KR20230050293A - Antifouling Composition - Google Patents

Abstract

The present invention relates to a marine antifouling coating composition, and more specifically to a marine antifouling coating composition comprising ethyl diethylene glycol acrylate (EDEGA) and triisopropylsilyl methacrylate (TISMA) or triisopropylsilyl acrylate (TISA). The present invention also relates to a method of protecting an object from contamination and an object coated with the antifouling coating composition of the present invention.

Description

Antifouling composition {Antifouling Composition}

The present invention relates to a marine antifouling coating composition, and more particularly, to a marine antifouling composition comprising ethyl diethylene glycol acrylate (EDEGA) and triisopropylsilyl methacrylate (TISMA) or triisopropylsilyl acrylate (TISA) It relates to coating compositions. The present invention also relates to a method for protecting an object from contamination and an object coated with the antifouling coating composition of the present invention.

Surfaces immersed in seawater are contaminated by green algae, brown algae, barnacles, mussels, tube worms and similar marine organisms. Such contamination in offshore structures such as ships, crude oil platforms, buoys, etc. is undesirable and results in economic loss. Fouling can lead to biological degradation of the surface, increased loading and accelerated corrosion. Fouling on ships increases frictional resistance, resulting in reduced speed and/or increased fuel consumption. This may reduce steering performance as well.

The risk of contamination is higher if contact of the surface with seawater is maintained for an extended period of time. For example, during rigging, the vessel sits idle for months and the risk of contamination is high. Vessels that are idle for long periods of time or slow vessels in trade are also at high risk of contamination. In order to prevent fouling in this situation, antifouling coatings with high polishing rates are required.

Antifouling paints are used to prevent sedimentation and propagation of marine organisms. These paints usually contain a film-forming binder along with different components such as pigments, fillers, solvents and biologically active materials.

The most successful self-polishing antifouling systems on the market today are based on silyl ester functional (meth)acrylate based copolymers. Examples of such coating compositions are described in EP 0 646 630, EP 0 802 243, EP 1 342 756, EP 1 479 737, EP 1 641 862, WO 00/77102, WO 03/070832 and WO 03/080747 .

Silyl ester functional (meth)acrylate-based copolymers are often used together with acrylates and other binders such as rosin or rosin derivatives to adjust the self-polishing properties and mechanical properties of antifouling coatings. Also fungicides such as copper oxide or 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile[tralopyril](4-bromo-2- Organic fungicides such as (4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile [tralopyril]) may also be included.

Silyl ester copolymers comprising hydrophilic acrylate comonomers have been previously disclosed. EP 0 646 630 discloses antifouling coatings in which the hydrophilic acrylate comonomer comprises 1-25 ethylene glycol repeating units. In one example, ethyl diethylene glycol acrylate (EDEGA) is used in combination with another hydrophilic acrylate comonomer having 9 repeating glycol units, methyl methacrylate and n-butyl acrylate. In this example, the silyl ester comonomer is tri(n-butyl)silyl methacrylate.

WO2014/096102 discloses a silyl ester copolymer with a hydrophilic comonomer, the silyl ester comonomer comprising two non-branching C1/C2 groups and a third group attached to silicon having at least two branches. . Examples of silyl ester comonomers include Thexyldimethylsilyl methacrylate and Thexyldimethylsilyl acrylate. Dexyldimethylsilyl-based monomers are currently not commercially available, making them less suitable as paint binders. In addition, the combination of dexyldimethylsilyl (meth)acrylate and ethyl diethylene glycol acrylate (EDEGA) has lower environmental crack resistance than the combination of triisopropylsilyl (meth)acrylate and ethyl diethylene glycol acrylate (EDEGA). An antifouling coating having properties is provided.

EP 1 016 681 discloses silyl ester copolymers with hydrophilic acrylate or methacrylate comonomers. Most of the exemplified polymers are copolymers of triisopropylsilyl acrylate and methyl methacrylate with a low content of hydrophilic acrylate or methacrylate having a hydroxyl group at the 2, 4 or 6 position. Also exemplified polymers are copolymers of triisopropylsilyl acrylate, methyl methacrylate and polyethylene glycol methacrylate with 5, 12 or 15 repeating polyethylene glycol units.

The inventors of the present invention have surprisingly found that a silyl ester copolymer comprising triisopropylsilyl methacrylate (TISMA) or triisopropylsilyl acrylate (TISA) and ethyl diethylene glycol acrylate (EDEGA) as comonomers has a suitable polishing rate. It was established to provide a self-polishing antifouling system with Furthermore, in a preferred embodiment of the present invention, this can be achieved by using a low content of the relatively expensive hydrophilic monomer EDEGA. Non-hydrophilic meta(acrylates) such as MMA and n-BA, EDEGA and hydrophilic monomers such as MEMA and MEA are relatively expensive. However, the use of EDEGA in silyl ester copolymers is economical compared to other hydrophilic monomers of the scale designed by the inventors.

Therefore, an object of the present invention is to provide an antifouling coating composition having a polishing rate suitable for preventing fouling under an environment in which an object is in contact with seawater for a long period of time (eg, a vessel idle for several weeks or several months), preferably an existing antifouling coating composition. for a lower cost than the coating of

This objective is achieved through the use of silyl ester copolymers comprising triisopropylsilyl methacrylate (TISMA) or triisopropylsilyl acrylate (TISA) and ethyl diethylene glycol acrylate (EDEGA) comonomers.

The present invention relates to a marine antifouling coating composition, and more particularly, to a marine antifouling composition comprising ethyl diethylene glycol acrylate (EDEGA) and triisopropylsilyl methacrylate (TISMA) or triisopropylsilyl acrylate (TISA) A coating composition is provided. In addition, the present invention provides a method for protecting an object from contamination and an object coated with the antifouling coating composition of the present invention.

In one embodiment of the present invention, the present invention,

(i) ethyl diethylene glycol acrylate (EDEGA); and

(ii) triisopropylsilyl (meth)acrylate; as a comonomer, preferably the ratio of (i): (ii) (mol/mol) is 5:95 to 60:40 (mol/mol) ) provides a silyl ester copolymer.

In a preferred embodiment of the present invention, the present invention,

(i) ethyl diethylene glycol acrylate (EDEGA); and

(ii) triisopropylsilyl methacrylate (TISMA); as a comonomer, preferably the ratio of (i): (ii) (mol/mol) is 5:95 to 60:40 (mol/ molar) silyl ester copolymer.

The content of (i) in the silyl ester copolymer is preferably 2 to 40 mol%. The content of (ii) of the silyl ester copolymer is preferably 5 to 60 mol%.

In one embodiment, the silyl ester copolymer includes one or more hydrophilic comonomers of formula (I).

R ¹ is H or CH ₃ , R ² is a C3-C18 substituent having at least one oxygen or nitrogen atom, R ² is preferably a C3-C18 substituent having at least one oxygen atom, and , the hydrophilic comonomer is not EDEGA.

In one embodiment, the silyl ester copolymer further includes one or more non-hydrophilic comonomers of formula (II).

R ^1' is H or CH ₃ , R ^2' is a C1-8 hydrocarbyl substituent, R ^2' is preferably a C1-8 alkyl substituent, and R ^2' is most preferably a C1-8 alkyl substituent. methyl, ethyl, n-propyl, 2-ethylhexyl or n-butyl

In a preferred embodiment of the present invention, the silyl ester copolymer contains 10 to 70 mol% of methyl methacrylate (MMA) as a comonomer.

The present invention also provides antifouling coating compositions comprising the disclosed copolymers dispersed in a solvent. The antifouling coating may further include an antifouling additive, preferably cuprous oxide and/or copper pyrithione.

The present invention also provides a method of protecting an object from contamination, the method comprising coating at least a portion of the soiled object with an antifouling coating composition as defined herein.

The present invention also relates to an object coated with the antifouling coating composition defined herein.

The terms used in the present invention are defined below.

The term "marine antifouling coating composition", "antifouling coating composition" or simply "coating composition" refers to a composition suitable for use in a marine environment. The antifouling coating composition requires antifouling additives (eg, biocides).

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

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

The term "rosin" is used in the sense of including "rosin or a derivative thereof".

The term “binder” defines the part of a composition that includes a silyl ester copolymer and any other components that together form a matrix that imparts material and strength to the composition. Typically the term "binder" refers to a silyl ester copolymer comprising any rosin that may be included therein.

The present invention can provide an antifouling coating composition having a polishing rate suitable for preventing contamination under an environment in which an object is in contact with seawater for a long period of time (eg, a vessel idle state for several weeks or several months), and is more economical than conventional coatings. great.

The antifouling coating composition of the present invention comprises a silyl ester copolymer comprising comonomers ethyl diethylene glycol acrylate (EDEGA) and triisopropylsilyl (meth)acrylate, ie TISMA or TISA, preferably TISMA. Additional silyl (meth)acrylate comonomers, hydrophilic (meth)acrylate comonomers and/or non-hydrophilic (meth)acrylate comonomers may additionally be present, the terms of which are defined herein.

Silyl ester copolymer

Silyl ester copolymers include at least the comonomers triisopropylsilyl meta(acrylate), namely TISMA and ethyl diethylene glycol acrylate (EDEGA), and as described herein, silyl (meth)acrylate copolymers monomers, hydrophilic meta (meth)acrylate comonomers and/or non-hydrophilic (meth)acrylate comonomers.

Given the mole percent of a given comonomer in a silyl ester copolymer, the mole percent relates to the sum (in moles) of each comonomer present in the copolymer. Thus, if TISMA and EDEGA are the only comonomers of the silyl ester copolymer, the mole percent of TISMA is calculated as (TISMA (mole) / (TISMA (mole) + EDEGA (mole))) x 100%. If only TISMA, EDEGA and methyl methacrylate (MMA) are present, the mole percent of TISMA is calculated as (TISMA (mole) / (TISMA (mole) + EDEGA (mole) + MMA (mole))) x 100% do. If only TISMA, EDEGA and methyl methacrylate (MMA) are present, the mole percent of TISMA is calculated as (TISMA (mole) / (TISMA (mole) + EDEGA (mole) + MMA (mole))) × 100% do. The weight percentage of the copolymer is calculated similarly. Preferably, the copolymer is >90%, preferably >95%, especially >98% by weight of silyl (meth)acrylate, hydrophilic (meth)acrylate and non-hydrophilic (meth)acrylate comonomers. am.

Component (i) is ethyl diethylene glycol acrylate (EDEGA) having the following structure:

Component (i) is preferably 2 to 40 mol% of the copolymer, preferably 2 to 30 mol% of the copolymer, more preferably 5 to 30 mol%, still more preferably 5 to 25 mol% of the copolymer. form %.

The EDEGA is used to prepare the silyl ester copolymer, and is used in a purity of ≧90%, preferably ≧95% or more preferably ≧97%. The use of high purity EDEGA offers certain advantages in terms of final properties of the dried composition.

Component (ii) is triisopropylsilyl (meth)acrylate, preferably (TISMA), preferably 5 to 60 mol%, preferably 15 to 50 mol%, more preferably 20 to 60 mol% of the copolymer. 45 mol%.

The ratio of (i):(ii) (mol/mole) is preferably in the range of 5:95 to 60:40, preferably in the range of 10:90 to 50:50, more preferably 20: It is in the range of 80 to 50:50, more preferably in the range of 30:70 to 50:50. In one embodiment of the present invention, the molar amount of (ii) in the copolymer is equal to or greater than the molar amount of (i) in the copolymer.

The amount of (i)+(ii) in the copolymer is preferably 85% by weight or less, 80% by weight or less, and more preferably 78% by weight or less. The amount of (i)+(ii) in the copolymer may range from 30 to 85% by weight or from 40 to 80% by weight.

The amount of (i)+(ii) in the copolymer is preferably 75 mol% or less, 70 mol% or less, more preferably 65 mol% or less. The amount of (i)+(ii) in the copolymer may range from 30 to 75 mol%, from 35 to 70 mol%, more preferably from 35 to 65 mol%.

Additional hydrophilic (meth)acrylate comonomer(s)

In certain embodiments of the present invention, the copolymer may include one or more comonomers of formula (I).

(I)

(I)

R ¹ is H or CH ₃ , R ² is a C3-C18 substituent having at least one oxygen or nitrogen atom, R ² is preferably a C3-C18 substituent having at least one oxygen atom, and , the comonomer of formula (I) is not EDEGA (which is separately counted as component (i)). As used herein, the structure defines a “hydrophilic” (meth)acrylate comonomer.

As shown in the formula above, the term “hydrophilic (meth)acrylate” requires that the R ² group of formula (I) contains at least one oxygen or nitrogen atom, and preferably contains at least one oxygen atom. As described below, there may also be additional non-hydrophilic (meth)acrylate comonomers in which the R ^2' unit consists only of C and H atoms.

In one embodiment of the present invention, in the silyl ester copolymer, the R ² group of Formula (I) is represented by the formula (CH ₂ CH ₂ O) _n -R ³ , wherein R ³ is C1-C10 alkyl or an aryl substituent of C6-C10, and n is an integer of 1 to 6, preferably 1 to 3, including at least one comonomer. Preferably, the R ² group is represented by the formula (CH ₂ CH ₂ O) _n -R ³ wherein R ³ is a C1-C10 alkyl substituent, preferably CH ₃ or CH ₂ CH ₃ . Moreover, n is an integer of 1-3, Preferably it is an integer of 1-2.

In one embodiment of the present invention, the silyl ester copolymer comprises one or more of methoxyethyl methacrylate (MEMA), methoxyethyl acrylate (MEA) and ethoxyethyl methacrylate (EEMA).

In one embodiment of the present invention, the silyl ester copolymer comprises a comonomer wherein the R ² group of Formula (I) is a saturated ring group containing at least one oxygen or nitrogen atom, preferably at least one oxygen atom. do. More preferably, R2 is a group W-R10, wherein R10 is a cyclic ether (optionally alkyl substituted oxolane, oxane, dioxolane, dioxane), and W is a C1-C4 alkylene. , and most preferably includes tetrahydrofurfuryl acrylate (THFA) having the following structure.

When the hydrophilic (meth)acrylate of formula (I) is present, a particularly preferred amount is 2 to 25 mol%, preferably 2 to 20 mol%, such as 5 to 15 mol%. When mixtures of comonomers of formula (I) are present, their amounts are related to the combined mole fractions of comonomers of formula (I) in the copolymer.

If a comonomer of formula (I) is present, more preferably the comonomer is methoxyethyl methacrylate (MEMA), methoxyethyl acrylate (MEA), ethoxyethyl methacrylate (EEMA), tetrahydride These include lofurfuryl acrylate (THFA), tetrahydrofurfuryl methacrylate (THFMA) and ethyl diethylene glycol methacrylate (EDEGMA).

In a preferred embodiment of the present invention, the copolymer does not contain any significant amount of comonomer of formula (I), i.e. the copolymer contains less than 10 mol % hydrophilic comonomer, more preferably less than 5 mol % co-monomer. monomers, more preferably less than 2 mole percent comonomers.

Additional non-hydrophilic (meth)acrylate comonomer(s)

* The silyl ester copolymer may further comprise one or more hydrophilic (meth)acrylate comonomers of formula (II).

(II)

(II)

R ^1' is H or CH ₃ , R ^2' is a C1-8 hydrocarbyl substituent, R ^2' is preferably a C1-8 alkyl substituent, and R ^2' is most preferably a C1-8 alkyl substituent. methyl, ethyl, n-propyl, 2-ethylhexyl or n-butyl. Comonomers according to formula (II) are defined herein as 'non-hydrophilic' comonomers.

In all embodiments of the present invention, the silyl ester copolymer preferably comprises at least one additional non-hydrophilic methacrylate and/or non-hydrophilic acrylate comonomer. When one or more non-hydrophilic (meth)acrylate comonomers are present, the sum of these (meth)acrylate comonomers in the silyl ester copolymer is preferably 80 mol% or less, preferably 70 mol% or less, 20 to 70 mol%, 30 to 60 mol%, more preferably 35 to 60 mol%.

In a preferred embodiment of the present invention, the comonomers TISMA, EDEGA and any non-hydrophilic (meth)acrylate comonomer according to formula (II) together form >80 mole%, preferably >85%, of the silyl ester copolymer. mol%, more preferably >90 mol% comonomer.

In a preferred embodiment of the present invention, the silyl ester copolymer comprises one or more non-hydrophilic comonomers methyl methacrylate (MMA) and/or n-butyl acrylate (n-BA).

In all embodiments of the present invention, it is preferred that methyl methacrylate (MMA) is included in addition to TISMA and EDEGA. When MMA is present, it is preferred that MMA is present at 10 to 80 mol % of the copolymer, preferably 30 to 60 mol %. According to a preferred embodiment of the present invention, TISMA, EDEGA and MMA together form a comonomer >80 mole%, preferably >85 mole%, more preferably >90 mole% in the silyl ester copolymer.

In a preferred embodiment of the present invention, the copolymer comprises 20-60 mole % TISMA, 2-40 mole % EDEGA and 10-70 mole % MMA; More preferably, it contains 20 to 50 mol% of TISMA, 5 to 30 mol% of EDEGA, and 30 to 60 mol% of MMA. In such an embodiment, additional silyl (meth)acrylate, hydrophilic (meth)acrylate and/or non-hydrophilic (meth)acrylate comonomers may be included.

When n-BA is present, n-BA is preferably present in an amount of 2 to 20 mol%, more preferably 2 to 15 mol%.

In one embodiment of the present invention, the silyl ester copolymer comprises comonomers TISMA, EDEGA, MMA and at least one hydrophilic or non-hydrophilic (meth)acrylate comonomer. In one embodiment of the present invention, the silyl ester copolymer comprises or consists of the following monomers: TISMA, EDEGA, MMA; TISMA, EDEGA, MMA and n-BA; or TISMA, EDEGA, MMA, n-BA and THFA.

Additional silyl (meth)acrylate comonomers

The silyl ester copolymer may include additional silyl (meth)acrylate comonomers. If present, any additional silyl (meth)acrylate comonomers other than triisopropylsilyl (meth)acrylate preferably form no more than 10 mol% of the copolymer, and preferably 5 mol% of the copolymer. form the following When present, a suitable silyl (meth)acrylate comonomer is preferably represented by formula (III).

(III)

(III)

At this time, R ⁴ and R ⁵ are each independently selected from linear or branched C _1-4 alkyl groups;

R ⁶ , R ⁷ and R ⁸ are each independently selected from linear or branched C1-20 alkyl groups, C3-C12 cycloalkyl groups, optionally substituted C6-C20 aryl groups and —OSi(R ⁹ ) ₃ groups;

each R ⁹ is independently a linear or branched C1-4 alkyl group;

N is an integer from 0 to 5;

X is an acryloyloxy group, a methacryloyloxy group, a (methacryloyloxy)alkylenecarbonyloxy group, and a (acryloyloxy)alkylenecarbonyloxy group. It is an ethylenically unsaturated group such as the (acryloyloxy)alkylenecarbonyloxy group. Since triisopropyl (meth)acrylate is inherently present in the copolymer, it should be considered excluded from formula (III).

The term "alkyl" is meant to encompass all linear or branched alkyl groups such as methyl, ethyl, isopropyl, propyl and butyl. Particularly preferably, the cycloalkyl group includes cyclohexyl and substituted cyclohexyl.

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

Ideally, preferred silyl ester monomers are based on compounds of formula (III) wherein n is 0, ie compounds of the general formula X-SiR ⁶ R ⁷ R ⁸ .

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

Triethylsilyl (meth)acrylate, tri-n-propylsilyl (meth)acrylate, tri-n-butylsilyl (meth)acrylate, triisobutylsilyl (meth)acrylate, tri- tert -butylsilyl ( meth)acrylate, tri-sec-butylsilyl (meth)acrylate, tri-n-pentylsilyl (meth)acrylate, triisopentylsilyl (meth)acrylate, tri-n-dodecylsilyl (meth)acrylate rate, triphenylsilyl (meth)acrylate, tri-(p-methylphenyl)silyl (meth)acrylate, tribenzylsilyl (meth)acrylate, ethyldimethylsilyl (meth)acrylate, n-propyldimethylsilyl (meth)acrylate )Acrylate, isopropyldimethylsilyl (meth)acrylate, n-butyldimethylsilyl (meth)acrylate, isobutyldimethylsilyl (meth)acrylate, tert-butyldimethylsilyl (meth)acrylate, n-pentyldimethyl Silyl (meth)acrylate, n-hexyldimethylsilyl (meth)acrylate, neohexyldimethylsilyl (meth)acrylate, dexyldimethylsilyl (meth)acrylate, n-octyldimethylsilyl (meth)acrylate, n- dexyldimethylsilyl (meth)acrylate, dodecyldimethylsilyl (meth)acrylate, n-octadecyldimethylsilyl (meth)acrylate, cyclohexyldimethylsilyl (meth)acrylate, phenyldimethylsilyl (meth)acrylate, Benzyldimethylsilyl (meth)acrylate, phenethyldimethylsilyl (meth)acrylate, (3-phenylpropyl)dimethylsilyl (meth)acrylate, p-tolydimethylsilyl (meth)acrylate, isopropyldiethylsilyl ( meth)acrylate, n-butyldiisopropylsilyl (meth)acrylate, n-octyldiisopropylsilyl (meth)acrylate, methyldi-n-butylsilyl (meth)acrylate, methyldicyclohexylsilyl ( meth)acrylate, methyldiphenylsilyl (meth)acrylate, tert-butyldiphenylsilyl (meth)acrylate, nonamethyltetrasiloxy (meth)acrylate, bis(trimethylsiloxy)methylsilyl (meth)acryl lattice, tris(trimethylsiloxy)silyl (meth)acrylate and other acrylic and methacrylic acids as described in WO2014/064048 and WO03/080747.

When the silyl ester copolymer contains triisopropylsilyl acrylate, it may additionally contain triisopropylsilyl methacrylate and vice versa. Formula (III) above is intended to include the presence of silyl ester comonomers other than triisopropylsilyl acrylate and triisopropylsilyl methacrylate.

Characteristics of Silyl Ester Copolymers

The polymer containing an organosilyl ester group can be obtained by polymerizing a monomer mixture in the presence of a polymerization initiator by any of a variety of conventional methods such as solution polymerization, bulk polymerization, emulsion polymerization and suspension polymerization or by controlled polymerization techniques. . When preparing a coating composition using such a polymer containing an organosilyl ester group, the polymer is preferably diluted with an organic solvent to provide a polymer solution having an appropriate viscosity. In this regard, it is preferable to use solution polymerization.

Examples of the polymerization initiator include dimethyl 2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(isobutyro nitrile) and 1,1'-azobis (cyanocyclohexane), tert -butyl peroxypivalate, tert -butyl peroxy-2-ethylhexanoate, tert -butyl peroxybenzoate and tert -butyl peroxyisopropylcarbonate, tert -amyl peroxypivalate, tert -amyl perox-2-ethylhexanoate, 1,1-di( tert -amyl peroxy)cyclohexane and dibenzoyl peroxide; contains the same peroxide. These compounds are used singly or in admixture 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; esters such as butyl acetate, tert -butyl acetate, amyl acetate, ethylene glycol methyl ether acetate; ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dibutyl ether, dibutyl ether, dioxane, tetrahydrofuran; alcohols such as n-butanol, isobutanol, and benzyl alcohol; ether alcohols such as butoxyethanol and 1-methoxy-2-propanol; aliphatic hydrocarbons such as white spirit; mixtures of any two or more solvents. These compounds are used alone or in a mixture of two or more. The copolymer is preferably a random copolymer.

The weight average molecular weight of the polymer containing organic silyl ester groups thus obtained is preferably 5,000 to 70,000, more preferably 10,000 to 60,000. Mw is determined as described in the Examples section.

The silyl ester copolymer can be provided as a polymer solution. The polymer solution is preferably adjusted to have a solid content of 30 to 90% by weight, preferably 40 to 85% by weight, more preferably 47 to 75% by weight.

The final antifouling coating composition of the present invention preferably contains 0.5 to 45% by weight (dry solids) of the silyl ester copolymer, 1.0 to 30% by weight, particularly 5 to 25% by weight of the silyl ester copolymer relative to the total coating composition. It is desirable to do

The copolymer preferably has a glass transition temperature (Tg) of at least 15°C, preferably at least 20°C, at least 22°C, all values determined according to the Tg test described in the Examples section. Values below 80°C are preferred, for example below 75°C, i.e. below 50°C.

The antifouling coating composition of the present invention is the entire coating composition optionally a silyl ester copolymer and other silyl esters of the present invention, as described for example in US Pat. No. 4,593,055, EP 0 646 630, WO 2009/007276 and EP 2 781 567. It may contain mixtures of copolymers.

Rosin Ingredients

Rosin can be used to adjust the self-polishing properties and mechanical properties of antifouling coatings. The antifouling coating composition of the present invention preferably comprises at least 0.5% by weight (dry solids) of rosin, for example 1% by weight. The upper limit of the rosin component may be 25% by weight, for example 15% by weight.

The rosin used in the present invention may be rosin or a derivative thereof, for example a salt thereof as described below. Examples of rosin materials include wood rosin, tall oil rosin and gum rosin; Hydrogenated and partially hydrogenated rosin, disproportionated rosin, dimerised rosin, polymerised rosin, maleic acid esters, fumaric acid esters, glycerol esters, methyl esters, pentaerythritol esters esters) and other rosins and esters of hydrogenated rosins, copper resinates, zinc resinates, calcium resinates, magnesium resinates and other metal resinates of rosins and polymerized rosins and other substances described in WO 97/44401 include Gum rosin and derivatives of gum rosin are preferred.

In the present invention, the antifouling composition as a whole preferably contains 0.5 to 25% by weight, preferably 1 to 15% by weight (dry solids) of rosin material, preferably 2 to 7% by weight (dry solids). include

The properties of the antifouling coating can be controlled by varying the relative contents of the silyl ester copolymer and rosin component.

Accordingly, in one preferred embodiment of the present invention, a binder comprising the silyl ester copolymer as defined above and rosin or a derivative thereof is provided.

Other Binder Ingredients

In addition to the silyl ester copolymer and optionally included rosin, additional binders may be used to adjust the properties of the antifouling coating. Examples of binders that may be used in addition to the silyl ester copolymers and rosins of the present invention include:

acid functional polymers of acid groups blocked by a divalent metal bonded to a monovalent organic moiety, such as examples described in EP 0 204 456 and EP 0 342 276; acid functional polymers of acid groups blocked by divalent metals bonded to hydroxyl moieties, such as examples described in GB 2 311 070 and EP 0 982 324; acid functional polymers with acid groups blocked by amines, such as examples described in EP 0 529 693;

hydrophilic copolymers of (meth)acrylate copolymers and poly( N -vinyl pyrrolidone) copolymers, for example described in GB 2 152 947, and other copolymers described in EP 0 526 441;

(meth)acrylic polymers and copolymers such as poly(n-butyl acrylate), poly(n-butyl acrylate-co-isobutyl vinyl ether) and other materials described in WO03/070832 and EP2128208, especially acrylate binders ;

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);

For example poly(lactic acid), poly(glycolic acid), poly(2-hydroxybutyric acid), poly(3-hydroxybutyric acid), poly(4-hydroxyvaleric acid), polycaprolactone and the above units aliphatic polyesters such as aliphatic polyester copolymers comprising two or more units selected from;

polyesters comprising metals other than copper, for example as described in EP 1 033 392 and EP 1 072 625;

alkyd resins and modified alkyd resins;

hydrocarbon resins, such as hydrocarbon resins formed by polymerization of at least one monomer selected from C5 aliphatic monomers, C9 aromatic monomers, indene coumarone monomers or terpenes or mixtures thereof, ie as described in WO2011/092143;

polyoxalates described in WO2009/100908 and other condensation polymers described in WO 96/14362.

If an additional binder is present in addition to the rosin and silyl ester copolymer, the weight ratio of the silyl copolymer (etc.): binder is 30:70 to 95:5, preferably 40:60 to 80:20, more preferably It may range from 50:50 to 70:30. This preferred weight ratio relates only to the content of the silyl copolymer(s) and additional binder, i.e. no rosin is included.

Particularly suitable further binders are (meth)acrylic polymers and copolymers.

disinfectant

The antifouling coating additionally includes a compound capable of preventing or removing marine fouling on or from a surface. Typically, the antifouling coating composition includes a copper biocide such as metallic copper, cuprous oxide, copper thiocyanate and the like.

The cuprous oxide material has a typical particle diameter distribution of 0.1 to 70 μm and an average particle size (d50) of 1 to 125 μm. The cuprous oxide material may contain a stabilizer (to prevent surface oxidation). Examples of commonly available cuprous oxide include Nordox Cuprous Oxide Red Paint Grade, Nordox XLT from Nordox AS, cuprous oxide from Furukawa Chemicals Co., Ltd.; Red Copp 97N, Purple Copp, Lolo Tint 97N, Chemet CDC, Chemet LD from American Chemet Corporation; Cuprous Oxide Red by Spiess-Urania; Includes Cuprous oxide Roast, Cuprous oxide Electrolytic from Taixing Smelting Plant Co., Ltd.

4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole[medetomidine] and 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H A range of organic fungicides can be used instead of copper fungicides such as -pyrrole-3-carbonitrile [tralopyril]. Commonly known disinfectants can be used in the present invention. The terms antifouling additive, antifouling agent, fungicide, insecticide are used to describe commonly known compounds that act on surfaces to prevent marine fouling. The antifouling agent of the present invention is a marine antifouling agent.

The coating composition may include a copper biocide, preferably cuprous oxide (Cu ₂ O) and/or copper pyrithione. The coating composition of the present invention may include other biocides as described in WO2014/064048. Preferably, the fungicide is cuprous oxide, copper thiocyanate, zinc pyrithione, copper pyrithione, zinc ethylenebis(dithiocarbamate) [zineb], 2-(tert -Butylamino)-4-(cyclopropylamino)-6-(methylthio)-1,3,5-triazine[cubutrin](2-(tert-butylamino)-4- (cyclopropylamino)-6- (methylthio)-l,3,5-triazine [cubutryne]), 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one [DCOIT] (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-phenylsulfamide [dichlorofluanid]), N-dichlorofluoromethylthio-N',N'-dimethyl-Np-tolisulfamide [tolifluanid] (N-dichlorofluoromethylthio-N',N' -dimethyl-Np-tolylsulfamide [tolylfluanid]), 4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole[medetomidine](4-[1-(2,3-dimethylphenyl)ethyl ]-1H-imidazole [medetomidine]), triphenylborane pyridine [TPBP] and 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile [tralopyril] (4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile [tralopyril]).

Mixtures of fungicides can be used because, as is commonly known, different fungicides act against different marine fouling organisms.

In an alternative embodiment, the antifouling coating is free of copper. In one such embodiment, the preferred combination of fungicides comprises a combination of one or more selected from tralopyril and zinc pyrithione, 4,5-dichloro-2-octyl-4-isothiazoli-3-one.

If a biocide combination is present, the amount of the biocide combination may form up to 70% by weight of the coating composition, for example from 4 to 60%, from 5 to 60% by weight. When copper is present, a suitable amount of biocide in the coating composition may be 20-60% by weight. If copper is not present, the biocide agent may be in a relatively small amount, for example 0.1 to 20% by weight, 0.2 to 15% by weight. The amount of disinfectant may differ depending on the end use and the disinfectant used.

Some biocides may be encapsulated or adsorbed in an inert carrier or bound to other substances for controlled release. This ratio refers to the amount of active biocide present and is not related to any carrier used.

Other Ingredients

The antifouling coating composition according to the present invention optionally further contains at least one component selected from other binders, inorganic or organic pigments, extenders and fillers, additives, solvents and diluents, in addition to a silyl ester copolymer and optionally selectable components. can include

Examples of the pigment include inorganic pigments such as titanium dioxide, iron oxide, zinc oxide and zinc phosphate; There are organic pigments such as phthalocyanine compounds, azo pigments and carbon black.

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

Examples of additives that may be added to the antifouling coating composition may include reinforcing agents, thixotropic agents, thickening agents, antisettling agents, wetting agents, dispersing agents, plasticizers and solvents.

Examples of reinforcing agents are flakes and fibers. Fibers include natural and synthetic inorganic fibers such as silicon-containing fibers, carbon fibers, oxide fibers, carbide fibers, nitride fibers, sulfide fibers, phosphate fibers, mineral fibers; metal fibers; natural and synthetic organic fibers such as cellulose fibers, rubber fibers, acrylic fibers, polyamide fibers, polyimide fibers, polyester fibers, polyhydrazide fibers, polyvinylchloride fibers, polyethylene fibers, and the fibers described in WO 00/77102; include Preferably, the fiber has an average length of 25 to 2,000 μm and an average thickness of 1 to 50 μm, and the ratio of the average length to the average thickness is at least 5.

Examples of the thixotropic agent, thickener and antisettling agent include fumed silica, organo-modified clay, amide wax, polyamide wax, amide derivatives, polyethylene wax, oxidized polyethylene wax, hydrogenated castor oil wax, ethyl cellulose, aluminum stearate and mixtures thereof.

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

Examples of the dehydrating agent and drying agent include anhydrous calcium sulfate, calcium sulfate hemihydrate, anhydrous magnesium sulfate, anhydrous sodium sulfate, anhydrous zinc sulfate, molecular sieve zeolite; orthoesters such as trimethyl orthoformate, triethyl orthoformate, tripropyl orthoformate, triisopropyl orthoformate, tributyl orthoformate, trimethyl orthoacetate and triethyl orthoacetate; ketal; acetal; enol ether; orthoborates such as trimethyl borate, triethyl borate, tripropyl borate, triisopropyl borate, tributyl borate and tri-tert-butyl borate; silicates such as trimethoxymethyl silane, tetraethyl silicate and ethyl polysilicate; and isocyanates such as p-toluenesulfonyl isocyanate.

Dehydrating agents and drying agents are preferably silicates and inorganic compounds.

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

Generally, these optional components may be present in an amount of 0.1 to 20% by weight of the antifouling composition, typically 0.5 to 20% by weight, preferably 0.75 to 15% by weight. The content of these optional ingredients may vary depending on the end use.

More preferably, the antifouling composition contains a solvent. The solvent is preferably volatile and is preferably an organic solvent. Examples of organic solvents and diluents include 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; esters such as butyl acetate, tert-butyl acetate, amyl acetate, isoamyl acetate, ethylene glycol methyl ether acetate, propyl propionate, butyl propionate; ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dibutyl ether, dioxane, and tetrahydrofuran; alcohols such as n-butanol, isobutanol, and benzyl alcohol; ether alcohols such as butoxyethanol and 1-methoxy-2-propanol; aliphatic hydrocarbons such as white spirit; and mixtures of two or more optionally selected solvents and diluents.

The solvent is preferably an aromatic solvent, more preferably a mixture of xylene and aromatic hydrocarbon.

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

On the other hand, the coating may be dispersed in organic non-solvents for coating compositions or film-forming compositions in aqueous dispersions.

The antifouling coating composition of the present invention preferably has a solids content of greater than 40% by volume, for example may have a content of greater than 45% by volume, greater than 50% by volume, preferably greater than 55% by volume.

More preferably, the antifouling coating composition should have a volatile organic compound (VOC) content of less than 500 g/L, preferably less than 400 g/L, for example less than 390 g/L. The VOC content can be calculated or measured (ASTM D5201-01), and preferably can be measured.

The antifouling coating composition of the present invention can be applied to all or part of any soiled object. The surface may be constantly or intermittently under water (eg due to tidal movement, loading or increasing of different cargoes). The object surface will typically be the hull of a ship or the surface of a fixed marine object such as an oil platform or buoy. Application of the coating composition may be effected by any convenient means, for example painting (eg with a brush or roller) or spraying of the coating onto the object. Typically the surface requires separation from seawater for coating. The action of the coating can be achieved through commonly known methods.

When an antifouling coating is applied to the surface of an object (such as a hull), the surface of the object is typically not protected with only a single antifouling coating. Depending on the nature of the surface, antifouling coatings can be applied directly over existing coating systems. Such coating systems may include multi-layer paints of different general types (e.g., epoxies, polyesters, vinyls or acrylics or mixtures thereof). If the surface is clean or has an antifouling coating that has not been damaged by previous action, the new antifouling paint can usually be applied in one or more coats, except in special cases.

On the other hand, artisans can start with uncoated surfaces (e.g. steel, aluminum, plastic, composites, fiberglass or carbon fiber). To protect the surface, full coating systems usually include one or two layers of anti-rust coating, one layer of tie-coat and one or two layers of antifouling paint. The skilled person will be familiar with such coating layers.

Exceptionally, an additional layer of antifouling paint may be applied.

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

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

Materials and Methods

General method for preparing copolymer solutions

An amount of solvent was charged to a temperature-controlled reaction vessel equipped with a stirrer, condenser, nitrogen inlet and feed. The reaction vessel was heated and maintained at the reaction temperature given in Table 1. A pre-mixture of monomer, initiator and solvent was prepared. The pre-mixture was charged to the reaction vessel at a constant rate over 2 hours under a nitrogen atmosphere. After 1 hour, the reaction vessel was held or heated to the boost reaction temperature given in Table 1. A post-addition of the boost initiator solution was then added to the reaction mixture. The reaction was held at the given temperature for an additional 2 h before cooling to room temperature.

Viscosity measurement of polymer solutions

The viscosity of the polymer was measured according to ASTM D2196-15 Test Method A, using a Brookfield DV-1 viscometer with a LV-2 or LV-4 spindle at 12 rpm. The polymer was adjusted to 23.0°C±0.5°C prior to measurement.

Determination of the content of non-volatile substances in polymer solutions

The content of non-volatile substances in the polymer solution was determined according to ISO 3251. A test sample of 0.5 g±0.1 g was taken out and dried in a ventilated oven at 150° C. for 30 minutes. The weight of the remaining material is considered as non-volatile material (NVM). Non-volatile content is expressed in weight percent. The value given is the average of three parallel lines.

Measurement of polymer average molecular weight distribution

Polymers are characterized by Gel Permeation Chromatography (GPC) measurements. Molecular weight distribution (MWD) was measured using two PLgel 5 μm Mixed-D columns of the Polymer Laboratories series, together with tetrahydrofuran (THF) as an eluent, and refractive index (RI) at a constant flow rate of 1 mL/min at room temperature. It was measured using a Polymer Laboratories PL-GPC 50 instrument with a detector. The column was calibrated using EasiVials PS-H, a polystyrene standard from Polymer Laboratories. The data were processed using Polymer Lab's Cirrus software. Samples were prepared by dissolving an amount of polymer solution corresponding to 25 mg of dry polymer in 5 ml of THF. The samples were kept at room temperature for a minimum of 3 hours before sampling for GPC measurements. Prior to analysis, the samples were filtered through a 0.45 μm nylon filter. Weight-average molecular weight (Mw), number-average molecular weight (Mn) and given values such as polydispersity index (PDI) and Mw/Mn are listed in the table.

Glass transition temperature measurement

The glass transition temperature (Tg) is obtained by differential scanning calorimetry (DSC) measurement. DSC measurements were performed on a TA Instruments DSC Q200. A small amount of the polymer solution was transferred to an aluminum pan and the sample was dried at 50°C for a minimum of 10 hours and then at 150°C for 3 hours. 10 mg dry polymer material was measured in an open aluminum pan and scans were recorded with a heating rate of 10° C./min and a cooling rate of 10° C./min relative to the empty pan. Data were processed using TA Instruments' Universal Analysis software. The inflection point of the glass transition range defined in ASTM E1356-08 of the second heat was recorded as the polymer's Tg.

General manufacturing method of antifouling coating composition

The ingredients were mixed in the proportions given in Table 2. The mixture was dispersed for 15 minutes in the presence of glass beads (diameter of about 2 mm) in a 250 ml paint can using a vibrational shaker. Glass beads were filtered prior to testing.

Paint Viscosity Measurement Using Cone and Plate Viscometers

The viscosity of the antifouling paint composition was measured according to ISO 2884-1: 1999 using a digital cone and plate viscometer set at a temperature of 23 ° C., 10000 s ^-1 It works at shear rates and provides a viscosity measurement range of 0-10P. Results were expressed as the average of three measurements.

Calculation of Volatile Organic Compound (VOC) Content of Antifouling Coating Compositions

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

Measurement of the polishing rate of an antifouling coating film on a rotating disc in seawater

The polishing rate was measured by measuring the film thickness decrease of the coating film over time. In this test, a PVC disc is used. The coating composition was applied in radial stripes on the disc using a film applicator. The thickness of the dry coating film was measured by a surface profiler. The PVC disk is mounted on a shaft and rotates within a container in which sea water flows. The speed of the rotating shaft gives an average simulated speed of 16 knots on the disk. Natural seawater that has been filtered and conditioned to a temperature of 25°C±2°C was used. A PVC disc was taken out at regular intervals and the film thickness was measured. The discs were washed and dried overnight at room temperature before measuring the film thickness.

Table 1a. Details of silyl ester copolymer solutions S1 to S11 and C1 to C5. Ingredients are given on a parts by weight basis. Also, monomer compositions are provided on a molar basis (see [in brackets]).

[Table 1a]

Table 1b. (Continuation of Table 1a)

Table 2: General components of coating compositions shown by parts by weight

Table 3: Details and test results for all paint examples. (n.d. = not determined)

Claims (30)

As an antifouling coating composition,
The antifouling coating composition includes one or more antifouling agents, rosin or a derivative thereof, and a silyl ester copolymer;
The silyl ester copolymer is a comonomer
(i) ethyl diethylene glycol acrylate (EDEGA); and
(ii) triisopropylsilyl methacrylate;
Which includes,
Antifouling coating composition. According to claim 1,
The antifouling coating composition of claim 1, wherein the ratio of (i):(ii) (mol/mol) in the copolymer is in the range of 5:95 to 60:40 (mol/mol). According to claim 1,
The content of (i) in the silyl ester copolymer is in the range of 2 to 40 mol% of the copolymer, antifouling coating composition. According to claim 3,
The content of (i) in the silyl ester copolymer is in the range of 2 to 30 mol% of the copolymer, antifouling coating composition. According to claim 3,
The content of (i) in the silyl ester copolymer is in the range of 5 to 25 mol% of the copolymer, antifouling coating composition. According to claim 1,
The content of (ii) in the silyl ester copolymer is in the range of 5 to 60 mol% of the copolymer, antifouling coating composition. According to claim 6,
The content of (ii) in the silyl ester copolymer is in the range of 15 to 50 mol% of the copolymer, antifouling coating composition. According to claim 6,
The content of (ii) in the silyl ester copolymer is in the range of 20 to 45 mol% of the copolymer, antifouling coating composition. According to claim 1,
The silyl ester copolymer further includes at least one hydrophilic comonomer of formula (I),

wherein R ¹ is H or CH ₃ , R ² is a C3-C18 substituent having at least one oxygen or nitrogen atom, and the hydrophilic comonomer of Formula (I) is not EDEGA, antifouling coating composition. According to claim 9,
Wherein R ² is a C3-C18 substituent having at least one oxygen atom, the antifouling coating composition. According to claim 9,
The at least one hydrophilic comonomer comprises R ² represented by the formula (CH ₂ CH ₂ O) _n -R ³ ,
Wherein R ³ is a C1-C10 alkyl or C6-C10 aryl substituent, wherein n is an integer of 1 to 6;
The comonomer is not EDEGA, the antifouling coating composition. According to claim 11,
Wherein n is an integer of 1 to 3, the antifouling coating composition. According to claim 9,
At least one hydrophilic comonomer is present and has R ² represented by the formula (CH ₂ CH ₂ O) _n -R ³ ,
Wherein R ³ is an alkyl substituent, wherein n is an integer of 1 to 3;
The comonomer is not EDEGA, the antifouling coating composition. According to claim 13,
Wherein R ³ is CH ₃ or CH ₂ CH ₃ , antifouling coating composition. According to claim 13,
Wherein n is an integer of 1 or 2, the antifouling coating composition. According to claim 1,
The silyl ester copolymer is methoxyethyl methacrylate (MEMA), methoxyethyl acrylate (MEA, methoxyethyl acrylate), ethoxyethyl methacrylate (EEMA, ethoxyethyl methacrylate) and tetrahydrofurfuryl acryl An antifouling coating composition further comprising at least one of THFA (tetrahydrofurfuryl acrylate). According to claim 1,
The silyl ester copolymer is a non-hydrophilic comonomer of formula (II):

(Wherein, R ^1' is H or CH ₃ , and R ^2' is a C1-8 hydrocarbyl substituent)
Further comprising one or more, antifouling coating composition. 18. The method of claim 17,
Wherein R ^2' is a C1-8 alkyl substituent, the antifouling coating composition. 18. The method of claim 17,
Wherein R ^2' is methyl, ethyl, n-propyl, 2-ethylhexyl or n-butyl, the antifouling coating composition. 18. The method of claim 17,
The silyl ester copolymer includes at least one of methyl methacrylate (MMA) and n-butyl acrylate (n-BA), antifouling coating composition. According to claim 1,
The silyl ester copolymer comprises MMA in an amount of 10 to 70 mol% as a comonomer, an antifouling coating composition. According to claim 21,
An antifouling coating composition comprising MMA as a comonomer in an amount of 30 to 60 mol%. According to claim 1,
The silyl ester copolymer comprises n-butyl acrylate (n-BA, n-butyl acrylate) as a comonomer in an amount of 2 to 20 mol%, antifouling coating composition. 24. The method of claim 23,
The n-butyl acrylate (n-BA) is contained in an amount of 2 to 15 mol% as a comonomer, antifouling coating composition. According to claim 1,
The silyl ester copolymer is comonomer TISMA; EDEGA; And the following a, b or c; containing, antifouling coating composition.
a. MMA
b. MMA and n-BA
c. MMA, n-BA and THFA According to claim 1,
The antifouling additive is an antifouling coating composition comprising cuprous oxide and / or copper pyrithione. As a method of protecting an object from contamination,
The above method
Coating at least a portion of the soiled object with the antifouling coating composition of any one of claims 1 to 8;
Including, method. An object coated with the antifouling coating composition of claim 26. 29. The method of claim 28,
The object is an object coated with an anticorrosive coating layer, a tie layer, and the antifouling coating composition of any one of claims 1 to 25. 29. The method of claim 28,
The object is coated with the antifouling coating composition of any one of claims 1 to 25, wherein the antifouling coating composition covers an antifouling composition already present on a substrate.