JP2019090019A - Antifouling coating composition - Google Patents

Abstract

To provide a new binder for antifouling coating composition, and an antifouling coating using the same.SOLUTION: A binder for antifouling coating is provided that includes: (A) a (meth)acrylate copolymer having Tg of 0°C or lower which includes at least one carboxylic acid-including comonomer in an amount of 0.70-8.6 wt.% based on the total weight of i) at least one (meth)acrylate of formula (I) and ii) the copolymer (A), in formula (I), Rrepresents H or CHand Ris Cto Chydrocarbyl substituent, wherein combination of (i) and (ii) is at least 80 wt.% of the copolymer (A); and (B) a cyclic monocarboxylic acid such as rosin and the derivative thereof.SELECTED DRAWING: None

Description

  The present invention relates to novel binders for antifouling coating compositions comprising acidic comonomers and (meth) acrylate copolymers having a low Tg. The binder enables the preparation of antifouling coatings with low fresh water absorption and coatings of optimum viscosity which can be applied without the need for excessive amounts of solvents.

  The surface immersed in seawater is polluted by marine organisms such as green algae, brown algae, barnacles, mussels, and tubeworms. In marine structures such as ships, oil platforms, buoys, such pollution is undesirable and has economic consequences. Fouling can result in biological degradation of the surface, increased loading, and accelerated corrosion. On ships, fouling causes increased frictional resistance, causing a decrease in speed and / or an increase in fuel consumption. Also, operability may be reduced.

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

  An important parameter when considering anti-soiling coatings on immersed surfaces is the absorption of water in fresh water. This parameter is important for coatings used in seawater. Many ocean-going vessels, such as those operating through the Panama Canal, navigate freshwater for a period of time. Freshwater absorption is also an important parameter, for example, in some parts of China where new structures are being built on freshwater rivers. In these cases, if the water absorption is large, excessive swelling may be caused, and in the worst case, the coating film may be broken. This property is an important indicator of seawater performance as coatings with long-term stability in fresh water work well in seawater. In seawater, the paint film absorbs water, but has a lower osmotic pressure compared to fresh water, resulting in reduced speed and volume.

  The antifouling coating is designed to be used for up to 7.5 years. Maintaining minimal water absorption throughout this period is an important factor in controlling the release of the active ingredient from the coating. Among any type of antifouling technology, there is a clear relationship between reliable performance and water absorption over time. Excessive water absorption results in faster release rates of the active ingredient than desired, which reduces performance over the life of the coating. Depending on the type of binder system used, increased water absorption can lead to accelerated hydrolysis, excessive erosion and accelerated leaching of the active ingredients, resulting in a thicker defect towards the surface of the coating A bed (leached bed) may be formed. In all cases, control of water absorption is an important parameter in designing high performance antifouling coatings such as those for new construction and dry docking.

  Surprisingly, the present inventors have found that compositions comprising (meth) acrylate copolymer binders, having a Tg of 0 ° C. or less and comprising a certain amount of acidic comonomers, give excellent results with regard to the absorption of fresh water. It has been found that it becomes a coating having Undesirably high fresh water absorption was observed when the acidic comonomer content was below the optimum range, and it was found to be high viscosity when it was above the optimum range. This means that a large amount of solvent is required to apply the paint. This is clearly undesirable when a paint with a low content of VOC is required, as there are many countries with limits on acceptable VOC levels.

  The literature contains many disclosures of binder polymers for antifouling coatings. In particular silyl ester copolymers and acrylate based polymers are well known. However, there is little disclosure of binders containing (meth) acrylic acid comonomers required by the present invention.

  In EP 1 288 234, antifouling coating compositions are prepared based on hydrophilic monomers and N-vinyl lactams. The polymers exemplified therein include functionalized copolymers of methacrylic acid, methyl methacrylate, butyl acrylate and vinyl pyrrolidone. Polymer Example 3 contains MAA: vinyl pyrrolidone: MMA: MA: BA (0.9: 18.6: 23.2: 49.3: 8 mole%), in an amount of 21% by weight vinyl pyrrolidone It means that it exists.

  In international application no. 9744401 the use of rosins, fibers and polymeric softeners in antifouling coatings is discussed. The examples use Zn-resinate with polymers based on various monomers. As commercial names are used throughout, the nature of the polymers used is not disclosed.

  WO 2008105122 describes antifouling coating compositions comprising a polymeric softener, a silyl copolymer and an antifouling agent. In these examples, various forms of rosin are used with polymers based on silyl ester and acrylate comonomers. Acrylic or methacrylic acid is not mentioned as possible monomer.

  International Application No. 2005005516 describes low molecular weight silyl ester copolymers. In these examples, the acrylate polymer and rosin are combined, but acrylic acid monomers are apparently not included.

  WO 2011131721 describes coating compositions produced by adding the different components in a specific order. In the examples, rosin is used with Neocryl B 725 (acrylate based copolymer). Neocryl B 725 has very high Tg values.

  International application WO 2014175140 describes silyl copolymers with specific end groups. TISA and TISMA copolymers are used in the examples. Rosin, hydrogenated rosin, zinc rosinate are used in the paint examples. There is no indication of the presence of acrylic acid monomers.

  EP 3078715 describes a coating composition comprising a silyl ester copolymer, tralopyryl and a stabilizer. In the examples, TISMA copolymers, gum rosins and acrylic polymers are used.

  Chinese Patent No. 105295630 (Patent Document 8) and Chinese Patent No. 105001358 (Patent Document 9) relate to a method of synthesizing a copper / zinc acrylate antifouling resin. Resins are made by reacting an acid functional acrylic prepolymer with a metal hydroxide and a monocarboxylic acid compound. The ratio of acrylic prepolymer to monocarboxylic acid compound in the examples is about 11: 1 to 4: 1.

  International Application No. 2003/027194 (Patent Document 10) or Japanese Patent Application Publication No. 2003246962 (Patent Document 11) is a non-aqueous dispersion resin having a core-shell structure comprising (a) a hydrophilic core component and (b) a shell component. The present invention relates to an antifouling coating composition containing The hydrophilic polymer in the core comprises 5 to 75% by weight of monomers having acid groups. Nonaqueous dispersion (NAD) is a system in which individual polymer particles are dispersed in a solvent. The non-aqueous dispersions of this document form opaque white dispersions. The copolymers of the invention form a clear solution. That is, the polymer is dissolved in the solvent and not in a separate phase from the solvent. The acid-containing core material has an estimated Tg of 60-75.degree.

  Korean Patent No. 20160081540 describes the preparation of a zinc acrylate resin in which an acid functional acrylic is reacted with a metal oxide, a half ester and a monocarboxylic acid compound.

  British patent specification No. 2204046 relates to antifouling paints comprising copolymers based on cyclic tertiary amides or imides, for example N-vinylpyrrolidone.

European Patent No. 1288234 International Application No. 9744401 International Application No. 2008105122 International Application No. 2005005516 International Application No. 2011131721 International Application No. 2014175140 European Patent No. 3078715 Chinese Patent No. 105295630 Chinese Patent No. 105001358 International Application No. 2003/027194 Unexamined-Japanese-Patent No. 2003246962 Korean Patent No. 20160081540 British Patent Specification No. 2204046

  The combination of components required in the claims is novel and gives remarkable results.

In a first aspect, the invention provides
(A) A (meth) acrylate copolymer having a Tg of 0 ° C. or less, and as a comonomer,
i) Formula (I)

At least one (meth) acrylate of the formula: wherein R ¹ is H or CH ₃ and R ² is a C _{1 to} C ₂₀ hydrocarbyl substituent;
ii) a combination of comonomers (i) and (ii) comprising at least one carboxylic acid containing comonomer which is 0.70 to 8.6% by weight, based on the total weight of the copolymer (A), (Meth) acrylate copolymer exhibiting at least 80% by weight of the comonomers present in the copolymer (A),
(B) A binder for an antifouling coating composition is provided, which comprises a cyclic monocarboxylic acid such as rosin or a derivative thereof (eg, a salt thereof).

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

  The invention also provides a process for protecting an object from fouling, wherein the process comprises coating at least a part of the object exposed to fouling with the antifouling coating composition as defined herein. Including.

The invention also relates to the use of the antifouling composition according to the invention for protecting an ocean surface from an object coated with an antifouling coating composition as defined herein, or from fouling.
Definitions "Marine antifouling coating composition", "antifouling coating composition" or simply "coating composition" refers to a composition that is suitable for use in a marine environment. The antifouling coating composition preferably contains an antifouling agent, such as a biocide.

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

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

  The term "rosin" as used below is used to include rosin or its derivatives.

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

  The term "Tg" means glass transition temperature.

  Where a weight percent of a given comonomer is given, the weight percent is relative to the total (weight) of each comonomer present in the copolymer.

The present invention relates to a binder for marine antifouling coatings with extremely low water absorption in fresh water. Thus, these compositions can provide protection against fouling at extended use intervals. A binder is a (meth) acrylate copolymer containing 0.70 to 8.6% by weight of a carboxylic acid-containing comonomer and having a Tg of less than 0 ° C. (hereinafter, “(meth) acrylate copolymer (A)” or “binder component ( A) "). The binder also comprises a second binder component (B) which is a cyclic monocarboxylic acid such as rosin or rosin derivatives.
Copolymer A
(Meth) acrylate copolymers (A) as comonomers:
i) Formula (I)

At least one (meth) acrylate of the formula: wherein R ¹ is H or CH ₃ and R ² is a C _{1 to} C ₂₀ hydrocarbyl substituent;
ii) based on the total weight of the copolymer (A), comprising 0.70 to 8.6% by weight of at least one carboxylic acid containing comonomer.

  The (meth) acrylate copolymer (A) has a glass transition temperature (Tg) such as 0 ° C. or less, for example −1 ° C. or less, −2 ° C. or less, or −4 ° C. or less, and all these values are It was measured according to the Tg test described in the example section. In particular, the (meth) acrylic ester copolymer (A) has a temperature of 0 to -60 ° C, for example, -1 to -60 ° C, or -5 to -55 ° C, preferably -10 to -50 ° C, particularly -15 to -45. It may have a Tg of ° C. By using (meth) acrylate copolymers (A) having a glass transition temperature (Tg) below 0 ° C., the viscosity of the final antifouling coating composition is reduced and thus the solvent content that may be required It is expected to decrease.

  The combination of comonomers defined in i) and ii) is at least 80%, for example at least 85%, preferably at least 90%, more preferably at least 95%, or at least 96% by weight of the copolymer (A). Made in%. In another particular embodiment, the combination of comonomers defined in i) and ii) represents up to 95% by weight of copolymer (A), for example up to 96% by weight or 99% by weight of copolymer (A).

  For clarity, "combination of comonomers defined by i) and ii)" includes the possibility of having two or more comonomers of formula (I) or two or more carboxylic acid-containing comonomers. The copolymer (A) preferably contains less than 10% by weight, preferably less than 5% by weight, of any comonomer other than the comonomers of formula (I) and the carboxylic acid containing compounds described in i) and ii) above. Preferably, it contains less than 4% by weight, preferably less than 2% by weight. In a particular embodiment, components (i) and (ii) constitute the entire comonomer component of copolymer (A).

  In certain embodiments, copolymer (A) does not contain hydrolyzable comonomers, such as silyl ester comonomers. Preferably, the copolymer (A) is nonhydrolyzable.

  Preferably, the copolymer (A) has a weight 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, etc. It has an average molecular weight (Mw). Polymer solution viscosity increases with increasing average molecular weight (Mw). Molecular weights in these ranges are preferred because they lower the viscosity of the polymer, thereby reducing the amount of solvent required for the antifouling coating composition and volatile organic compound (VOC) content. The copolymer (A) can have a PDI of 2 to 6.

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

  The (meth) acrylate comonomer (i) The (meth) acrylate comonomer used for the copolymer (A) is of the formula (I):

(Wherein R ¹ is H or CH ₃ , R ² is a C _{1 to} C ₂₀ hydrocarbyl, preferably a C ₁ to 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.

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

  In certain embodiments, the (meth) acrylate copolymer (A) is methyl methacrylate (MMA), n-butyl acrylate (n-BA), 2-ethylhexyl methacrylate (2-EHMA), 2-ethylhexyl acrylate (2-EHA) And at least one (meth) acrylate copolymer (A) of the formula (I) selected from n-butyl methacrylate (n-BMA). In certain embodiments, the (meth) acrylate copolymer comprises at least two different comonomers of Formula (I).

  In a particular embodiment, the (meth) acrylate copolymer (A) comprises methyl methacrylate (MMA) as one comonomer and at least one other comonomer of the formula (I). In a further particular embodiment, the (meth) acrylate polymer (A) comprises at least methyl methacrylate and butyl (meth) acrylate. When one or more (meth) acrylate comonomers of the formula (I) are present, the weight percentage of the sum of these (meth) acrylate comonomers in the (meth) acrylate copolymer is preferably at most 99.30% by weight, For example, at most 99.20 wt%, such as at most 99.0 wt%, such as at most 98.7 wt%, such as 98.6 wt%.

  Furthermore, if one or more (meth) acrylate comonomers of the formula (I) are present, the percentage by weight of the sum of these (meth) acrylate comonomers in the methacrylate copolymer is the total weight of the (meth) acrylate copolymer (A) Preferably, it is at least 80 wt%, such as at least 85 wt%, such as at least 90 wt%, such as at least 91.4 wt%).

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

  When present, n-butyl acrylate is preferably present in an amount of 50 to 99% by weight, preferably 55 to 99% by weight, preferably 65 to 99% by weight, for example 70 to 99% by weight.

Carboxylic acid-containing comonomer (ii)
The carboxylic acid containing comonomer (s) used for the (meth) acrylate copolymer (A) results in a coating with excellent results for fresh water absorption. Carboxylic acid-containing comonomer (s) are referred to herein as synonymous with the acidic comonomer. It has been found that undesirably high fresh water absorption is observed when the acid comonomer content is below the optimum range, but high viscosities are obtained when the acid comonomer content is above the optimum range. This means that a large amount of solvent is required to apply the paint.

  Thus, preferably, the acidic comonomer is present in an amount of 0.70 to 8.6% by weight, based on the weight of the (meth) acrylate copolymer (A). In a further specific embodiment, the carboxylic acid-containing comonomer is 0.8 to 8.6% by weight, for example 1.0 to 7.5% by weight, for example 1 based on the weight of the (meth) acrylate copolymer (A). In an amount of 2 to 7.0% by weight, such as 1.30 to 6.5% by weight, such as 1.4 to 6.0% by weight.

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

  The binder is preferably 10 to 50% by weight, preferably 15 to 30% by weight (dry solids) of component (A).

  In the present invention, the antifouling composition comprises 0.5 to 25% by weight, preferably 1 to 22% by weight, preferably 2 to 20% by weight, preferably 5 to 18% by weight (dry solids) of component (A) Is preferred.

  The amount of copolymer (A) in the binder is preferably so limited as to avoid anti-soiling coatings as it is very soft. The hardness of the coating film is determined by the binder mixture. Antifouling coatings that are very soft are susceptible to damage such as block marks in the shipyard, fender damage and scratches during operation, and in extreme cases cold flow of the coating.

Cyclic monocarboxylic acid component (B)
The binder according to the invention comprises at least one cyclic monocarboxylic acid (B). The cyclic monocarboxylic acid contains a single carboxyl functional group (which may be in the form of a salt thereof). The cyclic monocarboxylic acid may contain one ring or a plurality of cyclic rings. In particular, such a ring may be a fused ring. The cyclic monocarboxylic acid is preferably selected from resin acids, derivatives of resin acids, C6-20 cyclic carboxylic acids and mixtures thereof. Preferred monocarboxylic acids include resin acids such as abietic acid, neoabietic acid, dehydroabietic acid, dihydroabietic acid, tetrahydroabietic acid, pulstophosphoric acid, levopimaric acid, pimaric acid, isopimaric acid, sandaracopimaric acid, comnic acid, etc. Naphthenic acid; 1-methyl-3- (4-methyl-3-pentenyl) -3-cyclohexen-1-yl-carboxylic acid, 1-methyl-4- (4-methyl-3-pentenyl) -4-cyclohexene Methyl isohexenyl cyclohexene carboxylic acid such as -1-yl-carboxylic acid; 1,4,5-trimethyl-2- (2-methyl-1-propenyl) -3-cyclohexen-1-yl-carboxylic acid; 5,6-trimethyl-3- (2-methyl-1-propenyl) -4-cyclohexene-1-i - trimethyl isobutenyl cyclohexene carboxylic acid, such as carboxylic acids; and mixtures thereof. Ideally, the cyclic monocarboxylic acid is rosin or a derivative thereof.

  Monocarboxylic acids can be used to tailor 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, for example, a salt thereof as described below. Examples of rosin materials are: wood rosins, tall oil rosins and gum rosins; hydrogenated and partially hydrogenated rosins, disproportionated rosins, rosin derivatives such as maleic acid modified rosins, fumaric acid modified rosins; resin acid copper And zinc salts of resins, calcium salts of resins, metal salts of rosins and rosin derivatives such as magnesium resinates; and other rosins described in WO 97/44401. Preferred are gum rosin and derivatives of gum rosin.

  In the present invention, the antifouling composition comprises 0.5 to 25% by weight, preferably 1 to 22% by weight, preferably 2 to 20% by weight, preferably 5 to 18% by weight (dry solids) of component (B Is preferred.

  The binder is preferably 10 to 70% by weight, preferably 20 to 50% by weight (dry solids) of component (B).

  Preferably, in the binder of the present invention, the copolymer (A) and the component (B) are 1: 1 to 1:30, such as 1: 1 to 1:20, such as 1: 1 to 1:10, such as 1: 1 Present in a ratio (by weight) of 1: 5. Thus, typically, more (by weight) of component (B) than polymer (A) is present in the binder of the invention.

  The ratio of copolymer (A) to cyclic carboxylic acid compound (B) is important for the hardness of the coating film. The antifouling coating with more component (A) than component (B) is very soft and can have a block mark in the shipyard, a film of paint that is susceptible to fender damage and scratches during operation. In extreme cases, cold flow of the coating can occur.

  More preferably, components (A) and (B) together constitute at least 50% by weight, for example at least 60% by weight, of the binder of the antifouling coating composition of the present invention.

  In one embodiment, the binder comprises 10 to 50% by weight of component (A), preferably 15 to 30% by weight (dry solids), preferably 10 to 70% by weight of component (B), preferably 20 to 50 Contains wt% (dry solids).

Additional hydrolyzable copolymer (C)
The binder composition of the present invention may comprise additional components. These may be hydrolyzable copolymers, such as non-hydrolyzable (meth) acrylate or silyl ester copolymers.

  Thus, the compositions of the present invention may comprise hydrolysable binder components such as silyl ester (meth) acrylate copolymers. Hereinafter, the terms "hydrolyzable copolymer" or "hydrolyzable silyl ester copolymer" are used interchangeably and mean any silyl ester (meth) acrylate copolymer that may be present in the binder and antifouling coating composition of the present invention. Point to. These copolymers contain side chains that hydrolyze in natural seawater. Non-hydrolyzable (meth) acrylates do not contain side chains that undergo hydrolysis in natural seawater (e.g. methyl methacrylate and n-butyl methacrylate).

  The silyl (meth) acrylate comonomers suitable for use in such hydrolyzable silyl ester (meth) acrylate copolymers are preferably of the formula (II)

(In the formula,
R ³ is H or CH ₃ ,
Each R ⁴ is independently selected from a linear or branched C _1-4 alkyl group,
R ⁵ consists of a linear or branched C _{1 to} C ₂₀ alkyl group, a C _{3 to} C ₁₂ cycloalkyl group, an optionally substituted C _{6 to} C ₂₀ aryl group and an —OSi (R ⁶ ) ₃ group Each independently selected from the group
Each R ⁶ is independently a linear or branched C ₁ -C ₄ alkyl group,
p is an integer of 0 to 5).

  The term "alkyl" is intended to encompass 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 halogen, an alkyl group having 1 to about 8 carbon atoms, an aryl group substituted with at least one substituent selected from an acyl group or a nitro group. Particularly preferred aryl groups include substituted and unsubstituted phenyl, benzyl, phenanalkyl or naphthyl.

  Ideally, preferred silyl ester monomers are based on compounds of formula (II) where p is zero.

  More preferably, the silyl ester comonomer has the formula (III)

R ³ is H or CH ₃ ,
R ⁵ is each independently selected from the group consisting of linear or branched C ₁ -C ₁₀ alkyl groups.

Examples of monomers containing silyl ester functional groups are well known. As a monomer defined by general formula (II),
For example, tri-n-propylsilyl (meth) acrylate, triisopropylsilyl (meth) acrylate, tri-n-butylsilyl (meth) acrylate, triisobutylsilyl (meth) acrylate, tert-butyldimethylsilyl (meth) acrylate, thexyl Diethyldimethylsilyl (meth) acrylate, tert-butyldiphenylsilyl (meth) acrylate, nonamethyltetrasiloxanyl (meth) acrylate, bis (trimethylsiloxy) methylsilyl (meth) acrylate, tris (trimethylsiloxy) silyl (meth) acrylate And acrylic acid and methacrylic acid silyl ester monomers.

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

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

  Similar to the silyl ester comonomer (II), the hydrolyzable copolymer (C) ideally comprises the second comonomer. The second comonomer is preferably a non-hydrophilic comonomer of formula (I) or a hydrophilic comonomer of formula (IV) as defined hereinbelow. The hydrolyzable copolymer can also comprise a comonomer of formula (I) and a comonomer of formula (IV).

  The hydrophilic comonomers of formula (IV) have the formula

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

As shown in the above formula, the term "hydrophilic (meth) acrylate" means that the R ⁸ group of formula (IV) contains at least one oxygen or nitrogen atom, preferably at least one oxygen atom. Need. As explained in more detail below, the additional non-hydrophilic (meth) acrylate comonomers of formula (I) may be present in hydrolysable copolymers in which R ² units consist exclusively of C and H atoms .

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

  In one embodiment, as the hydrolyzable copolymer, 2-methoxyethyl acrylate (MEA), 2-methoxyethyl methacrylate (MEMA), 2-ethoxyethyl methacrylate (EEMA), 2- (2-ethoxyethoxy) ethyl acrylate ( Edega), 2- (2-ethoxyethoxy) ethyl methacrylate (EDEGMA), 2- (2-butoxyethoxy) ethyl acrylate (BDGA) or 2- (2-butoxyethoxy) ethyl methacrylate (BDGMA).

In one embodiment, the hydrolyzable copolymer comprises at least one comonomer of the above formula (IV), wherein the R ⁸ group is a saturated cyclic group comprising at least one oxygen or nitrogen atom, preferably at least one oxygen atom. Including. More preferably, R ⁸ is a W—R ¹⁰ group, wherein R ¹⁰ is a cyclic ether (eg, optionally alkyl substituted oxolane, oxane, dioxolane, dioxane) and W is C 1 -C 4 alkylene It is. Such monomers include furfuryl acrylate, tetrahydrofurfuryl acrylate, (1,3-dioxolan-4-yl) methyl acrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, (2,2-dimethyl-1,3-dioxolane -4-yl) methyl methacrylate may be used. Preferred cyclic ethers are those containing at least 4 atoms in the ring. Most preferably, in this embodiment the compounds of formula (IV) are tetrahydrofurfuryl acrylate (THFA) and tetrahydrofurfuryl methacrylate (THFMA).

  The comonomers of formula (IV) are preferably 2-methoxyethyl acrylate (MEA), 2-methoxyethyl methacrylate (MEMA), 2-ethoxyethyl methacrylate (EEMA), tetrahydrofurfuryl acrylate (THFA), tetrahydrofurfuryl methacrylate (THFMA), 2- (2-ethoxyethoxy) ethyl acrylate (EDEGA), 2- (2-ethoxyethoxy) ethyl methacrylate (EDEGMA), 2- (2-butoxyethoxy) ethyl acrylate (BDGA), or 2- (2) 2-butoxyethoxy) ethyl methacrylate (BDGMA).

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

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

  When present, the hydrolyzable copolymer (C) preferably comprises at least the comonomer triisopropylsilyl (meth) acrylate, and the comonomer of the formula (I) and the comonomer of the formula (IV). The preferred options of formula (I) above apply to hydrolysable copolymers.

  Preferably, the comonomer of formula (IV) forms at least 3% by weight of the hydrolysable copolymer component. Particularly preferred amounts of hydrophilic (meth) acrylate comonomers of the formula (IV) in the hydrolyzable copolymer are 3 to 50% by weight, preferably 3 to 30% by weight, for example 5 to 30% by weight, or 5 to 25% %. If mixtures of comonomers of the formula (IV) are present, these amounts are related to the total weight proportion of the comonomers of the formula (IV) in the copolymer.

  Preferably, the hydrolyzable copolymer is at least 10% by weight of non-hydrophilic comonomers of the formula (I), preferably at least 15% by weight, preferably at least 20% by weight, for example 10 to 60% by weight, preferably 15 to 50 % By weight, more preferably 20 to 40% by weight of comonomers of formula (I). If mixtures of comonomers of the formula (I) are present, these amounts are related to the total weight proportion of comonomers of the formula (I) in the copolymer.

  The hydrolyzable copolymer (C) preferably has a glass transition temperature (Tg) of at least 10 ° C., preferably at least 15 ° C., preferably at least 20 ° C., for example at least 22 ° C., or at least 30 ° C. All values are measured according to the Tg test described in the example section. Values below 80 ° C. are preferred, for example below 75 ° C., for example below 50 ° C.

  The hydrolyzable copolymer is preferably 5,000 to 70,000, preferably 10,000 to 60,000, in particular 10,000 to 50,000, 20,000 to 50,000 or 20,000 to 40,000. Have a weight average molecular weight of

  Typically, the hydrolyzable copolymer is free of carboxylic acid containing comonomers.

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

  When present, the hydrolyzable copolymer component (C) preferably forms 20 to 60% by weight, for example 25 to 50% by weight of the binder.

  In the present invention, the antifouling composition comprises 0.5 to 30% by weight, preferably 1 to 22% by weight, preferably 2 to 20% by weight, preferably 5 to 18% by weight (dry solids) of component (C). Is preferred.

Additional non-hydrolyzable polymer (D)
The binders of the invention, and thus the antifouling coating composition, may comprise additional non-hydrolyzable (meth) acrylate copolymers. Hereinafter, the terms "non-hydrolyzable copolymer", "non-hydrolyzable (meth) acrylate copolymer" are components of the present invention (A) that do not contain a side chain that hydrolyzes in natural seawater, such as silyl ester monomer residues Point to binders other than). Thus, when present, these binder components are present in addition to the copolymer (A), unlike the hydrolyzable binders (C) described above. Preferably, the non-hydrolyzable copolymer component contains no carboxylic acid monomer (ii).

  Preferably, such non-hydrolyzable polymers comprise 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 is MMA, and n-BA of formula (I), or EEMA or MEA of formula (IV), at least one of formula (I) and / or formula (IV) Containing two other comonomers. Typically, the non-hydrolyzable copolymer comprises MMA and at least one other comonomer selected from MEMA, MEA, EEMA, THFA, THFMA, EDEGA, BDGMA, BDGA and EDEGMA.

  Preferably, in such non-hydrolyzable polymers, the non-hydrophilic comonomer (s) of formula (I) is present in the copolymer in an amount of up to 95% by weight, for example up to 90% by weight, or up to 85% by weight Exists. Typically, the non-hydrophilic comonomer (s) of formula (I) is at least 30% by weight, such as at least 40% by weight, such as at least 50% by weight, eg 30-95% by weight, 40-90% in the binder. It is present in the range of 50% by weight or 50% by weight.

  It is preferred that the non-hydrolyzable copolymer has a glass transition temperature (Tg) of at least 0 ° C, preferably at least 5 ° C, preferably at least 10 ° C, preferably at least 15 ° C. Values of less than 80 ° C. are preferred, such as less than 75 ° C., less than 50 ° C., less than 40 ° C., less than 30 ° C.

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

  The nonhydrolyzable polymer preferably has a PDI of 2 to 6.

  When present, component (D) preferably forms 20 to 60% by weight, for example 25 to 50% by weight (dry solids) of the binder.

  In the present invention, the antifouling composition comprises 0.5 to 30% by weight, preferably 1 to 22% by weight, preferably 2 to 20% by weight, preferably 5 to 18% by weight of the component (D) (dry solids). It is preferable to include in.

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

Preparation of Polymer (A), and Polymers (C), and (D) Polymers can be prepared using polymerization reactions known in the art. Acrylic polymers are preferably prepared using addition polymerization or chain growth polymerization. Examples of suitable addition polymerization techniques include free radical polymerization, anionic polymerization and suitably controlled polymerization techniques. The polymer is controlled, for example, by any of various methods such as solution polymerization, bulk polymerization, emulsion polymerization, and suspension polymerization in a conventional manner, or in the presence of a polymerization initiator and optionally chain transfer agent It can be obtained by polymerizing the monomer mixture by polymerization techniques. When preparing a coating composition using this polymer, it is preferable to dilute the polymer with an organic solvent to obtain a polymer solution having an appropriate viscosity. From this point of view, it is desirable to use solution polymerization.

  Examples of polymerization initiators for free radical polymerization include dimethyl 2,2′-azobis (2-methyl propionate), 2,2′-azobis (2-methylbutyronitrile), 2,2′- Azo compounds such as azobis (isobutyronitrile) and 1,1′-azobis (cyanocyclohexane), and tert-butylperoxypivalate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxydiethylaceto Tart, tert-butylperoxyisobutyrate, di-tert-butylperoxide, tert-butylperoxybenzoate, tert-butylperoxyisopropyl carbonate, tert-amylperoxypivalate tert- amyl peroxy-2-ethylhexanoate, peroxides such as 1,1-di (tert- amyl peroxy) cyclohexane and dibenzoyl peroxide. These compounds are used alone or as a mixture of two or more.

  Examples of the organic solvent include aromatic hydrocarbons such as xylene, toluene and mesitylene; ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, methyl isoamyl ketone, cyclopentanone and cyclohexanone; butyl acetate, tert-butyl acetate Amyl acetate, ethylene glycol methyl ether acetate, butyl propionate, esters such as isobutyl propionate; ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dibutyl ether, dioxane, ethers such as tetrahydrofuran; n-butanol, isobutanol, benzyl alcohol Alcohols such as butoxyethanol and ether alcohols such as 1-methoxy-2-propanol; d-limonene etc. Cyclic terpenes, aliphatic hydrocarbons such as white spirit; by and optionally two or more solvents. These compounds are used alone or as a mixture of two or more.

  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 may be used to adjust the properties of the binder. Examples of further binder components are
Esters of rosins such as methyl esters, glycerol esters, poly (ethylene glycol) esters, pentaerythritol esters and esters of hydrogenated rosins, preferably gum rosins and esters of hydrogenated gum rosins;
Dimerization and polymerization rosin;
An acid functional polymer blocked with a divalent metal bound to a monovalent organic residue or a divalent metal bound to a hydroxyl residue;
Hydrophilic copolymers, for example (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);
Poly (lactic acid), poly (glycolic acid), poly (2-hydroxybutyric acid), poly (3-hydroxybutyric acid), poly (4-hydroxyvaleric acid), polycaprolactone, and two units selected from the above units Aliphatic polyesters, such as aliphatic polyester copolymers comprising above; and other condensation polymers such as polyoxalates;
Alkyd resins and modified alkyd resins;
Mention may be made of hydrocarbon resins such as hydrocarbon resins formed solely from the polymerization of at least one monomer selected from C5 aliphatic monomers, C9 aromatic monomers, indencoumarone monomers, or terpenes, or mixtures thereof.

Acyclic Monocarboxylic Acid In one embodiment, the antifouling coating of the present invention is a liquid acyclic C12-C24 monocarboxylic acid or a salt thereof, ie an acid containing a single -COOH moiety in the molecule, or a salt thereof Can be included. Such acids comprise an acidic "head group" and a nonpolar "tail group" which is preferably a branched chain of carbon atoms. The monocarboxylic acids preferably contain only C, H and O atoms.

  The use of such materials can improve the control of leaching layer formation (reduce the thickness) more than the non-acid component-containing comparison composition. Additionally, compositions containing an acid component should exhibit similar levels of polishing while maintaining or even reducing the viscosity of the paint.

  The component may comprise one or more monocarboxylic acids selected from liquid non-cyclic saturated C12-C24 monocarboxylic acids or liquid non-cyclic branched C12-C24 monocarboxylic acids. Thus, the acid should not be a linear unsaturated carboxylic acid. It is preferred that the acid be saturated.

The monocarboxylic acid is ideally of the formula R ¹¹ COOH, where R ¹¹ is a C 11-23 acyclic branched alkyl or alkenyl group, or a C 11-23 acyclic saturated linear or branched chain It is an alkyl group. R ¹¹ is preferably a C11-23 non-cyclic branched alkyl group.

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

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

  The acid component is preferably branched. Branched acids must contain a tertiary or quaternary carbon atom in their tail group.

  Many of the acids may be derived from natural sources, in which case, in isolated form, they are typically present as a mixture of acids having different degrees of branching and different chain lengths It is understood. 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 more than 90%. The percentage here is wt% (wt%). As an example, a C18 acid component having a degree of branching of at least 50% contains 50% or less of a linear C18 acid (such as n-stearic acid, n-oleic acid, n-linoleic acid) The remainder are branched C18 acids (generally, "isostearic acid", "isooleic acid", "isolinoleic acid") and the like.

  In a preferred embodiment, the acid is a C14-C20 monocarboxylic acid, preferably a C16-C20 monocarboxylic acid, in particular a C16-18 monocarboxylic acid. It is preferred that the carbon chains contain an even number of carbon atoms. In a preferred embodiment, the acid has a molecular weight of less than 350 g / mol, in particular less than 320 g / mol, in particular less than 300 g / mol.

  In a preferred embodiment, the acid has an acid number of less than 310, in particular less than 300, for example less than 290, or even less than 280. "Acid number" is a known parameter and is the mass of KOH (mg (milligram)) required to neutralize one gram of acid (ISO 660: 2009).

  In preferred embodiments, the acid has an iodine value of less than 50, such as less than 40, less than 30, or less than 20. In some embodiments, the acid may be a saturated acid having an iodine number of zero. "Iodine value" is a known parameter and is the mass of iodine that reacts with 100 grams of acid (g (grams)) (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 isopalmitic acid are available under the names Radiacid 0906, Radiacid 0907, and Radiacid 0909 (Oleon), with suitable degrees of branching. In particular the higher branched isostearic acid is Fine oxo call isostearic acid N product (Nissan Chemicals).

  Particularly preferred acids are isostearic acid and isopalmitic acid, in each case having a degree of branching of more than 70% and an iodine value of less than 30. Particularly preferred ingredients are fine oxo-col isostearic acid N (Nissan Chemicals) and Radiacid 0906, Radiacid 0907, or Radiacid 0909 (Oleon).

  It will be understood that any acid can form a salt when a metal ion is present. We propose to add the acid in its acid form, but it is also possible to add the acid in its salt form. The acid can also be converted to salt form in the composition. The weight percent of acid added to the composition is to be calculated assuming that the acid is in the form of an acid. This component can be considered as a further optional component of the binder.

  The binder typically forms 20 to 80% by weight, for example 25 to 70% by weight (dry solids) of the antifouling coating composition. This percentage refers to the total amount of binder components such as components (A) to (D) present.

  The binder composition of the present invention is ideally incorporated into the antifouling coating composition.

Antifouling Agent The antifouling coating preferably further comprises a compound capable of preventing or decontaminating marine fouling of the surface. The terms "antifouling agent", "antifouling agent", "biocide", "toxicant" are used to describe known compounds that act to prevent marine fouling of surfaces. It is used in industry. The antifouling agent of the present invention is a marine antifouling agent.

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

  Examples of inorganic antifouling agents include copper compounds such as copper and copper oxide, for example, copper (I) oxide and copper (II) oxide; copper alloys such as copper-nickel alloys; copper (I) thiocyanate and copper sulfide And copper salts. Examples of organometallic marine antifouling agents include zinc 2-pyridinethiol-1-oxide [zinc pyrithione]; copper 2-pyridinethiol-1-oxide [copper pyrithione], copper acetate, copper naphthenate, copper 8-quinolinolate [ Organic copper compounds such as oxine-copper], copper nonylphenol sulfonate, copper bis (ethylene diamine) bis (dodecyl benzene sulfonate) and copper bis (pentachlorophenolate); zinc bis (dimethyl dithiocarbamate) [ziram], zinc ethylene bis Examples include dithiocarbamate compounds such as (dithiocarbamate) [dineb], manganese ethylene bis (dithiocarbamate) [maneb], and manganese ethylene bis (dithiocarbamate) complex [mancozeb] with a zinc salt.

  Examples of organic marine antifouling agents include 2- (tert-butylamino) -4- (cyclopropylamino) -6- (methylthio) -1,3,5-triazine [sibutrin], 4,5-dichloro- 2-n-octyl-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one [DCOIT], 2- (thiocyanatomethylthio) -1,3-benzothiazole [benchazole], 3- Benzo [b] thien-2-yl-5,6-dihydro-1,4,2-oxathiazine 4-oxide [betoxazine] and 2,3,5,6-tetrachloro-4- (methylsulfonyl) Pyridine; urea derivatives such as 3- (3,4-dichlorophenyl) -1,1-dimethylurea [diuron]; amides and carboxylic acids, sulfonic acids, And imides of sulfenic acids, such as N- (dichlorofluoromethylthio) phthalimide, N'-dichlorofluoromethylthio-N ', N'-dimethyl-N-phenylsulfamide [dichlorofluanid], N'-dichlorofluoromethylthio- N ', N'-dimethyl-Np-tolylsulfamide [tolylfluanid] and N- (2,4,6-trichlorophenyl) maleimide; other organic compounds such as pyridine triphenyl borane, amine triphenyl Borane, 3-iodo-2-propynyl N-butylcarbamate [iodocarb], 2,4,5,6-tetrachloroisophthalonitrile [chlorothalonyl], p-((diiodomethyl) sulfonyl) toluene and 4-bromo-2 -(4-chlorophenyl) -5- (trifluoromethyl) Heterocyclic compounds such as 1H- pyrrole-3-carbonitrile [Toropiopiru] and the like.

  Other examples of marine antifouling agents include tetraalkylphosphonium halides, guanidine derivatives; imidazole-containing compounds such as 4- [1- (2,3-dimethylphenyl) ethyl] -1H-imidazole [medetomidine] and derivatives thereof Macrocyclic lactones including avermectins and their derivatives such as ivermectin; derivatives such as spinosyns and spinosads; their derivatives such as capsaicin and phenyl capsaicin; oxidases, proteolytic enzymes, hemicellulolytic enzymes, cellulolytic enzymes And lipolytically active enzymes, and enzymes such as amylolytically active enzymes.

  Traditionally, antifouling coating compositions contain copper biocides such as metallic copper, cuprous oxide, copper thiocyanate and the like.

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

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

  Preferred biocides are cuprous oxide, copper thiocyanate, zinc pyrithione, copper pyrithione, zinc ethylene bis (dithiocarbamate) [dineb], 2- (tert-butylamino) -4- (cyclopropylamino)- 6- (Methylthio) -1,3,5-triazine [cubutryne], 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one [DCOIT], N'-dichlorofluoromethylthio- N ′, N′-dimethyl-N-phenylsulfamide [dichlorofluanid], N′-dichlorofluoromethylthio-N ′, N′-dimethyl-N-p-tolylsulfamide [tolylfluanid], 4 -[1- (2,3-dimethylphenyl) ethyl] -1H-imidazole [medetomidine], triphenylborane pyridin [TPBP], and 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl)-1H-pyrrole -3-carbonitrile [Toraropiriru.

  Because different biocides act on different marine fouling organisms, mixtures of biocides can be used, as is known in the art. Mixtures of antifoulants are generally preferred.

  In one embodiment, the antifouling coating composition comprises cuprous oxide and / or copper thiocyanate, and copper pyrithione, zinc ethylene bis (dithiocarbamate), 4,5-dichloro-2-octyl-4-isothiazoline- It contains one or more biocides selected from 3-one and medetomidine.

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

  When present, the combined amount of biocide may be up to 70%, eg 4 to 60%, eg 5 to 60% by weight of the coating composition. When copper is present, a suitable amount of biocide may be 20-60% by weight in the coating composition. Where copper is avoided, small amounts (e.g. 0.2 to 15 wt%) such as 0.1 to 20 wt% may be used. It will be appreciated that the amount of biocide will vary depending on the end use and the biocide used. Some biocides can be encapsulated or adsorbed to an inert carrier or linked to other substances to control release. These percentages refer to the amount of active biocide present, and therefore not to any carrier used.

Other Components The antifouling coating composition according to the invention is optionally selected from inorganic or organic pigments, extenders and fillers, additives, solvents, and thinners, in addition to the binder and any of the above mentioned components. It can further comprise one or more components.

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. As an organic pigment, a phthalocyanine compound, an azo pigment, carbon black is mentioned.

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

  Preferably, the total amount of extenders, fillers and / or pigments present in the composition according to the invention is 0 to 70% by weight, more preferably 1 to 60% by weight, based on the total weight of the composition, furthermore More preferably, it is 2 to 50% by weight. One skilled in the art will appreciate that the content of extenders and pigments will vary depending on the other components 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 referred to as a water scavenger or desiccant. Preferably, the dehydrating agent is a compound that removes water from the composition in which water is present. The dehydrating agent removes water introduced from raw materials such as pigments and solvents, or water generated by the reaction of a carboxylic acid compound with a specific compound (for example, metal oxide) in the antifouling coating composition. Improves the storage stability of the antifouling coating composition comprising a water reactive compound such as, for example, a silyl ester copolymer. Dehydrating agents and dehumidifying desiccants that may be used in the antifouling coating composition include organic and inorganic compounds.

  Dehydrating agents can be combined with water as hygroscopic materials that absorb water, or as water of crystallization often referred to as a dehumidifying desiccant. Examples of dehumidifying 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 that react with water include: orthoformiate triethyl orthoformate, tripropyl orthoformate, triisopropyl orthoformate, tributyl orthoformate, tributyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate, tributyl orthoacetate, and triethyl orthopropynate Ketals; acetals; enol ethers; trimethyl orthoborate, triethyl borate, tripropyl borate, triisopropyl borate, tributyl borate and ortho-borates such as tri-t-butyl borate; trimethoxymethylsilane, vinyl Organosilanes such as trimethoxysilane, phenyltrimethoxysilane, tetraethoxysilane and ethylpolysilicate.

  Preferred dehydrating agents are those that react chemically with water. Particularly preferred dehydrating agents are organosilanes. Preferably, the dehydrating agent is present in the composition of the present invention in an amount of 0 to 5% by weight, more preferably 0.5 to 2.5% by weight, even more preferably 1.0, based on the total weight of the composition. Present in an amount of ̃2.0% by weight.

Solvents and Thinners The antifouling composition very preferably contains a solvent. The solvent is preferably volatile and preferably organic. Examples of organic solvents and thinners are aromatic hydrocarbons such as xylene, toluene and mesitylene; ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl isoamyl ketone, methyl amyl ketone, diisobutyl ketone, methyl propyl ketone, cyclopentanone and cyclohexanone Butyl acetate, tert-butyl acetate, amyl acetate, isoamyl acetate, ethylene glycol methyl ether acetate, propyl propionate, butyl propionate, esters such as isobutyl isobutyrate; ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dibutyl ether, dioxane, Ethers such as tetrahydrofuran; Alcohols such as n-butanol, isobutanol, benzyl alcohol; butoxyethano Le, 1-methoxy-2-propanol and ether alcohols such as; cyclic terpenes, such as d- limonene; a mixture of two or more solvents and thinners by and optionally, aliphatic hydrocarbons such as white spirit. Another example of thinner is water.

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

  The amount of solvent is preferably as low as possible. The solvent content may be up to 50% by weight of the composition, preferably up to 45% by weight of the composition, for example up to 40% by weight, but may be less than 15% by weight, for example 10% by weight or less . Again, one skilled in the art will appreciate that the solvent content will vary depending on the other components present and the end use of the coating composition.

  Alternatively, the coating can be dispersed in an organic nonsolvent for the film forming component in the coating composition or aqueous dispersion.

  The antifouling coating composition according to the invention preferably has a solids content of more than 40% by volume, for example more than 45% by volume, for example more than 50% by volume, preferably more than 55% by volume.

  More preferably, the antifouling coating composition has a content of volatile organic compound (VOC), such as less than 500 g / L, preferably less than 400 g / L, for example less than 390 g / L. The 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 ° C. in the range of 100 to 980 cP, preferably 150 to 950 cP, more preferably 200 to 900 cP, as measured according to ISO 2884-1: 1999. Can.

Other Additives Examples of other additives that can be added to the antifouling coating composition are reinforcing agents, thixotropic agents, thickeners, anti-settling agents, wetting and dispersing agents, plasticizers, and stabilizers. is there.

  Examples of reinforcing agents are flakes and fibers. Fibers include natural and synthetic inorganic fibers such as silicon-containing fibers, carbon fibers, oxide fibers, carbide fibers, nitride fibers, sulfide fibers, phosphate fibers and mineral fibers; metal fibers; cellulose fibers, rubber fibers, Natural and synthetic organic fibers such as acrylic fibers, polyamide fibers, polyimides, polyester fibers, polyhydrazide fibers, polyvinyl chloride fibers, polyethylene fibers, fibers described in WO 00/77102 and the like can be mentioned. Preferably, the average length of the fibers is 25 to 2000 μm, the average thickness is 1 to 50 μm, and the ratio of average length to average thickness is at least 5.

  Examples of thixotropic agents, thickeners and anti-settling agents are silicas such as fumed silica, organically modified clays, organic waxes, amide waxes, polyamide waxes, amide derivatives, polyethylene waxes, polyethylene oxide waxes, hydrogenated castor oil waxes, ethyl cellulose, stearic acid Aluminum, and mixtures thereof.

  Examples of plasticizers are chlorinated paraffin, phthalates, phosphoric esters, sulfonamides, adipic acid, and epoxidized vegetable oils.

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

  Generally, these optional components are present in an amount ranging from 0.1 to 20%, typically 0.5 to 20%, preferably 0.75 to 15% by weight of the antifouling composition. May be It will be understood that the amount of these optional components will vary depending on the end use.

  The antifouling coating composition of the present invention can be applied to all or part of the surface of any object susceptible to fouling. The surface may be underwater, permanently or intermittently (e.g., by tidal movement, loading or swelling of different cargoes). The object surface is typically the surface of a ship, the surface of a fixed marine object (e.g. an oil platform or buoy etc). Application of the coating composition can be accomplished by any convenient means, such as painting (eg, by a brush or roller), or spraying a coating onto an object. Typically, the surface needs to be separated from the seawater in order to be able to be coated. Application of the coating can be accomplished as is conventionally known in the art.

  When applying an antifouling coating to an object (e.g., a hull), the surface of the object is typically not protected solely by a single antifouling coating. Depending on the nature of the surface, the antifouling coating can be applied directly to existing coating systems. Such coating systems can include several layers of paint of different general types (eg, epoxy, polyester, vinyl, or acrylic, or mixtures thereof). When the surface is clean and the previously applied antifouling coating on the surface is intact, the new antifouling paint is typically directly as one or two additional coatings, exceptionally more It can be applied.

  Alternatively, one skilled in the art may begin with an uncoated surface (eg, steel, aluminum, plastic, composites, glass fibers or carbon fibers). In order to protect such surfaces, complete coating systems typically include one or two layers of anticorrosion coatings, one layer of bond coats, and one or two layers of antifouling coatings . One skilled in the art would be familiar with these coating layers.

  In exceptional cases, an additional antifouling paint layer can be applied.

  Thus, in a further embodiment, the present invention provides a substrate coated on top with an anticorrosion coating layer such as an epoxy primer, a bonding layer and an antifouling coating composition as defined herein.

The invention is defined with reference to the following non-limiting examples.
Example materials and methods

Solvesso 100 was supplied by Brenntag.

Measurement of Polymer Solution Viscosity The viscosity of the polymer solution was measured according to ASTM D2196-15 test method A using a Brookfield DV-1 viscometer equipped with an LV-2 or LV-4 spindle at 12 rpm. Before measurement, the polymer solution was adjusted to 23.0 ± 0.5 °.

Determination of the Non-Volatile Substance Content of the Polymer Solution The non-volatile substance content of the polymer solution was determined according to ISO 3251. Test samples of 0.5 g ± 0.1 g were removed and dried in a ventilated oven at 105 ° C. for 3 hours. The weight of the residue is considered to be non-volatile material (NVM). The non-volatile substance content is expressed in% by weight. The value given is the mean value of three parallel runs.
Measurement of Polymer Average Molecular Weight Distribution The polymer was characterized by gel permeation chromatography (GPC) measurement. Molecular weight distribution (MWD) was measured using two PLgel 5 μm Mixed-D columns (Agilent) in series using a Malvern Omnisec Resolve and Reveal system. The column was calibrated by conventional calibration using narrow polystyrene standards.

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

The analysis conditions are shown below.

Measurement of Glass Transition Temperature Glass transition temperature (Tg) is obtained by differential scanning calorimetry (DSC) measurement. DSC measurements were performed on a TA Instruments DSC Q200. One drop of polymer solution was added to an aluminum pan and dried at 50 ° C. for 18 hours, 150 ° C. for 3 hours in a heating cabinet (about 10 mg of dried polymer obtained). The measurement was performed by the heating-cooling-heating procedure (-80 ° C to 120 ° C) of an open aluminum pan. The scans were recorded at a heating rate of 10 ° C./min and a cooling rate of 10 ° C./min relative to the empty pan. Data were processed using Universal Analysis software (TA Instruments).

  The inflection point of the glass transition range defined in ASTM E 1356-08 for the second heat is recorded as the Tg of the polymer.

Determination of the acid number of the polymer The acid number of the polymer was determined according to ISO 2114: 2000 method A. Solvesso 100: xylene: butanol 60: 25: 15 was used as a solvent. Colorimetric titration with phenolphthalein was used. The titration was performed until the red color stabilized for 10-15 seconds. It was measured 2-3 times per polymer. The acid number of the dry polymer was calculated based on the measured non-volatile material.

General Procedure for the Preparation of the Antifouling Coating Composition The components were mixed in the proportions shown in Tables 3-4. The mixture was dispersed for 15 minutes in a 250 ml paint can in the presence of glass beads (about 2 mm in diameter) using a vibrating shaker. Glass beads were filtered off before testing.

Measurement of paint viscosity using a cone and plate viscometer The viscosity of the antifouling paint composition is a shear of 10000 s ⁻¹ using a digital cone and plate viscometer set at a temperature of 23 ° C. according to ISO 2884-1: 1999. It was operated at speed to obtain viscosity measurement range 0-10P. Results are shown as the average of 3 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 by weight method in fresh water / deionized water The absorption of water in the coating membrane was measured by weight method. The paint was applied to pre-weighed and numbered sandblasted glass panels (5.0 × 7.5 cm) using a film applicator with a gap size of 300 μm. The membrane was dried at 50 ° C. overnight for at least 1 day under ambient conditions and then vacuum dried in a desiccator for 24 hours. After drying, the coated glass panels were weighed and placed in a container filled with distilled water. For reading, the panel and the painted surface were quickly dried using compressed air. The panels were weighed ( _{m.sub.directly} ) and then allowed to dry under ambient conditions for 2 days, then placed in a desiccator under vacuum for 24 hours and then weighed again ( _m.sub.dry ). The difference in weight before and after drying relative to the dry weight of the paint film after exposure is expressed as a percentage of water absorption.

Water absorption amount = (m _directly- m _dry ) / (m _dry- m _{empty panel} )
The reading took place after 34 days. The results are shown in Tables 3 and 4.

Measurement of Polishing of Antifouling Coating Film on Rotating Disk in Sea Water Polishing was performed by measuring the decrease in the film thickness of the coating film. In this test, PVC disks were used. The coating composition was applied as radial stripes on the disc using a film applicator. The thickness of the dried coating was measured by surface profiler. A PVC disc was attached to the shaft and rotated in a vessel containing seawater. Natural seawater was filtered and adjusted to a temperature of 25 ° C ± 2 ° C. The speed of the rotating shaft resulted in an average simulation speed of 16 knots on the disc. The PVC disc was removed to measure the film thickness. The discs were rinsed and allowed to dry overnight at room temperature before measuring film thickness. The result was obtained as the amount of reduction of the film, ie the difference between 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)) A temperature controlled reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet and a supply port, 26.10 parts of xylene and 1-methoxy- 6.10 parts of 2-propanol were added. The reaction vessel was heated and maintained at 105 ° C. 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-2-propanol The reaction mixture was stirred at a constant speed for 2 hours 30 minutes under nitrogen atmosphere. After an additional hour of reaction, a post addition of 0.35 parts of dibenzoyl peroxide (50% in dicyclohexyl phthalate) and 4.20 parts of xylene in the boost initiator solution is added to the reaction vessel at a constant rate over a period of 15 minutes The The reaction vessel was maintained at reaction temperature for an additional hour and then cooled to room temperature. The amounts of ingredients are given in parts by weight.

Copolymer solution S-1 had a viscosity of 945 cP, 55.5 wt% non-volatile content, Mw 23600, PDI 2.60, and Tg 23.5 ° C.
General Procedure for the Preparation of Copolymer Solutions P1-P8 and CP1-CP6 All polymers tested were taken in a temperature controlled reaction vessel equipped with stirrer, reflux condenser, nitrogen inlet and feed port, 24.17 parts xylene and Prepared in the same manner by charging 9.81 parts of PM (solvent blend 1). The reaction vessel was heated and maintained at 85 ° C. 50.00 parts of a premix of monomers, 10.08 parts of xylene (solvent 2), and an initiator were prepared and charged to the reaction vessel at a constant rate over a period of 2 hours and 30 minutes under a nitrogen atmosphere. After reacting for an additional hour, the boost solution of initiator and a post-addition of 5.00 parts of xylene (solvent 3) were charged to the reaction vessel at a constant rate for 15 minutes. The reaction vessel was maintained at reaction temperature for an additional hour and then cooled to room temperature. The amount of solvent is shown in parts by weight.

  As an exception to this, the reaction temperature of polymers P4, P8, CP3 and CP6 was 95.degree. All polymers were made using 50.0 wt% theoretical non-volatile material.

Another exception is that polymer CP1 was made with the following amounts of solvent (parts by weight).
Solvent Blend 1: Xylene / PM 24.57 / 9.85
Solvent 2: Xylene 9.36
Solvent 3: Xylene 5.28
Another exception is that polymer CP6 was made with the following amounts of solvent (parts by weight).
Solvent Blend 1: Xylene / PM 23.63 / 7.00
Solvent 2: None Solvent 3: Xylene 3.40
Thinning before cooling: Xylene 14.92
A summary of the different polymers synthesized and the amount of initiator used is given in Table 1 and a summary of the polymer properties is given in Table 2.

As can be seen from the above data, compositions containing copolymers containing small amounts of carboxylic acid containing comonomers result in coatings having undesirably high water absorption values. This can be seen in the composition with the polymers CP1 and CP2. The polymers CP3 and CP4 give an undesirably high viscosity, thus indicating that exceeding a high content of carboxylic acid-containing monomers is undesirable. CP5 and CP6 have very high viscosities because their Tg is very high.

Claims (19)

(A) A (meth) acrylate copolymer having a Tg of 0 ° C. or less, and as a comonomer,
i) Formula (I)

At least one (meth) acrylate of: wherein R ¹ is H or CH ₃ and R ² is a C _{1 to} C ₂₀ hydrocarbyl, and ii) based on the total weight of the copolymer (A) 0.70 to 8.6% by weight of at least one carboxylic acid containing comonomer,
(Meth) acrylate copolymers, wherein the combination of comonomers (i) and (ii) represents at least 80% by weight of the monomers present in the copolymer (A),
(B) A binder for antifouling coating, comprising a cyclic monocarboxylic acid such as rosin or a derivative thereof (eg, a salt thereof).   The binder according to claim 1, wherein (B) is a rosin or rosin derivative selected from partially or fully hydrogenated rosin, rosin acid, or metal rosin acid salt, or a combination thereof. In the formula (I), ^{R 2} is C1~C8 alkyl substituents, preferably methyl, ethyl, n- propyl, 2-ethylhexyl or n- butyl, Binder according to claim 1 or 2.   Formula (I) represents at least one of methyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and n-butyl methacrylate, preferably methyl methacrylate, and n-butyl acrylate, 2-ethylhexyl, and n-butyl methacrylate The binder as described in any one of Claims 1-3.   The copolymer (A) is 0.8 to 8.6% by weight, preferably 1.0 to 7.56% by weight, of a carboxylic acid-containing comonomer, based on the total weight of the copolymer (A), more preferably 1.2 to 5. The binder according to any one of the preceding claims, comprising 7.0 wt%, more preferably 1.3 to 6.5 wt%, more preferably 1.4 to 6.0 wt%.   The binder according to any one of the preceding claims, wherein the carboxylic acid containing comonomer is selected from methacrylic acid or acrylic acid, or a combination thereof.   The copolymer (A) has a Tg of 0 ° C. or less, preferably 0 to −60 ° C., such as −5 to −55 ° C., preferably −10 to −50 ° C., in particular −15 to −45 ° C. The binder as described in any one of -6.   The binder according to any one of the preceding claims, wherein the copolymer (A) has a Mw of 50,000 or less.   The binder according to any one of the preceding claims, wherein the copolymer (A) and the component (B) are present in a weight ratio of 1: 1 to 1:30, preferably 1: 1 to 1:10.   10 to 50% by weight, preferably 15 to 30% by weight (dry solids) of component (A), and 10 to 70% by weight, preferably 20 to 50% by weight (dry solids) of component (B) The binder as described in any one of Claims 1-9. C) Hydrolyzable (meth) acrylate copolymers comprising hydrolyzable silyl containing monomers such as silyl containing (meth) acrylates, such as triisopropylsilyl acrylate or triisopropylsilyl methacrylate,
The binder according to any one of claims 1 to 10, further comprising at least one copolymer selected from and / or D) non-hydrolyzable (meth) acrylate copolymers.   The binder according to any one of the preceding claims, wherein the copolymer (A) has an acid number of 8.0 to 50 mg KOH / g of polymer.   An antifouling coating composition comprising the binder according to claim 1.   14. A composition according to claim 13, comprising 0.5 to 25 wt%, preferably 1 to 22 wt%, preferably 2 to 20 wt%, preferably 5 to 18 wt% (dry solids) of component (A). Antifouling coating composition.   The antifouling coating according to any of claims 13 to 14, further comprising an antifouling agent, preferably wherein said antifouling agent comprises cuprous oxide and / or copper pyrithione, and / or zinc ethylene bis (dithiocarbamate). .   The antifouling coating composition according to any one of claims 13 to 15, wherein the binder components (A) to (D) contain 20 to 70% by weight (dry solids) of the antifouling coating composition. .   17. A conical plate viscosity according to claim 13 having a cone and plate viscosity at 23 ° C in the range of 100 to 980 cP, preferably 150 to 950 cP, more preferably 200 to 900 cP when measured according to ISO 2884-1: 1999. Antifouling coating composition.   Process for protecting an object from fouling, wherein at least a part of said object being tainted is coated with the antifouling coating composition according to any one of claims 13 to 17. Process, including. An object coated with the antifouling coating composition according to any one of claims 13 to 17.