JP7178167B2 - antifouling composition - Google Patents

Description

The present invention relates to marine antifouling paint compositions, more specifically marine antifouling paints comprising ethyldiethylene glycol acrylate (EDEGA) and triisopropylsilyl methacrylate (TISMA) or triisopropylsilyl acrylate (TISA) composition. The invention further relates to methods of protecting objects from fouling and objects coated with the antifouling compositions of the invention.

Surfaces submerged in seawater are susceptible to adhesion of marine organisms such as green algae, brown algae, barnacles, mussels, tubeworms, and the like. Such fouling is undesirable and has an economic impact on offshore structures such as ships, oil platforms and buoys. The deposits can lead to biological degradation of the surface, increased weight, and accelerated corrosion. In ships, the deposits increase frictional resistance, causing a decrease in speed and an increase in fuel consumption. It can also cause reduced mobility.

The risk of fouling increases when surfaces in contact with seawater remain stationary for long periods of time. For example, ships that are being outfitted do not move for several months, increasing the risk of fouling. Vessels that are stationary or slowed down for long periods of time in commerce are also at high risk of fouling. Antifouling paints with high polish rates are desirable in these situations to prevent fouling.

Antifouling paints are used to prevent settlement and growth of marine organisms. The coating typically contains various ingredients such as pigments, fillers, solvents, biologically active substances in addition to film-forming binders.

The most successful self-polishing antifouling systems on the market today utilize silyl-esterified (meth)acrylic copolymers. Such coating compositions are disclosed for example in EP0646630, EP0802243, EP1342756, EP1479737, EP1641862, WO00/77102, WO03/070832 and WO03/080747.

To adjust the self-polishing and mechanical properties of antifouling coatings, silyl-esterified (meth)acrylic copolymers are often used together with other binders such as acrylates and rosin or rosin derivatives. Also included are biocides such as copper oxide, or organic biocides such as 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile [tralopyril]. Sometimes.

Silyl ester copolymers containing hydrophilic acrylate comonomers have already been disclosed. US Pat. No. 5,301,000 discloses antifouling paints in which the hydrophilic acrylate comonomer contains 1 to 25 ethylene glycol repeating units. In one example, ethyl diethylene glycol acrylate (EDEGA) is used along with other hydrophilic acrylate comonomers with 9 glycol repeating units, methyl methacrylate, and n-butyl acrylate. In this example the silyl ester comonomer is tri(n-butyl)silyl methacrylate.

US Pat. No. 6,300,001 discloses silyl ester copolymers using hydrophilic comonomers, where the silyl ester comonomers have two silicon-bonded unbranched C1/C2 groups and at least two branches. a third group attached to the silicon having Examples of the silyl ester comonomer include thexyldimethylsilyl methacrylate and thexyldimethylsilyl acrylate. Thexyldimethylsilyl-based monomers are currently not commercially available, making them a less attractive option for binders in paints. The combination of thexyldimethylsilyl (meth)acrylate and ethyldiethylene glycol acrylate (EDEGA) also provides an antifouling coating, compared to the combination of triisopropylsilyl (meth)acrylate and ethyldiethylene glycol acrylate (EDEGA). Then, the cracking resistance becomes inferior.

US Pat. No. 5,331,001 discloses silyl ester copolymers with hydrophilic acrylate or methacrylate comonomers. Many of the exemplified polymers are copolymers of triisopropylsilyl acrylate, methyl methacrylate, and small amounts of hydrophilic acrylates or methacrylates with hydroxyl groups at the 2, 4, or 6 positions. Also exemplified are copolymers of triisopropylsilyl acrylate, methyl methacrylate and polyethylene glycol methacrylate having polyethylene glycol units repeating 5, 12 or 15 times.

EP 0646630 WO2014/096102 European Patent No. 1016681

The present inventors have surprisingly found silyl ester copolymers incorporating both triisopropylsilyl methacrylate (TISMA) or triisopropylsilyl acrylate (TISA) and ethyldiethylene glycol acrylate (EDEGA) as comonomers. have shown to provide a self-polishing antifouling system with an adequate polishing rate. Moreover, in a preferred embodiment, this is achieved using a small amount of EDEGA, a relatively inexpensive hydrophilic monomer. Compared to non-hydrophilic (meth)acrylates such as MMA and n-BA, EDEGA and other hydrophilic monomers such as MEMA and MEA are relatively expensive. However, the use of EDEGA in silyl ester copolymers is economically feasible compared to other hydrophilic monomers on the scale envisaged by the inventors.

It is therefore an object of the present invention to provide an antifouling article having a polishing rate adequate to prevent fouling under conditions where objects are stationary and in contact with seawater for long periods of time (e.g., ships that do not move for weeks or months at a time). To provide a coating composition, preferably at a lower cost than existing coatings.

The above objects are achieved through the use of silyl ester copolymers containing triisopropylsilyl methacrylate (TISMA) or triisopropylsilyl acrylate (TISA) and ethyldiethylene glycol acrylate (EDEGA) as comonomers.

In a first aspect, the present invention provides a silyl ester copolymer comprising (i) ethyldiethylene glycol acrylate (EDEGA); and (ii) triisopropylsilyl (meth)acrylate as comonomers, preferably comprising the A silyl ester copolymer is provided wherein the ratio of (i):(ii) in the copolymer is in the range of 5:95 to 60:40 (mol/mol).

In a preferred embodiment, the present invention provides a silyl ester copolymer comprising (i) ethyldiethylene glycol acrylate (EDEGA); and (ii) triisopropylsilyl methacrylate (TISMA) as comonomers. A silyl ester copolymer is provided in which the ratio of (i):(ii) in the coalescence ranges from 5:95 to 60:40 (mol/mol).

Preferably, the amount of (i) in the silyl ester copolymer is 2-40 mol %. Preferably, the amount of (ii) in the silyl ester copolymer is 5-60 mol %.

In one embodiment, the silyl ester copolymer further comprises one or more hydrophilic comonomers represented by formula (I).

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

In some embodiments, the silyl ester copolymer further comprises one or more non-hydrophilic comonomers represented by formula (II).

wherein R ^1′ is H or CH ₃ and R ^2′ is a C1-C8 hydrocarbyl group, preferably a C1-C8 alkyl group, most preferably methyl, ethyl, n-propyl , 2-ethylhexyl or n-butyl.

In a preferred embodiment, said silyl ester copolymer comprises methyl methacrylate (MMA) as a comonomer in an amount of 10-70 mol %.

The present invention also provides an antifouling coating composition comprising the copolymer described herein dispersed in a solvent. Said antifouling paint may further comprise an antifouling agent, preferably cuprous oxide and/or copper pyrithione.

The present invention also provides a method of protecting an object from fouling, comprising coating at least a portion of said object prone to fouling with an antifouling coating composition as defined herein. .
The present invention also relates to objects coated with the antifouling coating composition defined herein.

(definition)
The terms "marine antifouling paint composition,""antifouling paint composition," or simply "coating composition" mean a composition suitable for use in a marine environment. The antifouling coating composition requires an antifouling agent, for example a biocide.

The term hydrocarbyl group means any group containing only C and H atoms, including alkyl, alkenyl, aryl, cycloalkyl, arylalkyl groups and the like.

The term "(meth)acrylate" means methacrylate or acrylate.
As used in the text below, the term "rosin" is used to include "rosin or its derivatives".

The term "binder" defines the portion of the composition comprising the silyl ester copolymer and other ingredients that together form the matrix that imparts substance and strength to the composition. do. Generally, the term "binder" as used herein refers to the silyl ester copolymer and rosin that may be included therewith.

The antifouling coating composition of the present invention contains, as comonomers, ethyldiethylene glycol acrylate (EDEGA) and triisopropylsilyl (meth)acrylate, TISMA or TISA, preferably a silyl ester copolymer containing TISMA. . Additional silyl (meth)acrylate comonomers, hydrophilic (meth)acrylate comonomers, and/or non-hydrophilic (meth)acrylate comonomers may additionally be present. These terms are defined here.

(silyl ester copolymer)
Said silyl ester copolymer comprises, as comonomers, at least triisopropylsilyl (meth)acrylate, such as TISMA, and ethyldiethylene glycol acrylate (EDEGA), but additionally, as described herein (meth) ) silyl acrylate comonomers, hydrophilic (meth)acrylate comonomers, and/or non-hydrophilic (meth)acrylate comonomers.

When citing mole percent of a comonomer in a silyl ester copolymer, the mole percent is relative to the total amount (in moles) of each comonomer present in said copolymer. That is, when TISMA and EDEGA are the only comonomers contained in the silyl ester copolymer, the mole % of TISMA is calculated as (TISMA (mol) / (TISMA (mol) + EDEGA (mol))) x 100%. . If only TISMA, EDEGA and methyl methacrylate (MMA) are present, the mole % of TISMA is calculated as (TISMA (moles)/(TISMA (moles) + EDEGA (moles) + MMA (moles))) x 100%. . The weight percentage of the copolymer is calculated similarly. Preferably, the copolymer comprises >90 wt. % by weight.

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

Component (i) represents 2 to 40 mol % of said copolymer, preferably 2 to 30 mol % of said copolymer, especially 5 to 30 mol % of said copolymer, especially 5 to 25 mol % of said copolymer. preferably configured.

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

Component (ii) is triisopropylsilyl (meth)acrylate, preferably TISMA, and constitutes 5-60 mol %, preferably 15-50 mol %, especially 20-45 mol % of said copolymer is preferred.

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

The amount of (i)+(ii) in the copolymer is preferably at most 85% by weight, such as at most 80% by weight, especially at most 78% by weight. The amount of (i)+(ii) in the copolymer may range from 30 to 85 wt%, alternatively from 40 to 80 wt%.

The amount of (i)+(ii) in the copolymer is preferably at most 75 mol %, such as at most 70 mol %, especially at most 65 mol %. The amount of (i)+(ii) in the copolymer may range from 30 to 75 mol %, such as 35 to 70 mol %, or especially 35 to 65 mol %.

(additional hydrophilic (meth)acrylate comonomer)
In some embodiments, the copolymer may contain one or more additional comonomers of formula (I).

wherein R ¹ is H or CH ₃ and R ² is a C3-C18 substituent containing at least one oxygen or nitrogen atom, preferably at least one oxygen atom. However, said comonomer of formula (I) is not EDEGA (which is a separate component, component (i)). As used herein, this structure defines a "hydrophilic" (meth)acrylate comonomer.

As shown in the formula above, the term "hydrophilic (meth)acrylate" means that the ^R2 group in formula (I) contains at least one oxygen or nitrogen atom, preferably at least one oxygen atom. should be included. Additional non-hydrophilic (meth)acrylate comonomers may also be present in which the R2 ^' unit consists solely of C and H atoms, as described in detail below.

In one embodiment, the silyl ester copolymer has the R ² group represented by the formula (CH ₂ CH ₂ O) _n —R ³ , wherein R ³ is a C1-C10 hydrocarbon group, preferably a C1-C10 It contains at least one comonomer represented by formula (I) above which is a C10 alkyl group or a C6-C10 aryl group and n is an integer ranging from 1 to 6, preferably from 1 to 3. Preferably, the R ² group has the formula (CH ₂ CH ₂ O) _n —R ³ where R ³ is a C1-C10 alkyl group, preferably CH ₃ or CH ₂ CH ₃ and n is 1 It is an integer ranging from to 3, preferably 1 or 2.

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

In certain embodiments, the silyl ester copolymer has the formula (I) above, wherein R ² is a saturated cyclic group containing at least one oxygen or nitrogen atom, preferably at least one oxygen atom. containing at least one comonomer More preferably, R ² is a WR ¹⁰ group, R ¹⁰ is a cyclic ester (eg, optionally alkyl-substituted oxolane, oxane, dioxolane, dioxane, etc.) and W is a C1-C4 alkylene and most preferably tetrahydrofurfuryl acrylate (THFA) having the structure:

A particularly preferred amount of the hydrophilic (meth)acrylate of formula (I), if present, is 2 to 25 mol %, preferably 2 to 20 mol %, eg 5 to 15 mol %. When a mixture of comonomers of formula (I) is present, these amounts refer to the sum of the mole fractions of comonomers of formula (I) in the copolymer.

When comonomers of formula (I) are present, particularly preferred comonomers are methoxyethyl methacrylate (MEMA), methoxyethyl acrylate (MEA), ethoxyethyl methacrylate (EEMA), tetrahydrofurfuryl acrylate (THFA ), tetrahydrofurfuryl methacrylate (THFMA), and ethyldiethylene glycol methacrylate (EDEGMA).

In one preferred embodiment, the comonomer does not contain a substantial amount of comonomers of formula (I). That is, said copolymer contains less than 10 mol-%, in particular less than 5 mol-%, in particular less than 2 mol-% of such hydrophilic comonomers.

(additional non-hydrophilic (meth)acrylate comonomer)
Said silyl ester copolymer may comprise one or more additional non-hydrophilic (meth)acrylate comonomers of formula (II).

wherein R ^1′ is H or CH ₃ and R ^2′ is a C1-C8 hydrocarbon group, preferably a C1-C8 alkyl group, most preferably methyl, ethyl, n-propyl, n- Butyl or 2-ethylhexyl. Comonomers represented by formula (II) are referred to herein as "non-hydrophilic" comonomers.

In all embodiments of the invention, said silyl ester copolymer preferably comprises one or more additional non-hydrophilic methacrylates and/or non-hydrophilic acrylates as comonomers. When one or more non-hydrophilic (meth)acrylate comonomers are present, the total amount of these (meth)acrylate comonomers in said silyl ester copolymer is preferably at most 80 mol %, preferably at most 70 mol % , for example in the range from 20 to 70 mol %, for example in the range from 30 to 60 mol %, especially in the range from 35 to 60 mol %.

In one preferred embodiment, TISMA, EDEGA and the non-hydrophilic (meth)acrylate comonomers represented by formula (II) as comonomers together represent >80 mol % of the comonomers in said silyl ester copolymer, preferably constitute >85 mol %, in particular >90 mol %.

In one preferred embodiment, the silyl ester copolymer comprises one or more of the 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. If MMA is present, it is preferably present in an amount of 10-70 mole %, preferably 30-60 mole % of said copolymer. In one preferred embodiment, TISMA, EDEGA and MMA together constitute >80 mol %, preferably >85 mol %, especially >90 mol % of the comonomers in said silyl ester copolymer.

In a particularly preferred embodiment, the copolymer contains 20-60 mol % TISMA, 2-40 mol % EDEGA and 10-70 mol % MMA, especially 20-50 mol % TISMA, 5-30 mol % EDEGA and , containing 30 to 60 mol % of MMA. Additional silyl (meth)acrylates, hydrophilic (meth)acrylates, and/or non-hydrophilic (meth)acrylate comonomers may be included in these embodiments.

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

In one embodiment, the silyl ester copolymer comprises TISMA, EDEGA, MMA, and at least one hydrophilic or non-hydrophilic (meth)acrylate comonomer as comonomers. In some embodiments, the silyl ester copolymer comprises as monomers TISMA, EDEGA, MMA; TISMA, EDEGA, MMA and n-BA; or TISMA, EDEGA, MMA, n-BA and THFA; , consisting essentially of or consisting of these.

(additional (meth) silyl acrylate comonomer)
Said silyl ester copolymer may contain an additional silyl (meth)acrylate comonomer. When present, additional silyl (meth)acrylate comonomers other than triisopropylsilyl (meth)acrylate constitute a maximum of 10 mol% of said copolymer, preferably a maximum of 5 mol% of said copolymer. is preferred. When present, a suitable silyl (meth)acrylate comonomer is preferably represented by formula (III).

wherein 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 a linear or branched C1-C20 alkyl group, a C3-C12 cycloalkyl group, an optionally substituted C6-C20 aryl group, and —OSi(R ⁹ ) selected from the group consisting of ₃ groups,
each R ⁹ is independently a linear or branched C1-4 alkyl group;
n is an integer of 0 to 5, and X is an ethylenically unsaturated group such as an acryloyloxy group, a methacryloyloxy group, a (methacryloyloxy)alkylenecarbonyloxy group, or a (acryloyloxy)alkylenecarbonyloxy group. It will be understood that triisopropylsilyl (meth)acrylate must be present in the copolymer and should be considered excluded from formula (III).

The term "alkyl" includes straight or branched chain alkyl groups such as methyl, ethyl, isopropyl, propyl, and butyl. Particularly preferred cycloalkyl groups include cyclohexyl and substituted cyclohexyl.

Examples of substituted aryl groups include aryl groups substituted with one or more substituents selected from halogen, alkyl groups having from 1 to about 8 carbon atoms, acyl groups, or nitro groups. Particularly preferred aryl groups include substituted or unsubstituted phenyl, benzyl, phenalkyl or naphthyl.

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

Examples of monomers containing silyl ester functional groups are well known. Monomers defined by general formula (III) include: Silyl ester monomers of acrylic and methacrylic acid, such as 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, (meth)acrylic acid Tri-n-hexylsilyl, tri-n-octylsilyl (meth)acrylate, tri-n-dodecylsilyl (meth)acrylate, triphenylsilyl (meth)acrylate, tri-(p-(meth)acrylate) methylphenyl)silyl, tribenzylsilyl (meth)acrylate, ethyldimethylsilyl (meth)acrylate, n-propyldimethylsilyl (meth)acrylate, isopropyldimethylsilyl (meth)acrylate, n-(meth)acrylate Butyldimethylsilyl, isobutyldimethylsilyl (meth)acrylate, tert-butyldimethylsilyl (meth)acrylate, n-pentyldimethylsilyl (meth)acrylate, n-hexyldimethylsilyl (meth)acrylate, (meth)acryl neohexyldimethylsilyl acid, sexyldimethylsilyl (meth)acrylate, n-octyldimethylsilyl (meth)acrylate, n-decyldimethylsilyl (meth)acrylate, dodecyldimethylsilyl (meth)acrylate, (meth)acrylate n-octadecyldimethylsilyl acrylate, cyclohexyldimethylsilyl (meth)acrylate, phenyldimethylsilyl (meth)acrylate, benzyldimethylsilyl (meth)acrylate, phenethyldimethylsilyl (meth)acrylate, (meth)acrylic acid ( 3-phenylpropyl)dimethylsilyl, p-tolyldimethylsilyl (meth)acrylate, isopropyldiethylsilyl (meth)acrylate, n-butyldiisopropylsilyl (meth)acrylate, n-octyldiisopropylsilyl (meth)acrylate, di-n-butylsilyl methyl acrylate (meth), dicyclohexyl methyl acrylate (meth), diphenylsilyl methyl acrylate (meth), tert-butyldiphenylsilyl (meth) acrylate, nonamethyltetrasiloxy (meth) acrylate, Bis(trimethylsiloxy)methyl (meth)acrylate Luciryl, tris(trimethylsiloxy)silyl (meth)acrylates and other compounds described in WO2014/064048 and WO03/080747.

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

(Physical properties of the silyl ester copolymer)
A polymer having an organosilyl ester group is prepared by any of various methods such as solution polymerization, bulk polymerization, emulsion polymerization, and suspension polymerization, using a conventional method or a controlled polymerization method, in the presence of a polymerization initiator, It can be obtained by polymerizing a monomer mixture. When preparing a coating composition using this polymer having an organosilyl ester group, it is preferable to dilute the polymer with an organic solvent to obtain a polymer solution exhibiting an appropriate viscosity. From this point of view, it is desirable to use solution polymerization.

Examples of polymerization initiators include dimethyl 2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(isobutyronitrile ), azo compounds such as azo compounds such as 1,1′-azobis (cyanocyclohexane), tert-butyl peroxypivalate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxydiethyl acetate , tert-butyl peroxyisobutyrate, di-tert-butyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, tert-amyl peroxypivalate, tert-amyl peroxy-2-ethyl Peroxides such as hexanoate, 1,1-di(tert-amylperoxy)cyclohexane, and benzoyl peroxide can be mentioned. These compounds may be used alone or as mixtures of two or more of these compounds.

Examples of organic solvents 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 tert-butyl acetate, amyl acetate, and ethylene glycol methyl ether acetate; 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 ethanol, 1-methoxy-2-propanol; aliphatic hydrocarbons such as white spirit; and optionally mixtures of two or more solvents. These compounds may be used alone or as mixtures of two or more of these compounds. Said copolymer is preferably a random copolymer.

The polymer having an organosilyl ester group thus obtained preferably has a weight average molecular weight of 5,000 to 70,000, preferably 10,000 to 60,000. Mw is measured as described in the Examples section.

The silyl ester copolymer may be provided as a polymer solution. The polymer solution is desirably 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 antifouling coating composition for the purpose of the present invention contains the silyl ester copolymer in an amount of 0.5 to 45% by weight (dry solid content), for example 1.0 to 30% by weight, particularly It is preferably contained in an amount of 5 to 25% by weight.

Said copolymer preferably has a glass transition temperature (Tg) of at least 15°C, preferably at least 20°C, for example at least 22°C. These values are measured according to the Tg test described in the Examples section. Values of less than 80°C, such as values of less than 75°C, such as values of less than 50°C, are preferred.

The antifouling coating compositions of the present invention are optionally mixtures of the silyl ester copolymers of the present invention and other silyl ester copolymers such as those described in US4593055, EP0646630, WO2009/007276, and EP2781567. may include

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

The rosin used in the present invention may be rosin or a derivative thereof, such as a salt thereof, such as those described below. Examples of rosin components include wood rosin, tall oil rosin, gum rosin; rosin derivatives such as hydrogenated and partially hydrogenated rosin, disproportionated rosin, dimerized rosin, polymerized rosin; maleic esters of rosin and hydrogenated rosin. , fumarate esters, glycerol esters, methyl esters, pentaerythritol esters, and other esters; resinates of rosin and polymerized rosins; acid salts; and rosin derivatives as described in WO97/44401. Preferred are gum rosin and gum rosin derivatives.

In the present invention, the antifouling composition as a whole contains 0.5 to 25% by weight, preferably 1 to 15% by weight (dry solid content), preferably 2 to 7% by weight (dry solid content) of the rosin component. is preferred.

The physical properties of the antifouling paint can be adjusted by changing the relative amounts of the silyl ester copolymer and the rosin component.
Accordingly, in one preferred embodiment, the present invention provides a binder comprising a silyl ester copolymer as defined above and rosin or a derivative thereof.

(other binder components)
In addition to the silyl ester copolymer and optional rosin, additional binders can be used to adjust the physical properties of the antifouling coating. Examples of binders that can be used in addition to the silyl ester copolymer and rosin of the present invention include:

Acid-functionalized polymers in which the acid groups are capped with divalent metals attached to monovalent organic residues (e.g. as described in EP0204456 and EP0342276); or divalent metals attached to hydroxyl groups. (e.g. as described in GB2311070 and EP0982324); or amines (e.g. as described in EP0529693);
hydrophilic copolymers such as (meth)acrylate copolymers as described in GB2152947, poly(N-vinylpyrrolidone) copolymers as described in EP0526441 and other copolymers;
(Meth)acrylic polymers and copolymers, especially acrylate binders, such as poly(n-butyl acrylate), poly(n-butyl acrylate-co-isobutyl vinyl ether) and are described in WO 03/070832 and EP 2128208 others such as;
vinyl ether polymers and copolymers such as poly(methyl vinyl ether), poly(ethyl vinyl ether), poly(isobutyl vinyl ether), poly(vinyl chloride-co-isobutyl vinyl ether);
Aliphatic polyesters such as polylactic acid, polyglycolic acid, poly(2-hydroxybutyric acid), poly(3-hydroxybutyric acid), poly(4-hydroxyvaleric acid), polycaprolactone, two units selected from the aforementioned units an aliphatic polyester copolymer comprising at least one species;
metal-containing polyesters, for example as described in EP1033392 and EP1072625 (where the metal is not copper);
alkyd resins and modified alkyd resins;
of at least one monomer selected from a hydrocarbon-based resin, e.g. Hydrocarbon-based resins formed solely from polymerization;
Polyoxalates as described in WO2009/100908 and other condensation polymers as described in WO96/14362.

When other binders are present in addition to the rosin and silyl ester copolymer, the silyl copolymer:binder weight ratio is from 30:70 to 95:5, preferably from 40:60 to 80:20, especially 50. :50 to 70:30. These preferred ratios relate only to the amount of silyl copolymer and additional binder, ie rosin is not included.
Particularly suitable additional binders are (meth)acrylic polymers and copolymers.

(biocide)
Antifouling paints additionally contain compounds that can prevent or remove marine fouling from surfaces. Conventionally, antifouling paint compositions contain copper biocides such as metallic copper, cuprous oxide, copper thiocyanate, and the like.

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

Instead of copper biocides, a range of organic biocides such as 4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole [medetomidine] and 4-bromo-2-(4- Chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile [tralopyril] can be used. Any known biocide can be used in the present invention. Terms such as antifouling agents, antifouling ingredients, biocides, and toxicants are used in the industry to describe known compounds that act to prevent marine fouling on surfaces. The antifoulant of the present invention is a marine antifoulant.

The coating composition may contain a copper biocide, preferably cuprous oxide (Cu ₂ O) and/or copper pyrithione. The coating composition of the present invention may contain other biocides as described in WO2014/064048. Preferred biocides are cuprous oxide, copper thiocyanate, zinc pyrithione, copper pyrithione, zinc ethylene bis(dithiocarbamate) [zineb], 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-Np-tolylsulfamide [tolylufluanid], 4-[1-(2 ,3-dimethylphenyl)ethyl]-1H-imidazole [medetomidine], triphenylboranepyridine [TPBP], and 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole- 3-carbonitrile [tralopyril].

Mixtures of biocides can be used as it is known in the art that different biocides act against different marine fouling organisms.

In another embodiment, the antifouling paint is copper-free. In this embodiment, a preferred biocide combination includes a combination of one or more selected from zinc pyrithione, 4,5-dichloro-2-octyl-4-isothiozoline-3-one, and tralopyril.

The total amount of biocide, if present, may constitute up to 70% by weight of the coating composition, eg 4-60%, eg 5-60%. When copper is present, a suitable amount of biocide may be 20-60% by weight in the coating composition. If copper is to be avoided, it may be used in lower amounts, eg 0.1-20% by weight, eg 0.2-15% by weight. It will be appreciated that the amount of biocide will vary depending on the intended application and the biocide used.

Certain biocides may be encapsulated or carried in an inert carrier or conjugated to other materials for sustained release. These proportions relate to the amount of active biocide present and not to the carrier used.

(other ingredients)
In addition to the silyl ester copolymer and the optional ingredients described above, the antifouling coating composition of the present invention optionally contains other binders, inorganic or organic pigments, extenders and fillers, additives, solvents, thinners. It may further contain one or more selected ingredients.

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

Examples of extenders and fillers are minerals such as dolomite, plastolite, calcite, quartz, barite, magnesite, aragonite, silica, wollastonite, talc, chlorite, mica, kaolin and feldspar; calcium carbonate, carbonate. Synthetic inorganic compounds such as magnesium, barium sulfate, calcium silicate and silica; uncoated or coated hollow and solid glass beads, uncoated or coated hollow and solid ceramic beads, polymethylmethacrylate, poly( It is a porous material made of polymeric materials such as methyl methacrylate-co-dimethacrylate), poly(styrene-co-dimethacrylate ethylene glycol), poly(styrene-co-divinylbenzene), polystyrene, and polyvinyl chloride. Polymeric and inorganic microspheres such as small diameter beads.

Examples of additives that can be added to the antifouling coating composition are reinforcing agents, thixotropic agents, thickening agents, anti-settling agents, wetting and dispersing agents, plasticizers, and solvents.

Examples of reinforcing materials 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 and rubber fibers. natural and synthetic organic fibers such as, acrylic fibers, polyamide fibers, polyimides, polyester fibers, polyhydrazide fibers, polyvinyl chloride fibers, polyethylene fibers, and other fibers as described in WO 00/77102. Preferably, said fibers have an average length of 25-2000 μm, an average thickness of 1-50 μm, and a ratio of said average length to said average thickness of at least 5.

Examples of thixotropic agents, thickeners and anti-settling agents are silicas such as fumed silicas, organically modified clays, amide waxes, polyamide waxes, amide derivatives, polyethylene waxes, oxidized polyethylene waxes, hydrogenated castor oil waxes, ethyl cellulose, stearin. aluminum acids, and mixtures thereof.

Examples of plasticizers are chlorinated paraffins, phthalates, phosphates, sulfonamides, adipic acid and epoxidized vegetable oils.

Examples of dehydrating and drying agents are anhydrous calcium sulfate, calcium hemihydrate, anhydrous magnesium sulfate, anhydrous sodium sulfate, anhydrous zinc sulfate, molecular sieves and zeolites; trimethyl orthoformate, triethyl orthoformate, tripropyl orthoformate, orthoformic acid orthoesters such as triisopropyl, tributyl orthoformate, trimethyl orthoacetate and triethyl orthoacetate; ketals; acetals; enol ethers; trimethyl borate, triethyl borate, tripropyl borate, triisopropyl borate, tributyl borate and boric acid orthoborates such as tri-tert-butyl; silicates such as trimethoxymethylsilane, tetraethylsilicate, ethylpolysilicate; and isocyanates such as p-toluenesulfonyl isocyanate.
Preferred dehydrating and drying agents are silicates and inorganic compounds.

Examples of stabilizers that contribute to the storage stability of the antifouling coating composition include bis(2,6-diisopropylphenyl)carbodiimide, poly(1,3,5-triisopropylphenylene-2,4-carbodiimide), etc. Carbodiimide compounds are other stabilizers as described in patent EP2725073.

Generally, any of these optional ingredients may be present in an amount ranging from 0.1 to 20%, usually 0.5 to 20%, preferably 0.75 to 15% by weight of the antifouling composition. It will be appreciated that the amounts of these optional ingredients will vary depending on the end use.

It is highly preferred that the antifouling composition contains a solvent. The solvent is preferably volatile and preferably organic. Examples of organic solvents and thinners include aromatic hydrocarbons such as xylene, toluene and mesitylene; Esters such as butyl acetate, tert-butyl acetate, amyl acetate, isoamyl acetate, ethylene glycol methyl ether acetate, propyl propionate, and butyl propionate; Ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dibutyl ether, dioxane, and tetrahydrofuran alcohols such as n-butanol, isobutanol, benzyl alcohol; ether alcohols such as butoxyethanol, 1-methoxy-2-propanol; aliphatic hydrocarbons such as white spirit; It is a mixture of
Preferred solvents are aromatic solvents, especially xylene, and mixtures of aromatic hydrocarbons.

It is preferred that the amount of solvent is as low as possible. The solvent content may be 50% by weight or less of the composition, preferably 45% by weight or less, for example 40% by weight or less, but may be as low as 15% by weight or less, for example 10% by weight or less. Again, those skilled in the art will appreciate that the solvent content will vary depending on the other ingredients present and the end use of the coating composition.
Alternatively, the coating may be dispersed in an organic non-solvent for the film-forming components in the coating composition or in the aqueous dispersion.

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

More preferably, the antifouling coating composition has an amount of volatile organic compounds (VOC) of less than 500 g/L, preferably less than 400 g/L, such as less than 390 g/L. VOC levels can be calculated (ASTM D5201-01) or measured, and are preferably measured.

The antifouling coating composition of the present invention can be applied to all or part of any object surface that is susceptible to fouling. The surface may be in water permanently or intermittently (eg, due to tidal movement, loading with different cargo or swelling). The object surface is usually the hull of a ship or the surface of a fixed marine object such as an oil platform or a buoy. Application of the coating composition can be accomplished by any convenient technique, such as painting (eg, with a brush or roller) or spraying the coating onto the object. Usually the surface should be kept away from seawater when the application is carried out. Application of the paint can be accomplished as is commonly known in the art.

When applying an antifouling paint to an object (eg, a ship's hull), the surface of the object is usually not protected by a single antifouling coat. Depending on the nature of the surface, antifouling paints may be applied directly to existing paint systems. Such paint systems may include multiple layers of paints of various common types (eg, epoxy, polyester, vinyl, acrylic, or mixtures thereof). If the surface has a clean, intact antifouling coating from a previous application, the new antifouling coating is applied directly, usually in one or two coats, and in exceptional cases more coats. can do.

Alternatively, an engineer may start with an uncoated surface (eg, steel, aluminum, plastic, composite, fiberglass or carbon fiber). To protect such surfaces, the overall coating system usually includes one or two antirust coatings, one tie-coat and one or two antifouling coatings. These coatings are well known to those skilled in the art.
In exceptional cases an additional antifouling coating may be applied.
Accordingly, in a further embodiment, the present invention provides a substrate having applied thereon an antirust coating, such as an epoxy primer, a tie layer, an antifouling coating composition as defined herein.

The invention will now be described in detail with reference to the following non-limiting examples.
(material and method)

(Overview of procedure for preparing copolymer solution)
A quantity of solvent is charged to a temperature controlled reactor equipped with a stirrer, cooler, nitrogen inlet and inlet. The reactor is heated to and maintained at the reaction temperature shown in Table 2. A premix consisting of monomer, initiator and solvent is prepared. The premix is charged into the reactor at a constant rate over 2 hours under a nitrogen atmosphere. The reactor is maintained at or heated to the additional reaction temperature indicated in Table 2 for an additional hour. A post-addition of additional initiator solution is then added to the reaction mixture. The reaction is maintained at temperature for an additional 2 hours and then cooled to room temperature.

(Measurement of viscosity of polymer solution)
Polymer viscosity is measured according to ASTM D2196-15 test method A at 12 rpm using a Brookfield DV-I viscometer with an LV-2 or LV-4 shaft. The polymer is temperature-controlled to 23.0°C ± 0.5°C before measurement.

(Measurement of non-volatile matter content of polymer solution)
The non-volatile content of polymer solutions is measured according to ISO 3251. A 0.5 g ± 0.1 g specimen is taken and dried in a ventilated oven at 150°C for 30 minutes. The weight of residue is considered non-volatiles (NVM). Non-volatile content is expressed in weight percent. Values shown are averages of three points.

(Measurement of average molecular weight distribution of polymer)
Polymers are identified by gel permeation chromatography (GPC) measurements. Molecular weight distribution (MWD) was measured using a Polymer Laboratories PL-GPC 50 device, two Polymer Laboratories PLgel 5 μm Mixed-D columns were connected, tetrahydrofuran (THF) was used as an eluent, normal temperature, and a steady flow rate of 1 mL/min. was measured with a refractive index (RI) detector. The column was calibrated using Polymer Laboratories polystyrene standards EasiVials PS-H. Polymer Labs. Data processing was performed using the software Cirrus from the company. 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. Samples were filtered through a 0.45 μm nylon filter prior to analysis. The weight average molecular weight (Mw), number average molecular weight (Mn), and polydispersity index (PDI) expressed as Mw/Mn are listed in each table.

(Measurement of glass transition temperature)
Glass transition temperature (Tg) is measured by differential scanning calorimetry (DSC) method. The DSC method was performed on a TA Instruments DSC Q200. Samples were prepared by transferring a small amount of polymer solution to an aluminum pan and drying at 50°C for a minimum of 10 hours followed by 150°C for 3 hours. A sample of approximately 10 mg of dry polymer was measured in an open aluminum pan and scans were recorded at a heating rate of 10° C./min and a cooling rate of 10° C./min, with an empty pan serving as a control. Data processing was performed using the software Universal Analysis from TA Instruments. The point at which the glass transition range changes on the second heat as defined in ASTM E1356-08 is reported as the Tg of the polymer.

(Overview of procedure for preparing antifouling paint composition)
The ingredients were mixed in the proportions shown in Table 4. The mixture was dispersed in a 250 mL paint can in the presence of glass beads (approximately 2 mm in diameter) using a shaker for 15 minutes. The glass beads were filtered out before testing.

(Measurement of paint viscosity using a cone and plate type viscometer)
According to ISO 2884-1: 1999, using a digital cone and plate type viscometer with the temperature set to 23 ° C., operating at a shear rate of 10000 s ^-1 , viscosity measurement range 0 to 10 P Viscosity of the antifouling paint composition was measured. Results are shown as the average of three measurements.

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

(Calculation of polishing rate of antifouling coating film on rotating disc in seawater)
The polishing rate is measured by measuring the decrease in film thickness of the coating film over time. PVC discs are used in this test. A film applicator is used to apply the coating composition to the disk in radial stripes. Measure the thickness of the dry coating with a surface profiler. A PVC disc is placed on a shaft and rotated in a vessel with seawater flowing through it. Let the speed of the rotating shaft be 16 knots at the average simulated speed on the disk. Pre-filtered and temperature-controlled natural seawater at 25°C ± 2°C is used. Periodically remove the PVC disc to measure the film thickness. The discs are washed and dried overnight at room temperature prior to measuring film thickness.

Claims (33)

(i) ethyl diethylene glycol acrylate (EDEGA); and (ii) a silyl ester copolymer containing triisopropylsilyl (meth)acrylate as a comonomer. The silyl ester copolymer according to Claim 1, wherein the ratio of (i):(ii) in said copolymer is in the range of 5:95 to 60:40 (mol/mol). 3. A silyl ester copolymer according to claim 1 or 2, wherein component (ii) is triisopropylsilyl methacrylate (TISMA). The silyl ester copolymer according to claim 1 or 2, wherein the amount of (i) in the silyl ester copolymer is 2-40 mol%. The silyl ester copolymer according to claim 4, wherein the amount of (i) in the silyl ester copolymer is 2-30 mol%. The silyl ester copolymer according to claim 4, wherein the amount of (i) in said silyl ester copolymer is 5-25 mol%. A silyl ester copolymer according to any one of claims 1 to 6, wherein the amount of (ii) in said silyl ester copolymer is from 5 to 60 mol% of said copolymer. A silyl ester copolymer according to claim 7, wherein the amount of (ii) in said silyl ester copolymer is from 15 to 50 mol% of said copolymer. A silyl ester copolymer according to claim 7, wherein the amount of (ii) in said silyl ester copolymer is from 20 to 45 mol% of said copolymer. The silyl ester copolymer according to any one of claims 1 to 9, wherein said silyl ester copolymer further comprises one or more hydrophilic comonomers represented by formula (I).

wherein R ¹ is H or CH ₃ and R ² is a C3-C18 substituent containing at least one oxygen or nitrogen atom. However, the hydrophilic comonomer represented by formula (I) is not EDEGA. The silyl ester copolymer according to claim 10, wherein R ² is a C3-C18 substituent containing at least one oxygen atom. one or more of said hydrophilic comonomers ^comprises an _R2 group represented by the formula ⁽ _CH2CH2O ) _n -R3 ^, wherein R3 is a C1-C10 alkyl group or a C6-C10 aryl group; A silyl ester copolymer according to claim 10 or 11, wherein n is an integer ranging from 1 to 6, provided that said comonomer is not EDEGA. The silyl ester copolymer according to claim 12, wherein n is 1-3. One or more hydrophilic comonomers of formula (I) are present, said hydrophilic comonomers comprising R ² groups of formula (CH ₂ CH ₂ O) _n —R ³ , where R ³ is alkyl and n is an integer ranging from 1 to 3, with the proviso that said comonomer is not EDEGA. _15. The silyl ester copolymer of claim 14 _, wherein R3 is ^CH3 or _CH2CH3 . 15. The silyl ester copolymer of claim 14, wherein n is 1 or 2. one or more hydrophilic comonomers of formula (I) are methoxyethyl methacrylate (MEMA), methoxyethyl acrylate (MEA), ethoxyethyl methacrylate (EEMA), and tetrahydrofurfuryl acrylate (THFA) 11. The silyl ester copolymer of claim 10 , selected from Silyl ester copolymer according to any one of claims 1 to 17, further comprising one or more non-hydrophilic comonomers represented by formula (II).

wherein R ^1′ is H or CH ₃ and R ^2′ is a C1-C8 hydrocarbyl group. The silyl ester copolymer according to claim 18, wherein R ^2' is a C1-C8 alkyl group. A silyl ester copolymer according to claim 18 or 19, wherein R ^2' is methyl, ethyl, n-propyl, 2-ethylhexyl or n-butyl. Any of claims 18-20, wherein the one or more non-hydrophilic comonomers of formula (II) are selected from among methyl methacrylate (MMA) and n-butyl acrylate (n-BA) The silyl ester copolymer according to item 1. A silyl ester copolymer according to any one of claims 1 to 21, comprising MMA as comonomer in an amount of 10 to 70 mol%. The silyl ester copolymer according to claim 22, comprising MMA as a comonomer in an amount of 30-60 mol%. A silyl ester copolymer according to any one of claims 1 to 23, comprising n-butyl acrylate (n-BA) as comonomer in an amount of 2 to 20 mol%. The silyl ester copolymer according to claim 24, comprising n-butyl acrylate (n-BA) as a comonomer in an amount of 2-15 mol%. The silyl ester copolymers are TISMA, EDEGA, and
a. MMA;
b. MMA and n-BA; or c. MMA, n-BA and THFA
The silyl ester copolymer according to any one of claims 1 to 25, comprising or consisting only of. A binder for an antifouling coating composition comprising the silyl ester copolymer according to any one of claims 1 to 26 and rosin or a derivative thereof. An antifouling paint composition comprising the copolymer according to any one of claims 1 to 26 and at least one antifouling agent. 29. The antifouling paint composition of claim 28, wherein the antifouling agent comprises cuprous oxide and/or copper pyrithione. A method of protecting an object from fouling, comprising:
30. A method comprising coating at least a portion of said object prone to fouling with the antifouling coating composition of claim 28 or 29. An object coated with the antifouling coating composition of claim 28 or 29. 32. An object according to claim 31 , wherein the object is coated with an anticorrosive coating, a tie layer and an antifouling coating composition according to claim 28 or 29. 32. An object according to claim 31, wherein the object is coated with the antifouling coating composition according to claim 28 or 29 which coats the antifouling coating composition pre-existing on the substrate.