20 Alkyl group, C3-C12 Cycloalkyl groups, optionally substituted C6-C20 An aryl group and an -OSi (R < ⁶ >) ₃ group;

Each R < ⁶ > is independently a linear or branched C1-C4 Alkyl group,

p is an integer from 0 to 5;

The term " alkyl " is intended to include both linear or 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 halogen, an alkyl group having from 1 to about 8 carbon atoms, an acyl group, 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 a compound of formula (II) wherein p is zero.

More preferably, the silyl ester comonomer is represented by formula (III): < EMI ID =

Wherein R ³ is H or CH ₃ ; And

Each R < ⁵ > is a linear or branched C1-C10 Alkyl < / RTI > group.

Examples of monomers containing silyl ester functional groups are well known. The monomers defined by formula (II) 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, tert -butyldimethylsilyl (meth) acrylate, tert -butyldiphenylsilyl Trimethylsiloxy) methylsilyl (meth) acrylate, tris (trimethylsiloxy) silyl (meth) acrylate.

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

Preferably, the hydrolyzable polymer comprises at least 10 wt% silyl ester comonomer, such as at least 15 wt%, such as 15 to 75 wt% or 15 to 65 wt% silyl ester comonomer component.

In addition to the silyl ester comonomer (II), the hydrolysable copolymer (C) ideally comprises a second comonomer as defined herein below. The second comonomer preferably comprises a non-hydrophilic comonomer of formula (I) or a hydrophilic comonomer of formula (IV). The hydrolyzable copolymer may also comprise a comonomer of formula (I) and a comonomer of formula (IV).

The hydrophilic comonomer of formula (IV) is of the formula:

Wherein R ⁷ is H or CH ₃ and R ⁸ is a C 3 -C 18 substituent with at least one oxygen or nitrogen atom, preferably at least one oxygen atom. As used herein, this structure defines a " hydrophilic " (meth) acrylate comonomer.

Requires group R ⁸ in the term "hydrophilic (meth) acrylate" formula (IV) to contain at least one oxygen or nitrogen atom, preferably at least one oxygen atom as illustrated above formula. As further detailed below, additional non-hydrophilic (meth) acrylate comonomers of formula (I) may also be present in the hydrolyzable copolymer, wherein the R ² unit consists only of C and H atoms.

In one embodiment, the hydrolyzable copolymer comprises at least one comonomer of formula (IV), wherein R ⁸ is a group of formula (CH ₂ CH ₂ O) _n -R ⁹ _wherein R ⁹ is a C1- C10 hydrocarbyl substituent, preferably a C1-C10 alkyl or C6-C10 aryl substituent, and n is an integer from 1 to 6, preferably from 1 to 3). Preferably R ⁸ is a formula _{(CH 2 CH 2 O) n} -R 9 (Wherein R ⁹ is a C 1 -C 10 alkyl substituent, preferably CH ₃ or CH ₂ CH ₃ , and n is an integer ranging from 1 to 3, preferably 1 or 2).

In one embodiment, the hydrolyzable copolymer is selected from the group consisting of 2-methoxyethyl acrylate (MEA), 2-methoxyethyl methacrylate (MEMA), 2-ethoxyethyl methacrylate (EEMA) Ethoxyethoxy) ethyl acrylate (EDEGA), 2- (2-ethoxyethoxy) ethyl methacrylate (EDEGMA), 2- (2-butoxyethoxy) ethyl acrylate (BDGA) 2-butoxyethoxy) ethyl methacrylate (BDGMA).

In one embodiment, the hydrolyzable copolymer comprises at least one comonomer of formula (IV), wherein the R ⁸ group is a saturated cyclic Lt; / RTI > More preferably, R ⁸ is a group WR ^{10 wherein} R ¹⁰ is a cyclic ether such as oxolane, oxane, dioxolane, dioxane optionally alkyl-substituted and W is C 1 -C 4 alkylene. Such monomers include furfuryl acrylate, tetrahydrofurfuryl acrylate, (1,3-dioxolan-4-yl) methyl acrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, 2-dimethyl-1,3-dioxolan-4-yl) methyl methacrylate. Preferred cyclic ethers should contain at least four atoms in the ring. Most preferably, in this embodiment, the compound of formula (IV) is tetrahydrofurfuryl acrylate (THFA) and tetrahydrofurfuryl methacrylate (THFMA).

The comonomer of formula (IV) is preferably selected from the group consisting of 2-methoxyethyl acrylate (MEA), 2-methoxyethyl methacrylate (MEMA), 2-ethoxyethyl methacrylate (EEMA), tetrahydrofurfuryl Acrylate (THFA), tetrahydrofurfuryl methacrylate (THFMA), 2- (2-ethoxyethoxy) ethyl acrylate (EDEGA), 2- (2-ethoxyethoxy) ethyl methacrylate ), 2- (2-butoxyethoxy) ethyl acrylate (BDGA) or 2- (2-butoxyethoxy) ethyl methacrylate (BDGMA).

Particularly preferred hydrophilic comonomers of formula (IV) used in the hydrolysable binder are EDEGA, THFA, MEA and MEMA, in particular EDEGA and THFA.

Preferred hydrophobic comonomers, i.e. those of formula (I), include MMA, n-BA, n-BMA and 2-EHA. Preferably, the hydrolyzable copolymer comprises a mixture of MMA or MMA and n-BA.

The hydrolyzable copolymer (C), if present, preferably comprises at least comonomer triisopropylsilyl (meth) acrylate and a comonomer of formula (I) and a comonomer of formula (IV). The preferred choice of formula (I) above applies to hydrolyzable copolymers.

Preferably, the comonomer of formula (IV) forms at least 3 wt% of the hydrolyzable copolymer component. A particularly preferred amount of the hydrophilic (meth) acrylate comonomer of formula (IV) in the hydrolyzable copolymer is 3 to 50 wt%, preferably 3 to 30 wt%, such as 5 to 30 wt%, or 5 to 25 wt% to be. When a mixture of comonomers of formula (IV) is present, these amounts are associated with a combined wt fraction of the comonomer of formula (IV) in the copolymer.

 Preferably, the hydrolyzable copolymer comprises at least 10 wt% of the non-hydrophilic comonomer of formula (I), preferably at least 15 wt%, preferably at least 20 wt%, such as 10-60 wt% Comprises 15-50 wt%, more preferably 20-40 wt% comonomers of formula (I). When a mixture of comonomers of formula (I) is present, these amounts are associated with a combined wt fraction of the comonomer of formula (I) in the copolymer.

The hydrolyzable copolymer (C) preferably has a glass transition temperature (Tg) of at least 10 캜, preferably at least 15 캜, preferably at least 20 캜, such as at least 22 캜 or at least 30 캜, Is determined according to the Tg test described in the Example section. A value of less than 80 DEG C is preferred, and an example thereof is less than 75 DEG C, for example less than 50 DEG C.

 The hydrolyzable copolymer preferably has a weight average molecular weight of 5,000 to 70,000, preferably 10,000 to 60,000, especially 10,000 to 50,000, 20,000 to 50,000, or 20,000 to 40,000.

Typically, the hydrolyzable copolymer will be free of carboxylic acid-containing comonomers.

The hydrolyzable copolymer preferably has a PDI of from 2 to 6.

If present, the hydrolysable copolymer component (C) preferably forms from 20 to 60 wt%, such as from 25 to 50 wt% of the binder.

In the present invention, the antifouling composition preferably contains 0.5 to 30 wt.%, Preferably 1 to 22 wt.%, Preferably 2 to 20 wt.%, Preferably 5 to 18 wt.% (Dry solid) ).

The additional non-hydrolyzable polymer (D)

The binder and antifouling coating composition of the present invention may comprise additional non-hydrolyzable (meth) acrylate copolymers. Hereinafter, the terms 'non-hydrolyzable copolymer', 'non-hydrolyzable (meth) acrylate copolymer' refer to a component (A) of the present invention which does not contain side-chains such as silyl ester monomer residues which are hydrolyzed in natural seawater ). ≪ / RTI > These binder components, if present, thus differ from the hydrolyzable binder (C) described above and are present in addition to the copolymer (A). Preferably, such a non-hydrolyzable copolymer component will not contain a carboxylic acid monomer (ii).

Preferably, such a non-hydrolyzable polymer comprises at least one non-hydrophilic monomer of formula (I) such as MMA, n-BA, n-BMA, 2-EHA. In certain embodiments, the non-hydrolyzable copolymer comprises a hydrophilic comonomer of formula (IV) as described above. Preferably, the non-hydrolyzable polymer comprises at least one comonomer of formula (I) and at least one comonomer of formula (IV). In a particularly preferred embodiment, the non-hydrolyzable copolymer comprises MMA. In a further preferred embodiment, the non-hydrolyzable polymer comprises MMA and at least one other comonomer of formula (I) and / or (IV), such as n-BA for formula (I) Includes EEMA or MEA for. Typically, the non-hydrolyzable copolymer will comprise at least one other comonomer selected from MMA and MEMA, MEA, EEMA, THFA, THFMA, EDEGA, BDGMA, BDGA and EDEGMA.

Preferably, in such a non-hydrolyzable polymer, the non-hydrophilic comonomer (s) of formula (I) is present in the copolymer in an amount of up to 95 wt%, such as up to 90 wt% or up to 85 wt% do. Typically, the non-hydrophilic comonomer (s) of formula (I) comprise at least 30 wt%, such as at least 40 wt%, such as at least 50 wt%, such as 30-95 wt%, 40-90 wt% Is present in the binder in an amount ranging from 50 to 85 wt%.

The non-hydrolyzable copolymer preferably has a glass transition temperature (Tg) of at least 0 캜, preferably at least 5 캜, preferably at least 10 캜, preferably at least 15 캜. A value of less than 80 DEG C is preferred, examples of which are less than 75 DEG C, such as less than 50 DEG C, less than 40 DEG C, or less than 30 DEG C.

The non-hydrolyzable polymer preferably has a weight average molecular weight of 5,000 to 70,000, preferably 10,000 to 60,000, especially 10,000 to 50,000, 15,000 to 50,000, or 15,000 to 40,000, or 20,000 to 35,000.

The non-hydrolyzable polymer preferably has a PDI of 2 to 6.

If present, component (D) preferably forms a binder of 20 to 60 wt%, for example 25 to 50 wt% (dry solids).

In the present invention, the antifouling composition preferably contains from 0.5 to 30 wt.%, Preferably from 1 to 22 wt.%, Preferably from 2 to 20 wt.%, Preferably from 5 to 18 wt.% (Dry solid) ).

It is generally preferred to use component (D) alone or both components (C) and (D).

Preparation of Polymer (A) and Polymers (C) and (D)

The polymers may be prepared using polymerization reactions known in the art. The acrylic polymer is preferably prepared using addition polymerization or chain growth polymerization. Examples of suitable addition polymerization techniques include free radical polymerization, anionic polymerization and suitable controlled polymerization techniques. Polymers may be prepared, for example, by conventional methods, by any of a variety of methods such as solution polymerization, bulk polymerization, emulsion polymerization, and suspension polymerization, or by controlled polymerization techniques, in the presence of a polymerization initiator and optionally a chain transfer agent. Can be obtained by polymerization. When such a polymer is used as a coating composition, the polymer is preferably diluted with an organic solvent to obtain a polymer solution having an appropriate viscosity. From this viewpoint, it is preferable to use solution polymerization.

Examples of the polymerization initiator for free radical polymerization include azo compounds such as dimethyl 2,2'-azobis (2-methylpropionate), 2,2'-azobis (2-methylbutyronitrile) azobis (isobutyronitrile) and 1,1'-azobis (cyano cyclohexane) and peroxides, for example tert - butyl peroxypivalate, tert - butyl peroxy-2-ethylhexanoate, tert - butyl peroxydicarbonate ethyl acetate, tert - butylperoxy isobutyrate, di -tert - butyl peroxide, tert- butylperoxy Benoit J agent, and tert- butylperoxy 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, mesitylene; Ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, methyl isoamyl ketone, cyclopentanone, cyclohexanone; Esters such as butyl acetate, tert -butyl acetate, amyl acetate, ethylene glycol methyl ether acetate, butyl propionate, isobutyl isobutyrate; Ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dibutyl ether, dioxane, tetrahydrofuran, alcohols such as n-butanol, isobutanol, benzyl alcohol; Ether alcohols such as butoxyethanol, 1-methoxy-2-propanol; Cyclic terpenes such as d-laimonen; Aliphatic hydrocarbons such as white spirit; And optionally a mixture of two or more solvents. These compounds are used alone or as a mixture of two or more thereof.

The copolymers (A), (C) and (D) are preferably random copolymers.

Other binder components

In addition to components (A) and (B), and optional additional binder components (C) and (D), other components can be used to tailor the properties of the binder. Examples of additional binder components include:

Esters of rosins and hydrogenated rosins, such as methyl esters, glycerol esters, poly (ethylene glycol) esters, pentaerythritol esters (preferred are esters of chol rosin and hydrogenated rosin);

Dimerized and polymerized rosin;

An acid functional polymer blocked with a divalent metal bonded to a monovalent organic moiety or a divalent metal bonded to a hydroxyl moiety;

Hydrophilic copolymers such as (meth) acrylate copolymers such as 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, Polyester copolymers containing two or more units selected from the above-mentioned units; And other condensation polymers such as polyoxalates;

 Alkyd resins and modified alkyd resins;

A hydrocarbon resin formed solely by polymerization of at least one monomer selected from hydrocarbon resins such as C5 aliphatic monomers, C9 aromatic monomers, indenecumarone monomers, or terpenes or mixtures thereof.

The non-cyclic monocarboxylic acid

In one embodiment, the antifouling coating of the present invention may comprise a liquid acyclic C12-C24 monocarboxylic acid or a salt thereof, i.e., an acid containing a single -COOH moiety within the molecule or its salt. Such acids contain an acid "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 materials may allow improved control of leached layer formation (reduced thickness) than comparative compositions that do not contain acid components. In addition, compositions containing an acid component should exhibit similar levels of abrasion while maintaining or even reducing the viscosity of the paint.

These components may comprise at least one monocarboxylic acid selected from liquid, acyclic, saturated C12-C24 monocarboxylic acids or liquid, acyclic, branched C12-C24 monocarboxylic acids. The acid must therefore not be a linear unsaturated carboxylic acid. It is preferable if the acid is saturated.

The monocarboxylic acid is ideally represented by the formula R ₁₁ COOH wherein R ₁₁ is a C 11-23 acyclic, branched alkyl or alkenyl group or a C 11-23 acyclic, saturated, linear or branched alkyl group. It is preferable that R < ₁₁ > is a C11-23 acyclic or branched alkyl group.

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

The acid is preferably liquid at room temperature and pressure (23 < 0 > C and 1 atm).

It is preferable that the acid component is branched. The branched acid must contain tertiary or quaternary carbon atoms in its tail group.

It will be appreciated that many acids may be derived from natural sources and in this case exist in isolated form, typically in the form of a mixture of acids of different chain length, with varying degrees of branching. If the acid used is a mixture of components, the acid may have a degree of branching of more than 50%, preferably more than 70%, more than 80% or even more than 90%. The percentage of the present invention is wt%. By way of example, a C18 acid component having a branching degree of at least 50% will contain no more than 50 linear C18 acids (n-stearic acid, n-oleic acid, n-linoleic acid, etc.) and the remainder being branched C18 acids Quot; isostearic acid, " isoleic acid ", " isoleinic acid ", and the like).

In a preferred embodiment, the acid is a C14-C20 monocarboxylic acid, preferably a C16-C20 monocarboxylic acid, especially a C16-18 monocarboxylic acid. It is preferred if the carbon chain contains an even number of carbon atoms. In a preferred embodiment, the acid has a molecular weight of less than 350 g / mol, especially less than 320 g / mol, and especially less than 300 g / mol.

In a preferred embodiment, the acid has an acid value of less than 310, in particular less than 300, such as less than 290 or even less than 280. [ &Quot; Acid value " is a known parameter and is the mass (in milligrams) of KOH required to neutralize 1 gram of acid (ISO 660: 2009).

In a preferred embodiment, the acid has an iodine number of less than 50, such as less than 40, less than 30, or less than 20. In some embodiments, it may be a saturated acid having an iodine number of zero. "Iodine" is a known parameter and is the mass (grams) of iodine reacted with 100 grams of acid (AOCS Tg 1a-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 each case, the acid may be natural or synthetic. Blends of isostearic acid and isophthalic acid are available with the appropriate degree of branching under the designations Radiacid 0906, Radiacid 0907 and Radiacid 0909 (Oleon). Particularly high grade branched isostearic acid is the product Fineoxocol Isostearic acid N (Nissan Chemicals).

Particularly preferred acids are isostearic acid and isophthalic acid and in each case the degree of branching has a degree of branching of more than 70% and an iodine number of less than 30. Particularly suitable components are the products Fineoxocol Isostearic acid N (Nissan Chemicals), and Radiacid 0906, Radiacid 0907 or Radiacid 0909 (Oleon).

Any acid will be recognized to form salts if metal ions are present. The inventors suggest adding an acid in its acid form, but can also add an acid in its salt form. Acids can also be converted to the salt form in the composition. The wt% of acid added in the composition should be calculated assuming that the acid is in its acid form. Such components can be considered as additional optional components of the binder.

The binder typically forms an antifouling coating composition of 20 to 80 wt%, such as 25 to 70 wt% (dry solids). This percentage refers to the total amount of binder component, e. G., Components (A) to (D) present.

The binder compositions of the present invention are ideally incorporated into antifouling coating compositions.

Antifouling agent

The antifouling coating preferably further comprises a compound capable of preventing or eliminating marine pollution on or from the surface. Terms Antifoulant, antifoulant, biocide, toxicant are used in the business to describe known compounds that have been acted on to prevent marine pollution on the surface. The antifouling agent of the present invention is an antifouling agent.

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

Examples of inorganic antifouling agents include copper and copper compounds such as copper oxide, such as copper (I) oxide and copper (II) oxide; Copper alloys, for example copper-nickel alloys; Copper salts such as copper (I) thiocyanate and copper sulfide. Examples of organic metal marine antifouling agents include zinc 2 pyridine thiol-1-oxide [zinc pyrithione]; (Oxydiphenylsulfonate), copper bis (ethylenediamine) s, and the like can be used as the organopolysiloxane compound. Examples of the organopolysiloxane compound include, but are not limited to, organotin compounds such as copper 2-pyridinethiol-1-oxide [copper pyrithione], copper acetate, copper naphthenate, copper 8- Bis (dodecylbenzene sulfonate) and copper bis (pentachlorophenolate); (Dithiocarbamate) [zinene], manganese ethylene bis (dithiocarbamate) [maneb], and zinc salts with zinc dithiocarbamate compounds such as zinc bis (dimethyldithiocarbamate) Complexed manganese ethylene bis (dithiocarbamate) [manganese zeolite].

Examples of organic marine antifouling agents include heterocyclic compounds such as 2- ( tert- butylamino) -4- (cyclopropylamino) -6- (methylthio) -1,3,5-triazine [cybutrin], 4 2- n- octyl-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one [DCOIT], 2- (thiocyanatomethylthio) -1,3 -Benzothiazole [benzothiazole], 3-benzo [b] thien-2-yl-5,6-dihydro-1,4,2-oxathiazine 4-oxide [ 5,6-tetrachloro-4- (methylsulfonyl) pyridine; Urea derivatives such as 3- (3,4-dichlorophenyl) -1,1-dimethyl urea [diion]; Carboxylic acid, sulfonic acid and sulfonic pensan of amides and imides, for example N- (a-fluoro dichloro methylthio) phthalimide, N- methyl-dichloro-fluoro-thio - N '', N '' - dimethyl - N- phenylsulfanyl polyimide [ dichloride flu no de], a N- dichloro-fluoro methylthio - N '', N '' - dimethyl - Np- tolyl sulfamic polyimide [fluorene-tolyl no de] and N- (6-trichloro-phenyl) Maleimide; Other organic compounds such as pyridine triphenylborane, amine triphenylborane, 3-iodo-2-propynyl N- butyl carbamate [iodocarb], 2,4,5,6-tetrachloroisophthalonitrile carbonyl], p - ((DI Goto methyl) sulfonyl) in toluene and 4-bromo-2- (4-chlorophenyl) (trifluoromethyl) -5- -1H- pyrrole-3-carbonitrile [in Neutral Lt; / RTI >

Other examples of marine antifouling agents include tetraalkylphosphonium halogens, guanidine derivatives; Imidazole-containing compounds such as 4 [1 (2,3-dimethylphenyl) ethyl] -1H-imidazole [medetomidine] and derivatives thereof; Macrocyclic lactones such as ivermectin, including avermectin and its derivatives; Spinosyns and derivatives such as spinosad; Capsaicin and derivatives such as phenyl capsaicin; And enzymes such as oxidase, proteolysis, half-fiber degradation, fibrin degradation, lipolysis and starch degrading enzymes.

Conventionally, antifouling coating compositions contain copper biocides such as metal copper, copper oxide, copper thiocyanate, and the like.

The cuprous oxide material has a typical particle diameter distribution of 0.1-70 μm and an average particle size (d50) of 1-25 μm. The copper oxide material may contain stabilizers to prevent surface oxidation and caking. Examples of commercially available copper oxides include: Nordox Cuprous Oxide Red Paint Grade, Nordox XLT (Nordox AS), Cuprous oxide (Furukawa Chemicals Co., Ltd.); Red Copp 97N, Purple Copp, Lolo Tint 97N, Chemet CDC, Chemet LD (American Chemet Corporation); Cuprous Oxide Red (Spiess-Urania); Cuprous oxide Roast, Cuprous oxide Electrolytic (Taixing Smelting Plant Co., Ltd.).

A series of organic biocides are prepared by reacting a copper biocide such as 4- [1- (2,3-dimethylphenyl) ethyl] -1H-imidazole [medetomidine] and 4- ) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile [tralopyril] can be used instead. Any known biocide can be used in the present invention.

A preferred biocide is cuprous, copper thiocyanate oxide, zinc pyrithione, copper pyrithione, zinc ethylene bis (dithiocarbamate) [centipede bracket], 2- (tert - butylamino) -4- (cyclopropyl Dichloro-2-n-octyl-4-isothiazolin-3-one [DCOIT], N (methylthio) -Dichlorofluoromethylthio-N ', N'-dimethyl-N-phenylsulfamide [dichlorofluanid], N-dichlorofluoromethylthio-N', N'-dimethyl- (4-chloro-2-methylphenyl) ethyl] -1H-imidazole [Medtomidine], triphenylboranpyridine [TPBP] Phenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile [trilopyryl].

The mixture of biocides can be used as is, as is known in the art, since different biocides act on different marine polluting organisms. Mixtures of antifouling agents are generally preferred.

In one embodiment, the antifouling coating composition comprises at least one of copper oxide and / or copper thiocyanate and copper pyrithione, zinc ethylene bis (dithiocarbamate), 4,5-dichloro-2-octyl- 3-one and medetomidine. ≪ / RTI >

In an alternative embodiment, the antifouling coating is an inorganic copper biocide. In this embodiment, the preferred biocide combination is selected from the group consisting of trilopyryl, zinc pyrithione, zinc ethylene bis (dithiocarbamate), 4,5-dichloro-2-octyl-4-isothiazolin- And < RTI ID = 0.0 > medetomidine. ≪ / RTI >

If present, the combined amount of biocide can form up to 70 wt%, such as 4 to 60 wt%, e.g. 5 to 60 wt%, of the coating composition. When copper is present, a suitable amount of biocide may be 20 to 60 wt% in the coating composition. When copper is avoided less amount can be used, for example 0.1 to 20 wt%, for example 0.2 to 15 wt%. It will be appreciated that the amount of biocide will vary depending on the end use and the biocide used.

Some biocides may be encapsulated or adsorbed onto an inert carrier or may be bound to other materials for controlled release. These percentages refer to the amount of active biocide present and thus do not refer to any carrier used.

Other Ingredients

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

Pigments, extenders and fillers

The pigments may be inorganic pigments, organic pigments or mixtures thereof. Inorganic pigments are preferred. Examples of inorganic pigments include titanium dioxide and iron oxide. Examples of organic pigments include phthalocyanine compounds, azo pigments and carbon black.

Examples of extenders and fillers include minerals such as dolomite, plastite, 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 deacid, magnesium carbonate, barium sulfate, calcium silicate pulverized silica and precipitated silica; Polymers and inorganic microspheres such as uncoated or coated hollow and solid glass beads, uncoated or coated hollow and solid ceramic beads, 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).

Preferably, the total amount of extenders, fillers and / or pigments present in the composition of the present invention is 0-70 wt%, more preferably 1-60 wt%, and even more preferably 2- 50 wt%. Skilled artisans will appreciate that the extender and pigment content will vary depending upon the other ingredients in which they are present and the end use of the coating composition.

Dehydrating agent

The antifouling coating composition of the present invention optionally comprises a dehydrating agent, also called a water trapping agent or desiccant. Preferably, the dehydrating agent is a compound that removes water from an existing composition. The dehydrating agent can be a water-reactive compound, for example, a water-reactive compound, for example, by removing water formed from a raw material such as a pigment and a solvent, or water formed by reaction between a carboxylic acid compound and a specific compound, Lt; RTI ID = 0.0 > silyl ester < / RTI > copolymer. Dewatering agents and desiccants that may be used in the antifouling coating compositions include organic and inorganic compounds.

The dehydrating agent may be a hygroscopic substance that absorbs water or results in binding as a crystal water 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 which chemically reacts with water. Examples of dehydrating agents which react with water include ortho esters such as trimethyl orthoformate, triethyl orthoformate, tripropyl orthoformate, triisopropyl orthoformate, tributyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate, Tributyl orthoacetate and triethylorthpropionate; Ketal; Acetal; Enol ether; Orthoborates such as trimethyl borate, triethyl borate, tripropyl borate, triisopropyl borate, tributyl borate and tri-t-butyl borate; Organosilanes such as trimethoxymethylsilane, vinyltrimethoxysilane, phenyltrimethoxysilane, tetraethoxysilane, and ethylpolysilicate.

Preferred dehydrating agents are those which chemically react with water. A particularly preferred dehydrating agent is an organosilane.

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

Solvent and thinner

It is highly desirable that the antifouling composition contains a solvent. Such solvents are preferably volatile, preferably organic. Examples of organic solvents and thinners include aromatic hydrocarbons such as xylene, toluene, mesitylene; Ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl isoamyl ketone, methyl amyl ketone, diisobutyl ketone, methyl propyl ketone, cyclopentanone, cyclohexanone; Esters such as butyl acetate, tert- butyl acetate, amyl acetate, isoamyl acetate, ethylene glycol methyl ether acetate, propyl propionate, butyl propionate, isobutyl isobutyrate; Ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dibutyl ether, dioxane, tetrahydrofuran; Alcohols such as n- butanol, isobutanol, benzyl alcohol; Ether alcohols such as butoxyethanol, 1-methoxy-2-propanol; Cyclic terpenes such as d-laimonen; Aliphatic hydrocarbons such as white spirit; And optionally a mixture of two or more solvents and a thinner. Examples of other thinners include water.

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

The amount of solvent should preferably be as low as possible. The solvent content may be up to 50 wt% of the composition, preferably up to 45 wt% of the composition, e.g., up to 40 wt% of the composition, but may be as low as 15 wt% or less, such as 10 wt% or less. It will also be appreciated by those skilled in the art that the solvent content will vary depending upon the other components present and the final concentration of the coating composition.

Alternatively, the coating may be dispersed in an organic non-solvent for the film-forming component in the coating composition or in an aqueous dispersion.

The antifouling coating compositions of the present invention should preferably have a solids content of greater than 40 vol%, such as greater than 45 vol%, such as greater than 50 vol%, preferably greater than 55 vol%.

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

The antifouling coating composition of the present invention has a cone and plate viscosity at 23 DEG C in the range of 100-980 cP, preferably 150-950 cP, more preferably 200-900 Cp, as measured according to ISO 2884-1: 1999 Lt; / RTI >

Other additives

Examples of other additives that may be added to the antifouling coating composition are reinforcing agents, thixotropic agents, thickeners, antiseposition agents, wetting and dispersing agents, plasticizers and stabilizers.

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 fiber; Natural and synthetic organic fibers such as cellulosic fibers, rubber fibers, acrylic fibers, polyamide fibers, polyimides, polyester fibers, polyhydraid fibers, polyvinyl chloride fibers, polyethylene fibers and others as described in WO 00/77102 . Preferably, the fibers have an average length of 25 to 2,000 μm and an average thickness of 1 to 50 μm, the ratio between the average length and the average thickness being at least 5.

Examples of thixotropic agents, thickeners and antiseposition inhibitors include silica, such as fumed silica, organo-modified clays, amide waxes, polyamide waxes, amide derivatives, polyethylene waxes, oxidized polyethylene waxes, hydrogenated castor oil waxes, ethylcellulose, Aluminum stearate, and mixtures thereof.

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

Examples of stabilizers that contribute to the storage stability of the antifouling coating compositions include carbodiimide compounds such as bis (2,6-diisopropylphenyl) carbodiimide and poly (1,3,5-triisopropylphenylene- , 4-carbodiimide) and others as described in patent EP 2725073.

In general, any of these optional components may be present in an amount ranging from 0.1 to 20 wt%, typically 0.5 to 20 wt%, preferably 0.75 to 15 wt% of the antifouling composition. It will be appreciated that the amount of these optional ingredients will vary with the end use.

The antifouling coating composition of the present invention may be applied to all or part of the surface of any object subjected to contamination. The surface may be permanently or intermittently underwater (e.g., through algae movement, different delivery object loading or swelling). The object surface will typically be the surface of a fixed marine object such as an oil platform or buoy, or the hull of a vessel. Application of the coating composition may be accomplished by any convenient means, for example by painting (e.g., with a brush or roller) or spraying the coating on the object. Typically, the surface will need to be separated from the seawater to permit coating. Application of the coating can be accomplished as is conventionally known in the art.

When an antifouling coating is applied to a subject (e.g. a hull), the surface of the object is typically not protected solely by a single coat of antifouling. Depending on the nature of the surface, the antifouling coating can be applied directly to existing coating systems. Such a coating system may comprise several layers of paint of different general types (e.g. epoxy, polyester, vinyl or acrylic or mixtures thereof). If the surface is a clean and intact antifouling coating from the previous application, the new antifouling paint can be applied directly, typically as 1 or 2 coats, in exceptional cases.

Alternatively, the skilled person may start with an uncoated surface (e.g., steel, aluminum, plastic, composite, glass fiber or carbon fiber). To protect such surfaces, the entire coating system will typically include one or two layers of anti-corrosive coating, one layer of tie-coat and one or two layers of antifouling paint. The skilled artisan will be familiar with these coating layers.

In exceptional cases, additional antifouling paint layers can be applied.

In a further embodiment, the invention therefore provides a substrate upon which an anti-corrosive coating layer such as an epoxy primer, a tie layer and an anti-fouling coating composition as defined herein has been coated.

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

Example

Materials and methods

Measurement of viscosity of polymer solution

The viscosity of the polymer solution was determined according to ASTM D2196-15 Test Method A using a Brookfield DV-I viscometer with LV-2 or LV-4 spindles at 12 rpm. The polymer solution was relaxed to 23.0 ° C ± 0.5 ° C before measurement.

Determination of non-volatile content of polymer solution

The non-volatile content of the polymer solution was determined according to ISO 3251. 0.5 g ± 0.1 g of the test sample was taken out and dried in a ventilated oven at 105 ° C. for 3 hours. The weight of the remaining material is considered to be non-volatile (NVM). The non-volatile matter content is expressed in weight percent. The value given is the average of the three parallel lines.

Measurement of Polymer Average Molecular Weight Distribution

The polymer was characterized by gel permeation chromatography (GPC) measurements. Molecular weight distribution (MWD) was determined using the Malvern Omnisec Resolve and Reveal system with two PLgel 5 μm mixed-D columns from Agilent in tandem. The column was calibrated with a conventional calibration using a narrow polystyrene standard.

The sample was prepared by dissolving the amount of polymer solution corresponding to 25 mg dry polymer in 5 mL THF. Samples were maintained at room temperature for at least 3 hours prior to sampling for GPC measurements. Samples before analysis were filtered through a 0.45 μm nylon filter. The polydispersity index (PDI) and weight average molecular weight (Mw) given as Mw / Mn are reported.

The analysis conditions are given below:

Measurement of glass transition temperature

The glass transition temperature (Tg) is obtained by differential scanning calorimetry (DSC) measurement. DSC measurements were performed on a TA Instruments DSC Q200. A drop of the polymer solution was added to the aluminum pan and dried in a heating cabinet for 18 hours at 50 ° C for 18 hours and at 150 ° C for 3 hours (about 10 mg dry polymer was obtained). It was measured by a heat-cooling-thermal procedure (-80ºC to 120ºC) in an aluminum pan. The scan was run at a heating rate of 10 [deg.] C / min and a cooling rate of 10 [deg.] C / min with an empty pan as reference. The data was processed using a conventional analysis software from TA Instruments.

The inflection point of the glass transition range, as defined in ASTM E1356-08, of the second heating is reported as the Tg of the polymer.

Measurement of acid value of polymer

The acid value of the polymer was measured according to ISO 2114: 2000 Method A. Solvesso 100: xylene: butanol 60:25:15 was used as the solvent. A colorimetric titration using phenolphthalein was used. The red color was titrated until stable for 10-15 seconds. Polymer was measured 2 to 3 times. The acid value for the dry polymer was calculated based on the measured non-volatile material.

General procedure for the preparation of antifouling coating compositions

Ingredients were mixed at the ratios given in Tables 3-4. The mixture was dispersed in the presence of glass beads (diameter: approximately 2 mm) in a 250 ml paint can using a vibration shaker for 15 minutes. The glass beads were filtered off and then tested.

Measurement of paint viscosity using cone and plate viscometer

The viscosity of the antifouling paint composition was measured using a digital cone and plate viscometer set at a temperature of 23 DEG C and operating at a shear rate of 10000 s < ^-1 > and ISO 2884-1: 1999 . The results are given as the average of three measurements.

The results are shown in Tables 3 and 4.

Calculation of volatile organic compound (VOC) content of antifouling coating composition

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

Water absorption in fresh water / deionized water

Water absorption in the coating film was determined by gravimetric method. The paint was applied on a pre-weighed and numbered sand blasted glass panel (5.0 x 7.5 cm) using a 300 μm gap size film applicator. The films were dried for at least 1 day under ambient conditions, overnight at 50 < 0 > C, and then under vacuum in a desiccator for 24 hours. After drying, the coated glass panel was weighed and placed in a container filled with distilled water. Upon reading, the panels and paint surfaces were quickly dried using compressed air. The panels were weighed (m _directly ) then dried under ambient conditions for 2 days and then placed in a desiccator under vacuum for 24 hours and then weighed again (m _dry ). The difference in dry weight before and after drying relative to the dry weight of the coating after exposure is expressed as a percentage absorption of moisture.

Amount of water absorption = (m _directly - m _dry) / _(dry m - m _{blank panel)}

The reading was carried out after 34 days. The results are shown in Tables 3 and 4.

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

Polishing was determined to be a decrease in the film thickness of the coating film. PVC discs were used for these tests. The coating composition was applied as a radial strip on the disc using a film applicator. The thickness of the dry coating film was measured by a surface profiler. The PVC disc was mounted on the shaft and rotated in a container where the seawater had flowed. Natural sea water being filtered and temperature-regulated at 25 ° C ± 2 ° C was used. The speed of the rotated shaft provided an average simulated speed of 16 knots on the disk. PVC discs were taken for film thickness measurements. The discs were rinsed and dried overnight at room temperature and then the film thickness was measured. The result was given as the difference between the film reduction, the initial film thickness and the thickness measured at a given time.

A summary of the different polymers tested is given in Table 1.

Example:

Preparation of acrylic copolymer solution S-1 (non-hydrolyzable copolymer (D))

26.10 parts of xylene and 6.10 parts of 1-methoxy-2-propanol were charged into a temperature-controlled reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet and a feed inlet. The reaction vessel was heated and maintained at 105 ° C. A mixture of 29.90 parts of methyl methacrylate, 22.90 parts of 2-methoxyethyl acrylate, 1.65 parts of dibenzoyl peroxide (50% in dicyclohexyl phthalate), 5.90 parts of xylene and 2.90 parts of 1-methoxy- The mixture was prepared and charged to the reaction vessel under a nitrogen atmosphere over a period of 2 hours and 30 minutes at a constant rate. After an additional 1 hour reaction, post-addition of 0.35 parts of dibenzoyl peroxide (50% in dicyclohexyl phthalate) and 4.20 parts of xylene in the boost initiator solution was charged to the reaction vessel at a constant rate over 15 minutes. The reaction vessel was held at the reaction temperature for an additional hour and then cooled to room temperature. The amount of component is given in parts by weight.

Copolymer solution S-1 had a viscosity of 945 cP, a non-volatile content of 55.5 wt%, Mw 23 600, PDI 2.60 and Tg 23 캜.

General procedures for the preparation of copolymer solutions P1 to P8 and CP1 to CP6

All polymers tested were produced in the same manner by charging 24.17 parts of xylene and 9.81 parts of PM (solvent blend 1) into a temperature-controlled reaction vessel equipped with a stirrer, reflux condenser, nitrogen inlet and feed inlet. The reaction vessel was heated and maintained at 85 占 폚. A pre-mixture of monomer, 10.08 parts xylene (solvent 2) and 50.00 parts of initiator was prepared and charged to the reaction vessel under a nitrogen atmosphere over a period of 2 hours 30 minutes at a constant rate. After an additional 1 hour reaction, the reaction vessel was charged with the initiator and 5.00 parts of xylene (solvent 3) after-feed of the boost initiator solution over a period of 15 minutes at a constant rate. The reaction vessel was held at the reaction temperature for an additional hour and then cooled to room temperature. The amount of solvent is given in parts by weight.

An example from this was that the polymers P4, P8, CP3 and CP6 had a reaction temperature of 95 캜. All polymers were made of 50.0 wt% theoretical non-volatile material.

One further example was that the polymer CP1 was produced in the following amount of solvent (parts by weight): < RTI ID = 0.0 >

Solvent blend 1: xylene / PM 24.57 / 9.85

Solvent 2: xylene 9.36

Solvent 3: xylene 5.28

One additional exception was that polymer CP6 was produced in the following amount of solvent (parts by weight): < RTI ID = 0.0 >

Solvent blend 1: xylene / PM 23.63 / 7.00

Solvent 2: None

Solvent 3: xylene 3.40

Dilution before cooling: Xylene 14.92

A summary of the different polymers synthesized and the amounts of initiator used are given in Table 1 and outlined in Table 2 of the polymer properties.

As can be seen from the above data, a composition comprising a copolymer having a small amount of carboxylic acid-containing comonomer provides a coating having undesirably high water absorption values. This can be seen in compositions with polymers CP1 and CP2. Polymers CP3 and CP4 provide undesirably high viscosities, indicating that exceeding the high content of carboxylic acid containing monomers is undesirable. CP5 and CP6 have an ultrahigh viscosity because their Tg is very high.

Claims (19)

Binders for antifouling coating compositions comprising:
(A) having a Tg of 0 DEG C or less and having as comonomer:
i) at least one (meth) acrylate of formula (I):

Wherein R ¹ is H or CH ₃ and R ² is a C ¹ -C 20 hydrocarbyl,
ii) from 0.70 to 8.6 wt%, based on the total weight of copolymer (A), of at least one carboxylic acid-containing comonomer
(Meth) acrylate copolymer, wherein the combined monomers (i) and (ii) represent at least 80 wt% of the monomer present in the copolymer (A); And
(B) cyclic monocarboxylic acids such as rosin or derivatives thereof such as salts thereof. The binder according to claim 1, wherein (B) is a rosin derivative selected from rosin or partially or fully hydrogenated rosin, rosin acid, or metal rosinate, or a combination thereof. 3. The binder according to claim 1 or 2, wherein in the formula (I), R ² is a C 1 -C 8 alkyl substituent, preferably methyl, ethyl, n-propyl, 2-ethylhexyl or n-butyl. The composition according to any one of claims 1 to 3, wherein the formula (I) is selected from the group consisting of methyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and n-butyl methacrylate, preferably methyl methacrylate and n-butyl acrylate, 2-ethylhexyl acrylate, and n-butyl methacrylate. The copolymer (A) according to any one of claims 1 to 4, wherein the copolymer (A) is used in an amount of 0.8-8.6 wt%, preferably 1.0-7.56 wt%, more preferably 1.2-8.5 wt%, based on the total weight of the copolymer By weight of a carboxylic acid-containing comonomer of from about 7.0 to about 7.0% by weight, more preferably from about 1.3 to about 6.5% by weight, more preferably from about 1.4 to about 6.0% by weight. The binder according to any one of claims 1 to 5, wherein the carboxylic acid-containing comonomer is selected from methacrylic acid or acrylic acid, or a combination thereof. The copolymer (A) as claimed in any one of claims 1 to 6, wherein the copolymer (A) has a melting point of 0 ° C or lower, preferably 0 to -60 ° C, such as -5 to -55 ° C, preferably -10 to -50 ° C, Lt; RTI ID = 0.0 > 15 C < / RTI > The copolymer according to any one of claims 1 to 7, wherein the copolymer (A) has a Mw of 50,000 or less. The binder according to any one of claims 1 to 8, wherein the copolymer (A) and the component (B) are present in a weight ratio of from 1: 1 to 1:30, preferably from 1: 1 to 1:10. Component (A), preferably 15 to 30 wt.% (Dry solids) and 10 to 70 wt.% Of component (B), preferably 20 to 50 wt.%, To 50 wt% (dry solids). The binder according to any one of claims 1 to 10, further comprising at least one copolymer selected from the following:
C) hydrolyzable silyl-containing monomers such as hydrolyzable (meth) acrylate copolymers containing silyl-containing (meth) acrylates such as triisopropylsilyl acrylate or triisopropylsilyl methacrylate;
And / or
D) Non-hydrolyzable (meth) acrylate copolymer. The binder according to any one of claims 1 to 11, wherein the copolymer (A) has an acid value of 8.0-50 mg KOH / g of polymer. An anti-fouling coating composition comprising a binder as claimed in any one of claims 1 to 12. A process according to claim 13, characterized in that it contains 0.5 to 25 wt% of component (A), preferably 1 to 22 wt%, preferably 2 to 20 wt%, preferably 5 to 18 wt% Coating composition. The antifouling coating according to claim 13 or 14, further comprising a antifouling agent, wherein the antifouling agent preferably comprises copper and / or copper pyrithione and / or zinc ethylenebis (dithiocarbamate) Composition. The antifouling coating composition according to any one of claims 13 to 15, wherein the binder components (A) to (D) comprise 20 to 70 wt% (dry solids) of the antifouling coating composition. Process according to any one of claims 13 to 16, characterized in that it has a viscosity of from 100 to 980 cP, preferably from 150 to 950 cP, more preferably from 200 to 900 cP, measured according to ISO 2884-1: Cone and plate viscosity. As a method for protecting an object from contamination,
A method, comprising coating at least a portion of said object to be contaminated with an anti-fouling coating composition as claimed in any one of claims 13 to 17. A subject coated with the antifouling coating composition as claimed in any of claims 13 to 17.