JP2019090020A - Antifouling composition - Google Patents

Abstract

To provide a binder for antifouling coating composition including a silyl group-containing acrylic resin.SOLUTION: The binder for antifouling coating includes (i) a hydrophilic copolymer that has a glass transition temperature of at least 0°C and includes at least 10 wt.% of two kinds of (meth)acrylate monomers and less than 15 wt.% of a comonomer other than the monomer, (ii) a cyclic monocarboxylic acid such as rosin and the derivative thereof, and (iii) a silyl ester copolymer including at least 15 wt.% of a silyl ester monomer.SELECTED DRAWING: None

Description

  The present invention relates to binders for marine antifouling coating compositions, more particularly comprising a three-component binder based on hydrophilic (meth) acrylate copolymers, cyclic monocarboxylic acids and silyl esters or (meth) acrylic polymers Marine antifouling coating composition. The present invention further relates to a method of protecting an object from fouling and to an object coated with the antifouling composition of the present invention.

  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. Motility can also be reduced.

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

  The most successful self-polishing antifouling systems currently marketed are based on silyl ester functional (meth) acrylic copolymers. Silyl ester functional (meth) acrylic copolymers are often used in conjunction with other binders such as acrylates and rosins or rosin derivatives to tailor the self-polishing and mechanical properties of the antifouling coating film.

  Marine antifouling paints are designed to work in seawater, but it is also important that these coatings work in fresh water. In particular, it is important that the coating does not receive excessive water absorption in fresh water.

  It is not immediately clear why freshwater absorption is important for coating on ships operated at sea. However, many vessels trade in freshwater for a period of time. For example, the Panama Canal contains freshwater. There are also many new structures in the freshwater river in China. In these cases, excessive water absorption can lead to excessive swelling and, in the worst case, breakage of the coating.

  The ability to resist water absorption in freshwater is also an important indicator for operation in seawater. It is a good indicator that the coating has long term stability. In seawater, the coating absorbs water, but its low osmotic pressure reduces its speed and reduces its volume. Excessive water absorption in fresh water indicates that in the long run, water absorption in seawater will increase.

  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.

  The inventors have found that the use of specific binders in antifouling paints surprisingly reduces the absorption of water in fresh water. The binder is comprised of three components, a hydrophilic (meth) acrylate copolymer comprising certain hydrophilic monomers, a cyclic monocarboxylic acid component and an acrylic / silyl ester copolymer component. When the binder is used together in the antifouling coating composition, the binder reduces the amount of water absorbed by the film. Therefore, the antifouling coating containing the binder of the present invention extends the use interval for a long time.

  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 comprising a blend of the three binder components required in the present invention.

  In EP 2 128 208, antifouling coating compositions are prepared which comprise a silyl ester copolymer, a rosin component and a plastic resin of very low glass transition temperature. As established in the examples, when the hydrophilic (meth) acrylate polymer has a low Tg, high water absorption is a problem with binders.

  In WO 3070832, copolymer A (a silyl copolymer), polymer B (which is incompatible with copolymer A and may contain hydrophilic comonomers) and optionally polymer C (in many cases) Coating compositions which are non-hydrophobic copolymers). None of the paint examples use cyclic monocarboxylic acids. The use of such acids and the like is advantageous as it allows the viscosity of the coating composition to be reduced, and thus a coating composition having a lower VOC can be produced.

  WO 2014175246 describes an antifouling coating composition comprising a binder based on styrene and a copolymer based on glycidyl (meth) acrylate, a silyl ester copolymer. Although rosin is used in Example 15, the copolymer (i) required in the present invention is not disclosed because of the presence of a large amount of excess styrene. Among them the copolymer, eg A-13, has a Tg much lower than 0 ° C.

  WO 97/44401 describes the use of rosin or rosin equivalents, fibers and polymeric softeners in antifouling coating compositions. There are no paint examples that contain two types of (meth) acrylic copolymers.

  EP 1 288 234 describes film-forming polymers prepared from binders with low hydrolyzable monomer content. The only hydrophilic comonomers exemplified are vinyl pyrrolidone and methacrylic acid, and no examples based on combinations of acrylic copolymers exist.

  WO 2005/005516 describes silyl ester copolymers with low Mw and their use in antifouling coatings. Example 7 describes a coating composition comprising an unidentified silyl ester copolymer, rosin and a binder based on Degaran LP 64/12 (non-hydrophilic BMA / MMA copolymer). None of the silyl copolymers disclosed have a hydrophilic monomer content of more than 10% by weight, ie the hydrophilic binder component of the present invention is not present.

  WO 2011/131721 describes coating compositions (e.g. desiccants) which are produced by adding the different components in a specific order. In the examples, rosin is used with Neocryl B 725 (non-hydrophilic BMA / MMA copolymer) and Polyace NSP-100 (silyl acrylate). Hydrophilic comonomers have not been used for Neocryl B 725.

  WO 2014/175140 describes silyl copolymers with specific end groups.

  EP 3078715 is directed to an antifouling coating composition comprising a silyl ester copolymer, tralopyryl and a stabilizer. In the examples, triisopropylsilyl methacrylate copolymer, gum rosin and acrylic polymers are used. The polymer properties of the monomer composition or the acrylic copolymer are not specified.

  WO 2009/149919 is directed to the use of caprolactone modified comonomers in silyl copolymers. No additional acrylic polymer is used.

  In EP 2489 710, the antifouling coating is illustrated and two acrylic acid copolymers T3 and T4 are illustrated. They are combined with rosin and vinyl chloride-isobutyl vinyl ether copolymer).

  In EP 21 61 316 and related U.S. Patent Publication No. 2011/0166253, the binder is based on a rosin component and a silyl ester component, i.e. the third binder component of the present invention is not present.

European Patent No. 2128208 WO 3070832 International Publication No. 2014175246 WO 97/44401 European Patent No. 1288234 WO 2005/005516 International Publication No. 2011/131721 International Publication No. 2014/175140 European Patent No. 3078715 International Publication No. 2009/149919 European Patent No. 2489710 European Patent No. 2161316

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

In a first aspect, the present invention is a binder for an antifouling coating composition,
(I) at least one formula (I) having a glass transition temperature of at least 0 ° C.

Wherein R ¹ is H or CH ₃ and R ² is a C ₃ to C 18 substituent having at least one oxygen or nitrogen atom, preferably at least one oxygen atom, or R ² is At least 10% by weight of monomers of poly (alkylene glycol) chains),
And at least one formula (II)

Comprising a monomer of formula wherein R ^{1 ′} is H or CH ₃ and R ^{2 ′} is a C _{1 to} C ₂₀ hydrocarbyl,
Hydrophilic copolymers comprising less than 15% by weight of comonomers other than those of formula (I) or (II),
(Ii) cyclic monocarboxylic acids such as rosin or a derivative thereof (eg, a salt thereof);
(Iii) Silyl ester monomers and / or non-hydrophilic (meth) acrylic polymers comprising less than 10% by weight of monomers according to formula (I), preferably less than 5% by weight, most preferably 0% by weight of monomers of formula (I) And at least 15% by weight of the silyl ester copolymer.

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

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

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

  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. "Binder" comprises polymer components (i) and (iii) together with a cyclic monocarboxylic acid (ii).

  The term non-hydrophilic (meth) acrylic polymer comprises at least one (meth) acrylic acid monomer or at least one (meth) acrylate monomer (or potentially both) but the monomers according to formula (I) A polymer is defined which comprises less than wt%, preferably less than 5 wt%, most preferably 0 wt% of the monomer of formula (I). If less than 10% by weight of monomers of formula (I) are present, this is considered to be non-hydrophilic.

  Where a weight percent of a given monomer is given, the weight percent is relative to the total (weight) of each monomer present in the copolymer. Thus, if 2-methoxyethyl acrylate (MEA) and methyl methacrylate (MMA) are the only monomers in copolymer component (i), then the weight percent of MEA is (MEA (weight) / (MEA (weight) + MMA (weight) ))) Calculated as 100%.

  The present invention relates to a binder for marine antifouling coatings with extremely low water absorption in fresh water. Thus, these compositions have a long service life. The antifouling coating composition of the present invention comprises a binder containing at least three components.

Copolymer component (i)
The present invention requires the use of certain hydrophilic (meth) acrylate-based copolymers. The term hydrophilicity is used herein to mean the presence of at least 10% by weight of at least one monomer of formula (I). Thus, the copolymer component (i) comprises at least one formula (I):

(Wherein R ¹ is H or CH ₃ and R ² is a C ₃ to C 18 substituent containing at least one oxygen or nitrogen atom, preferably at least one oxygen atom, or R ² is a poly (Indicating an alkylene glycol) group). As used herein, this structure defines a hydrophilic (meth) acrylate monomer.

As shown in the above formula, the term "hydrophilic (meth) acrylate" means that the R ² group of formula (I) contains at least one oxygen or nitrogen atom, preferably at least one oxygen atom. I need. Additional non-hydrophilic (meth) acrylate monomers are also present in component (i) of the binder as monomers of formula (II), as described in detail below, wherein R ^{2 ′} units are It consists only of C atoms and H atoms.

In one embodiment, binder copolymer composition (i) comprises at least one polymer of formula (I) as described above wherein the R ² group is a formula (CH ₂ CH ₂ O) _n -R ^{3 wherein} R ³ is a C1-C10 hydrocarbyl substituent, preferably a C1-C10 alkyl, or a C6-C10 aryl substituent, and n is an integer in the range of 1-5, preferably 1-3).

Preferably, R ² is of the formula (CH ₂ CH ₂ O) n -R ^{3 wherein} R ³ is a C 1 to C 10 alkyl substituent, preferably CH ₃ or CH ₂ CH ₃ and n is 1 to 3 , Preferably 1 or 2.). Such monomers include 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-butoxyethyl acrylate, 2- (2-methoxyethoxy) ethyl acrylate, 2- (2-ethoxyethoxy) ethyl acrylate, 2- (2) -Butoxyethoxy) ethyl acrylate, 2- [2- (2-methoxyethoxy) ethoxy] ethyl acrylate, 2- [2- (2-ethoxyethoxy) ethoxy] ethyl acrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate , 2-butoxyethyl methacrylate, 2- (2-methoxyethoxy) ethyl methacrylate, 2- (2-ethoxyethoxy) ethyl methacrylate, 2- (2-butoxyethoxy) ethyl methacrylate, 2- [2- (2-methoxy) Butoxy) ethoxy] ethyl methacrylate, it may be 2- [2- (2-ethoxyethoxy) ethoxy] ethyl methacrylate.

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

In another embodiment, copolymer component (i) comprises at least one monomer of formula (I) above, wherein the R ² group is a poly (alkylene glycol) group, such as a poly (ethylene glycol) group. Such groups are of the formula _{(CH 2 CH 2 O) m} -R 13 or _{(CH 2 CH (CH 3)} O) m -R 13 may have a ^{(wherein, R 13} is C1~C10 hydrocarbyl substituent And is preferably a C1-C10 alkyl or C6-C10 aryl substituent, m is an integer ranging from 5 to 100, preferably 5 to 20). Such monomers may be poly (ethylene glycol) methyl ether acrylate, poly (ethylene glycol) ethyl ether acrylate, poly (ethylene glycol) methyl ether methacrylate, poly (ethylene glycol) ethyl ether methacrylate. Such a monomer preferably has a number average molecular weight (Mn) of 300 to 4000, more preferably 300 to 1000.

In one embodiment, at least one monomer of the above formula (I), wherein the copolymer component (i) is a saturated cyclic group wherein the R ² group comprises at least one oxygen or nitrogen atom, preferably at least one oxygen atom including. More preferably, R ² 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 (I) are tetrahydrofurfuryl acrylate (THFA) and tetrahydrofurfuryl methacrylate (THFMA).

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

  The monomers of formula (I) preferably form at least 15% by weight of the copolymer (i). A particularly preferred amount of hydrophilic (meth) acrylate monomer of formula (I) in binder component (i) is 15 to 65% by weight, preferably 18 to 62% by weight, for example 20 to 50% by weight. If mixtures of monomers of the formula (I) are present, these amounts relate to the total weight proportion of the monomers of the formula (I) in the copolymer.

  The comonomers of the formula (I) 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).

Non-hydrophilic (meth) acrylate monomer (s)
The copolymer component (i) according to the invention also comprises one or more compounds of the formula (II)

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

  In all embodiments of the invention, the copolymer component (i) comprises at least one non-hydrophilic methacrylate and / or non-hydrophilic acrylate monomer (II) together with at least one monomer of the formula (I). The monomers of formula (II) are preferably in the range of at most 85% by weight of component (i), preferably 35 to 85% by weight, for example 38 to 82% by weight, for example 40 to 80% by weight. When mixtures of monomers of formula (II) are present, these preferred amounts relate to the total weight fraction of monomers of formula (II) in the copolymer.

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

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

  Preferred choices of monomers of formula (II) are: methyl methacrylate (MMA), n-butyl acrylate (n-BA), n-butyl methacrylate (n-BMA), 2-ethylhexyl acrylate (2-EHA) or 2- Ethyl hexyl methacrylate (2-EHMA) is mentioned. In all embodiments of the invention it is preferred that methyl methacrylate (MMA) or n-butyl acrylate (n-BA) is included in the copolymer component (i).

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

  Copolymer component (i) contains less than 15% by weight of any monomer other than the monomers of formulas (I) and (II) above. Thus, copolymer component (i) is less than 15% by weight of any silyl ester monomer of formula (III) defined below, preferably less than 10% by weight of any silyl ester monomer of formula (III) defined below It is required to contain In some embodiments, component (i) can be composed of monomers of formulas (I) and (II) only.

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

  Copolymer component (i) preferably does not contain any metal ion-containing comonomers.

In a preferred embodiment, the hydrophilic copolymer (i) is
(I) at least one type of formula (I)

Wherein R ¹ is H or CH ₃ and R ² is a C ₃ to C 18 substituent having at least one oxygen or nitrogen atom, preferably at least one oxygen atom, or R ² is 15 to 65% by weight of monomers of poly (alkylene glycol) chain),
At least one type of formula (II)

35 to 85% by weight of monomers of the formula in which R ^{1 ′} is H or CH ₃ and R ^{2 ′} is a C _{1 to} C ₂₀ hydrocarbyl,
It also contains less than 15% by weight of comonomers other than those of formula (I) or (II).

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

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

  The copolymer component (i) preferably has a glass transition temperature (Tg) of at least 0 ° C. The copolymer preferably has a glass transition temperature (Tg) of at least 5 ° C., preferably at least 10 ° C., for example at least 15 ° C., all values being measured according to the Tg test described in the example section. Values of less than 80 ° C., such as less than 75 ° C., for example less than 50 ° C., are preferred. While not wishing to be limited by theory, it is believed that the higher Tg contributes to the decrease in water absorption observed in the examples. If the Tg is less than 0 ° C., the water absorption will be higher.

  The copolymer component (i) is preferably not partially or completely compatible with the blend of the other binder components. Not compatible means that the binder components are not compatible according to the test method described in the section of the following examples.

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

  The final antifouling coating composition according to the invention comprises 0.5 to 45% by weight (dry solids), for example 1.0 to 30% by weight, in particular 5.0 to 25% by weight of copolymer component (i) preferable.

  The antifouling coating composition of the invention may optionally comprise a mixture of copolymer components (i) of the invention.

Polymer component (iii)
The binder of the present invention further comprises a polymer component (iii). This component is different from component (i). Component (iii) is based on non-hydrophilic (meth) acrylic acid polymers, non-hydrophilic (meth) acrylate polymers (iii-2) or silyl ester copolymers (iii-1) comprising at least 15% by weight of silyl ester monomers It may be Component (iii) may be a non-hydrophilic (meth) acrylic polymer (referred to herein as (iii-2)). Component (iii) may be a mixture of copolymer (iii-1) and polymer (iii-2). Thus, component (iii) is different from component (i).

Silyl ester comonomer component (iii-1)
Component (iii-1) comprises at least one silyl (meth) acrylate monomer. The silyl (meth) acrylate monomers which are suitable for use in component (iii) are preferably of the formula (III)

(In the formula,
R ⁴ is H or CH ₃ ;
R ⁵ is each independently selected from a linear or branched C _1-4 alkyl group,
R ⁶ 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 ⁷ ) ₃ group Each independently selected from the group
Each R ⁷ 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 (III) where p is zero.

  More preferably, the silyl ester monomer is of the formula (IV)

(Wherein, R ⁴ is H or CH ₃ ,
R ⁶ 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 (III),
For example, tri-n-propylsilyl (meth) acrylate, triisopropylsilyl (meth) acrylate, tri-n-butylsilyl (meth) acrylate, triisobutylsilyl (meth) acrylate, tert-butyldimethylsilyl (meth) acrylate, thexyl Dimethylsilyl (meth) acrylate, tert-butyldiphenylsilyl (meth) acrylate, nonamethyltetrasiloxanyl (meth) acrylate, bis (trimethylsiloxy) methylsilyl (meth) acrylate, tris (trimethylsiloxy) silyl (meth) acrylate, etc. And silyl ester monomers of acrylic acid and methacrylic acid.

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

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

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

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

  The silyl ester comonomer preferably comprises at least a triisopropylsilyl (meth) acrylate monomer, a monomer of formula (I) and a monomer of formula (II). The preferred options of the above formulas (I) and (II) apply independently to the embodiment of component (iii). Preferred choices of monomers of formula (II) are: methyl methacrylate (MMA), n-butyl acrylate (n-BA), n-butyl methacrylate (n-BMA), 2-ethylhexyl acrylate (2-EHA) or 2- Ethyl hexyl methacrylate (2-EHMA) is mentioned. In all embodiments of the invention it is preferred that methyl methacrylate (MMA) or butyl acrylate (n-BA) is included in the copolymer component (iii).

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

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

  The silyl ester copolymer preferably has a glass transition temperature (Tg) of at least 15.degree. C., preferably at least 20.degree. C., for example at least 25.degree. C., all values being determined according to the Tg test described in the example section. Be done. Values of less than 80 ° C., such as less than 75 ° C., for example less than 50 ° C., are preferred.

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

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

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

(Meth) acrylic polymer component (iii-2)
Alternatively or additionally, component (iii) is non-hydrophilic (including at least one (meth) acrylic acid monomer or at least one (meth) acrylate monomer (or both), such as those of formula (II) Contains meta) acrylic polymers. Component (iii-2) may be a homopolymer or a copolymer, preferably a copolymer. In particular, when a (meth) acrylic acid monomer is present, it is preferred to form a copolymer when a second monomer is present. The second monomer in this embodiment is preferably a monomer of formula (II) as defined herein.

  The non-hydrophilic (meth) acrylic polymer comprises less than 10% by weight of any monomer of formula (I) and preferably does not contain any monomer of formula (I). The non-hydrophilic (meth) acrylic polymer is also preferably free of any silyl ester monomers.

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

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

  The content of (meth) acrylic acid in the copolymer component (iii-2) is preferably in the range of 0.5 to 10% by weight. The monomers of formula (II) preferably form at least 50% by weight, for example at least 75% by weight, in particular 90 to 99.5% by weight of the (meth) acrylic acid copolymer.

  Alternatively, the non-hydrophilic (meth) acrylic polymer component (iii-2) can comprise one or more monomers of the formula (II). Thus, in one embodiment, the non-hydrophilic (meth) acrylic polymer component (iii-2) is a (meth) acrylate homopolymer, such as, for example, a monomer of formula (II).

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

  In all embodiments of the invention it is preferred that methyl methacrylate (MMA) or n-butyl acrylate (n-BA) is included in the copolymer component (iii-2).

  The (meth) acrylic polymer component (iii-2) preferably has a glass transition temperature (Tg) of less than 0 ° C., preferably less than −20 ° C., for example less than −22 ° C., all values being in accordance with the examples Measured according to the Tg test described in Values above -60 ° C., for example above 50 ° C., are preferred.

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

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

  The binder composition according to the invention preferably comprises 0.5 to 25% by weight (dry solids), for example 1.0 to 22% by weight, of (meth) acrylic polymer component (iii-2), if present. In particular, 2.0 to 18% by weight is included.

  Generally, the amount of component (iii) in the binder (total amount of (iii-1) + (iii-2)) is preferably 5 to 70 wt%, preferably 10 to 60 wt%, preferably 10 to 50 % By weight, in particular 15 to 50% by weight (dry solids).

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

  The antifouling coating composition according to the invention preferably comprises at least 0.5% by weight, for example at least 1% by weight, of component (iii) (dry solids). The upper limit of component (iii) may be 20% by weight, for example 15% by weight.

Preparation of Copolymer Component (i) and Polymer Component (iii) The polymer 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. Copolymer component (i) or (iii) is preferably a random copolymer.

Cyclic monocarboxylic acid component (ii)
The binder of the present invention comprises at least one cyclic monocarboxylic acid. 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 amount of component (ii) in the binder is preferably in the range 10 to 70 wt% (dry solids), preferably 20 to 50 wt%.

  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 such as magnesium resinate and the like; and metal salts of rosin derivatives; 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 20% by weight (dry solids), preferably 3 to 15% by weight (dry solids) of a cyclic monocarboxylic acid substance. It is preferable to include.

Thus, in one embodiment of the binder according to the invention, the amount of component (i) is in the range of 20 to 60% by weight of the binder (dry solids),
The amount of component (ii) is in the range of 10 to 70% by weight (dry solids) of the binder,
The amount of component (iii) is in the range of 10 to 60% by weight (dry solids).

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

Other Binder Components In addition to components (i)-(iii) above, additional binder components can be used to adjust the properties of the antifouling coating film. Examples of binders that can be used 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;
Dimerized rosin and polymerized 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 comprises a liquid C12-C24 monocarboxylic acid or a salt thereof, ie an acid containing a single -COOH moiety in the molecule, or a salt thereof Can. 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 parts by weight or less of a linear C18 acid (such as n-stearic acid, n-oleic acid or n-linoleic acid) And the rest are branched C18 acids (generally, "isostearic acid", "isooleic acid", "isolinoleic acid") and the like.

  In a preferred embodiment, the acid is a non-cyclic C14-C20 monocarboxylic acid, preferably a non-cyclic C16-C20 monocarboxylic acid, in particular a non-cyclic 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.

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

  In a preferred embodiment of the binder, the weight ratio (dry solids) of copolymer (i): component (ii) is 20:80 to 80:20, preferably 30:70 to 70:30, more preferably 40:60. To 60:40.

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

  In one embodiment, the components of the binder (i) (determination of the incompatibility of the hydrophilic copolymer in the binder mixture of components (i), (ii) and (iii)) as determined by the method of the experimental section ) Are partially or completely incompatible, ie, do not form a homogeneous mixture with the other binder components present.

  The binder composition of the present invention is ideally incorporated into the antifouling coating composition. The antifouling coating composition of the present invention may comprise 15 to 50% by weight of binder, and in particular the antifouling coating composition of the present invention comprises the binder components (i) to (iii) 15 to 15 according to claim 1. Contains 50% by weight.

Biocides The antifouling coating preferably further comprises a compound capable of preventing marine fouling of the surface or removing marine fouling from 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 biocides, 4- [1- (2,3-dimethylphenyl) ethyl] -1H-imidazole [medetomidine] and 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) A series of organic biocides such as 1H-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 present invention may optionally contain, in addition to the binder and any of the above mentioned components, other binders, inorganic or organic pigments, extenders and fillers, additives, solvents, and thinners. Can further comprise one or more components selected from

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 A and mixtures of any of two or more solvents and thinners; le, 1-methoxy-2-propanol and ether alcohols such as; d-cyclic terpenes, such as limonene, 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).

Other Additives Examples of other additives which can be added to the antifouling coating composition are reinforcing agents, thixotropy agents, thickening agents, 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 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, a 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.
Materials and methods

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

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. The sample was prepared by drawing down on a glass panel using an applicator with a gap size of 100 μm. The glass panels were dried in a ventilated heating cabinet for 24 hours at 23 ° C., 24 hours at 50 ° C. Approximately 10 mg of dried polymeric material was collected from the glass panel and transferred to a covered aluminum pan. The measurement was performed by heating-cooling-heating procedure (-80 C to 120 C) at a heating rate of 10 C / min and a cooling rate of 10 C / min. Use empty bread as a reference. 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.

Measurement of paint viscosity using a cone and plate viscometer The viscosity of the antifouling paint composition is in accordance with ISO 2884-1: 1999, using a digital cone and plate viscometer at a temperature of 23 ° C., at a shear rate of 10000 s ⁻¹ It turned on and obtained the viscosity measurement range 0-10P. Results are shown as the average of 3 measurements.
The results are shown in Tables 8-13.

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. At the time of reading, the panel and the paint 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 8-13.

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.
Determination of the Incompatibility of the Hydrophilic Copolymer (i) in the Binder Mixture of Components (i), (ii) and (iii) A Mixture of Binder Components (i), (ii), (iii) and Irgazin Red L 3670 HD Were mixed in a 10 ml glass vial. The ratios are shown in Tables 3-7. The vials were mixed for 3 minutes using a Collomix Viba vibratory shaker. After the samples were left at room temperature for at least 24 hours, the incompatibility was assessed visually. Copolymer (i) is considered to be incompatible if at least two different phases are found. Phase separation was made more visually apparent by adding Irgazin Red L 3670 HD. The results are shown as incompatible (I) or compatible (C) in Tables 3-7. The binder mixture should have a solids content of 52-57% by weight. Xylene: PM shall be used in a weight ratio of 85:15 to 95: 5.

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.

General Preparation Procedure for Copolymer Solutions P1-P12 and C1-C8 (Copolymer Component (i)) All polymers tested were placed in a temperature controlled reaction vessel equipped with a stirrer, reflux condenser, nitrogen inlet and feed port, xylene Manufactured in the same manner by charging 28.84 parts and PM 6.75 parts. The reaction vessel was heated and maintained at 95 ° C. A premix of monomers, 6.57 parts xylene, 3.25 parts PM 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 an additional hour of reaction, the initiator boost initiator solution and a post-addition of 4.6 parts of xylene were charged into 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. As an exception to this, polymers P4 and P6 had reaction temperatures of 105 ° C. and 85 ° C., respectively.
A summary of the different polymers synthesized is given in Tables 1 and 2. The amounts of constituents are given in parts by weight.

Preparation of Acrylic Copolymer Solution A-1 (Polymer Component (iii-2)) In a temperature-controlled reaction vessel equipped with a stirrer, reflux condenser, nitrogen inlet and inlet, 19.20 parts of xylene and 1-methoxy-2- 7.70 parts of propanol were added. The reaction vessel was heated and maintained at 85 ° C. 53.80 parts of n-butyl acrylate, 3.40 parts of n-butyl methacrylate, 2.40 parts of methyl methacrylate, 0.40 parts of methacrylic acid, 0.93 parts of 2,2'-azobis (2-methylbutyronitrile) A premix of 8.00 parts of and xylene was prepared and charged to the reaction vessel at a constant rate over 2 hours and 30 minutes under nitrogen atmosphere. After reacting for an additional hour, the post addition of 0.20 parts of 2,2'-azobis (2-methylbutyronitrile) and 4.00 parts of xylene is reacted at a constant rate over 15 minutes I put it in a container. The reaction vessel was maintained at reaction temperature for an additional hour and then cooled to room temperature. The amounts of constituents are given in parts by weight.

  Comonomer solution A-1 had a viscosity of 327 cP, a non-volatile content of 61.7 wt%, Mw 36200, PDI 3.23 and Tg-39 ° C.

Preparation of silyl ester acrylic copolymer solution A-2 (polymer component (iii-1)) 35.00 parts of xylene was placed in a temperature controlled reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet and a feed port. The reaction vessel was heated and maintained at 85 ° C. 16.50 parts of methyl methacrylate, 3.50 parts of 2-methoxyethyl acrylate, 30.00 parts of triisopropylsilyl acrylate, 0.50 parts of 2,2'-azobis (2-methylbutyronitrile) and 5.00 parts of xylene The premix was prepared and charged to the reaction vessel at a constant rate over 2 hours under a nitrogen atmosphere. After reacting for an additional hour, the post addition of 0.10 parts of 2,2'-azobis (2-methylbutyronitrile) and 5.00 parts of xylene is reacted at a constant rate over 15 minutes I put it in a container. The reaction vessel was maintained at reaction temperature for a further 2 hours. The temperature of the reaction vessel was raised to 120 ° C. and maintained for 30 minutes, then cooled to room temperature. The amounts of constituents are given in parts by weight.

  Copolymer solution A-2 had a viscosity of 152 cP, a non-volatile content of 50.5 wt%, a Mw of 28000, a PDI of 3.61 and a Tg of 35 ° C.

Preparation of silyl ester acrylic copolymer solution A-3 (polymer component (iii-1)) 35.50 parts of xylene was placed in a temperature controlled reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet and a feed port. The reaction vessel was heated and maintained at 85 ° C. 11.83 parts of methyl methacrylate, 2.96 parts of n-butyl acrylate, 11.83 parts of tetrahydrofurfuryl acrylate, 32.54 parts of triisopropylsilyl methacrylate and 2,2'-azobis (2-methylbutyronitrile) 0. 71 parts of the premix were prepared and charged into the reaction vessel at a constant rate for 2 hours under nitrogen atmosphere. After an additional 0.5 hours of reaction, a post initiator addition of 0.12 parts of 2,2'-azobis (2-methylbutyronitrile) and 4.50 parts of xylene, at a constant rate over 20 minutes In the reaction vessel. The reaction vessel was maintained at reaction temperature for a further 2 hours. The temperature of the reaction vessel was raised to 110 ° C. and maintained for 30 minutes, then cooled to room temperature. The amounts of constituents are given in parts by weight.

  Copolymer solution A-3 had a viscosity of 1275 cP, a non-volatile content of 60.2 wt%, a Mw of 31000, a PDI of 3.10 and a Tg of 46 ° C.

General Procedure for the Preparation of Antifouling Coating Compositions The components were mixed in the proportions shown in Tables 8-13. 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 before testing.

  The combination of binder component (i), component (ii) and component (iii) is necessary to fine-tune the hydrophilic / hydrophobic balance of the coating. This balance affects coating properties such as water absorption, polishing rate, crack resistance and paint viscosity. If the hydrophilic monomer is very low (see Comparative Example C8), the polishing is slow. If only component (i) + (ii) is used in the binder (see comparative example CP19), the water absorption is high.

Claims (20)

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

(Wherein, R ¹ is H or CH ₃ , R ² is a C ₃ to C 18 substituent having at least one oxygen or nitrogen atom, preferably at least one oxygen atom, or R ² is a poly A monomer of (alkylene glycol) chain,
And at least one formula (II)

Comprising a monomer of formula wherein R ^{1 ′} is H or CH ₃ and R ^{2 ′} is a C _{1 to} C ₂₀ hydrocarbyl,
Said hydrophilic copolymer comprising less than 15% by weight of comonomers other than those of formula (I) or (II)
(Ii) cyclic monocarboxylic acids such as rosin or a derivative thereof (eg, a salt thereof);
(Iii) A binder comprising a silyl ester copolymer comprising at least 15% by weight of silyl ester monomers and / or a non-hydrophilic (meth) acrylic polymer comprising less than 10% by weight of monomers of formula (I).   The binder according to claim 1, wherein component (iii) comprises a silyl ester copolymer and the monomer is triisopropylsilyl methacrylate (TISMA) or triisopropylsilyl acrylate (TISA). The hydrophilic copolymer (i) is
(A) at least one formula (I)

(Wherein R ¹ is H or CH ₃ , R ² is a C ₃ -C 18 substituent having at least one oxygen or nitrogen atom, preferably at least one oxygen atom, or R ² is poly ( 15 to 65% by weight of the monomer (which is an alkylene glycol) chain)
(B) at least one formula (II)

85 to 35% by weight of monomers of the formula in which R ^{1 ′} is H or CH ₃ and R ^{2 ′} is a C _{1 to} C ₈ hydrocarbyl;
The binder according to any of the preceding claims, wherein the hydrophilic copolymer (i) comprises less than 15% by weight of comonomers other than those of formula (I) or (II).   4. A binder according to any of the preceding claims, wherein the amount of component (ii) is in the range 10 to 70 wt% of the binder (dry solids).   Binder according to any of the preceding claims, wherein component (ii) is rosin or a derivative thereof such as a salt thereof. R ² is a group of the formula (CH ₂ CH ₂ O) _n -R ³ (wherein R ³ is a C1-C10 alkyl or a C6-C10 aryl substituent, and n is an integer in the range of 1 to 6) The binder according to any one of claims 1 to 5, which is a group of   The binder according to any of the preceding claims, wherein the amount of component (i) is in the range of 20-60% by weight of the binder (dry solids).   Said monomers of formula (I) are 2-methoxyethyl methacrylate (MEMA), 2-methoxyethyl acrylate (MEA), 2-ethoxyethyl methacrylate (EEMA), 2- (2-ethoxyethoxy) ethyl acrylate (EDEGA), And the binder according to any of the preceding claims, which is tetrahydrofurfuryl acrylate (THFA).   Any of the foregoing, wherein said monomer of formula (II) is methyl methacrylate (MMA), n-butyl methacrylate (n-BMA), 2-ethylhexyl acrylate (2-EHA) and n-butyl acrylate (n-BA) Binder according to any of the claims.   10. A silyl ester copolymer (iii) comprising at least 15 wt% of silyl ester monomers and a non-hydrophilic (meth) acrylic polymer comprising less than 10 wt% of monomers of formula (I) Described binder.   11. Binder according to any of the preceding claims comprising a non-hydrophilic (meth) acrylic acid copolymer (iii-2) comprising less than 10% by weight of monomers of formula (I).   A binder according to any of the preceding claims comprising 10 to 60 wt% of component (iii) (dry solids).   The binder according to any one of claims 1 to 10, wherein Tg of the non-hydrophilic (meth) acrylic polymer (iii-2) is less than 0 ° C.   An antifouling coating composition comprising the binder according to any one of claims 1 to 13 and at least one antifouling agent.   The antifouling coating composition according to claim 14, wherein the antifouling agent comprises cuprous oxide and / or copper pyrithione and / or zinc ethylene bis (dithiocarbamate).   16. The antifouling coating composition according to claim 14 or 15, wherein the binder comprises 15 to 50% by weight of the antifouling coating composition.   Process for protecting an object from fouling, comprising coating at least a part of said object that is tainted with the antifouling coating composition according to any of the claims 14-16. ,process.   An object coated with the antifouling coating composition according to any one of claims 14 to 16.   The object of claim 17, wherein the object is coated with an anticorrosion coating layer, a tie layer, and the antifouling coating composition of claims 14-16.   The object according to claim 18, wherein the object is coated with the antifouling coating composition according to claims 14 to 16 covering an existing antifouling coating composition on a substrate.