WO2001060932A1 - Antifouling paint composition - Google Patents

Abstract

An antifouling paint composition containing, as a binder, a resin having groups of the formula (1): -S(O)2-O-(Si(R?4)(R5)-O)¿n-Si(R?1)(R2)R3¿, wherein n is 0-200, preferably 0-10, and each of R?1, R2, R3, R4 and R5¿ which are independent of one antoher, is a hydrocarbon group selected from the group consisting of C¿1-18? alkyl groups, C1-18 alkoxy groups, C7-19 aralkyl groups, C3-9 cycloalkyl groups and C6-18 aryl groups, in its molecule.

Description

ANTIFOUHNG PAINT COMPOSITION

FIELD OF THE INVENTION

The present invention relates to an antifouhng paint composition for preventing attachment of marine organisms on the surface of objects in the sea for a long period of

BACKGROUND OF THE INVENTION

Various marine organisms will attach on the surface of fishing nets, maritime structures or bottom shell platings of ships or vessels located under the sea water surface, and there will be problems such that in the case of ships or vessels, efficient navigation will be hindered, and in the case of maritime structures and fishing nets, the useful life will be remarkably shortened To cope with such problems, it is common to use antifouhng paints containing various antifouhng agents

Typical antifouhng paints which have heretofore been used, include insoluble matrix type antifouhng paints having an antifouhng agent incorporated to a binder comprising a resm insoluble in sea water, such as a vinyl type resm, an alkyd resm or chlorinated rubber, and rosin soluble in sea water, and soluble matrix type antifouhng paints containing as a binder a tin-containing resm which gradually hydrolyses in sea water and having an antifouhng agent incorporated as the case requires

However, with the above-mentioned insoluble matrix type antifouhng paints, the antifouhng agent will elute together with rosin into sea water, whereby a constant antifouhng effect for a long period of time can not be expected, and further, the insoluble resm component remaining in the coating film, will form a skeleton structure, whereby particularly when applied to ships or vessels, the fπctional resistance between sea water and the coating film surface will increase, thus leading to drawbacks such as a decrease in the speed and an increase of the fuel costs On the other hand, the above-mentioned soluble matrix type antifouhng paint containing a tin-containing resm as a binder component, has an excellent antifouhng effect, but is problematic from the viewpoint of safety and sanitation, or environmental protection In Japan, its use is prohibited by regulations Under the circumstances, as antifouhng paints having the above-mentioned problems of the soluble matrix type antifouhng paint solved, there have been proposed an antifouhng paint containing as a binder a carboxyl group-containing resin having a high acid value, for example, in JP 9132736 A; an antifouhng paint containing as a binder, a hydrolysable resin containing silyl groups, for example, in WO 84/02915; an antifouhng paint containing as a binder, a hydrolysable resin containing a metal such as zinc or copper, for example, in EP 0 204 456 B1 ; and an antifouhng paint containing as a binder, a hydrolysable resin containing sulfonic groups reacted with an amine compound, for example, in JP 6040812 A , JP 6073312 A or JP 6122842 A.

However, these antifouhng paints were all inferior in the long term antifouhng properties as compared with the conventional antifouhng paint using a tin-containing resin as a binder. Further, the antifouhng paints disclosed in the above-mentioned JP 9132736 A and WO 84/02915 were inferior in the storage stability when a metal-containing antifouhng agent was incorporated.

DESCRIPTION OF THE INVENTION

The present invention provides and possible improved solutions to these problems of the tin-free paint of the prior art, and it is an object of the present invention to provide an antifouhng paint composition which has little problem from the viewpoint of safety and sanitation, or environmental protection, and which is capable of preventing attachment of various marine organisms on the surface of objects such as fishing nets, maritime structures or bottom shell platings of ships or vessels located under the sea water surface for a long period of time.

The present inventors have conducted an extensive study to accomplish the above object and as a result, have found it possible to accomplish the object by using a resin having silylated sulfonate groups of a specific structure, as a binder for an antifouhng paint. The present invention has been accomplished on the basis of this discovery.

Thus, the present invention provides an antifouhng paint composition containing, as a binder, a resin having groups of the formula (1):

-S(0)₂-0-(Si(R⁴)(R⁵)-0)_n-Si(R¹)(R²)R³ (1) wherein n is 0-200, preferably 0-10 and each of R¹, R² R³ R⁴ and R⁵ which are independent of one another, is a hydrocarbon group selected from the group consisting of d ₁₈ alkyl groups, Ci ₁₈ alkoxy groups, C_{7 19} aralkyl groups, C_{3 9} cycloalkyl groups and C_{6 18} aryl group, in its molecule

Now, the present invention will be described in detail with reference to the preferred embodiments

The antifouhng paint composition of the present invention comprises the above binder, optionally an antifouhng agent and a solvent as the main constituting components and may further contain various additives pigments, dyes, further binder components such as rosin or modified rosins and fibres as the case requires This will be explained in more detail below

The above-mentioned binder is a resm having silylated sulfonate groups of the formula (1)

-S(0)₂-0-(Sι(R⁴)(R⁵)-0)_n-Sι(R¹)(R²)R³ (1)

as defined above

One presently preferred class of silylated sulfonate groups of the formula (1) are those with the formula (1a)

-S(0)₂-0-Sι(R¹)(R²)R³ (1a)

wherein R¹, R² and R³ have the same meanings as R¹, R² and R³ in the formula (1), corresponding to the formula (1) where n is 0

A typical example of the resin having such silylated sulfonate groups, is an organic solvent-soluble type resm prepared by a copolymeπsation reaction of a polymeπsable unsaturated monomer (a) having a silylated sulfonate group of the above formula (1) with other polymeπsable unsaturated monomer(s) (b) copolymeπsable with the monomer (a), in an organic solvent in the presence of a polymerisation initiator in accordance with a usual method, for example, at a temperature of from 40 to 150°C such as 80 to 150°C for from 2 to 15 hours such as 3 to 15 hours

The above polymensable unsaturated monomer (a) is one which is obtainable by reacting (i) a monomer having a polymensable unsaturated double bond and a sulfonic acid group with (n) an organosilyl compound of the formula

H-(Sι(R⁴)(R⁵)-0)_n-Sι(R¹)(R )R³ (2) or

X-(Sι(R⁴)(R⁵)-0)_n-Sι(R¹)(R²)R³ (3)

wherein n, R¹, R² R³ R⁴ and R⁵ have the same meanings as n, R¹, R² R³ R⁴ and R⁵ in the formula (1) and X designates a halogen atom such as chlorine or bromine, preferably chlorine, for example, in an organic solvent in the presence of a catalyst at a temperature of from 0 to 120°C for from 2 to 8 hours In case of an organosilyl compound of the formula (2), platinum, palladium, aluminium, rhodium or ruthenium type is suitable as the catalyst mentioned above On the other hand, in case of an organosilyl compound of the formula (3), a basic compound such as tπethylamine or imidazole is suitable

Presently preferred organosilyl compounds leading to silylated sulfonates of the formula (1 a) are the tnorganosilyl compounds of formula

H-Sι(R¹)(R²)R³ (2a) or

X-Sι(R¹)(R )R³ (3a)

When the resins are not of the formula (1a), i e n is different from 0, n is typically in the range of 1-200, preferably 1-10, particularly in the range of 1-4 such as 1 , 2 or 3

The monomers (i) are typically monomers of the formula CH₂=CR-(C(0)-0)_k-(Q)-S(0)₂OH where k is 0 or 1 , and wherein R is hydrogen or methyl and Q is selected from linear or branched C^-alkylene and C₆ is arylene (such as phenylene), for example

(meth)acrylsulfonιc acid, 2-sulfoethyl (meth)acrylate, sulfopropyl(meth)acrylate, 4- sulfobutyl (meth)acrylate, styrenesulfonic acid, vmylsulfonic acid, allylsulfonic acid, or of the formula CH₂=CR-C(0)-NH-(Q)-S(0)₂OH wherein R and Q are as above, for example 2-(meth)acryiamιde-2-methylpropanesulfonιc acid The monomers may also be present in the form of the alkali metal salt, e g the sodium salt The organosilyl compound (u) is a compound of the formula (2) or (3), (2a) or (3a), respectively wherein each of R¹, R² R³ , R⁴ and R⁵ have the same meanings as n, R , R² R³ R⁴ and R⁵ in the formula (1)

Here, the d ₁₈ alkyl group may be linear or branched The alkyl group is typically a Ci ₈ alkyl group and may, for example, be a methyl group, an ethyl group, a n-propyl group, an iso-propyl group, a n-butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group or an octyl group A preferred alkyl group is one having a carbon number of from 3 to 6 The term "linear or branched C^ ₈-alkylene" for Q is intended to mean any biradical of a Ci ₈-alkyl group

The Ci is alkoxy group may be linear or branched The alkoxy group is typically a C-i ₁₈ alkoxy group and may, for example, be a methoxy group, an ethoxy group, a n-propoxy group, an iso-propoxy group, an butoxy group, an iso-butoxy group, a sec-butoxy group, a tert-butoxy group, a pentoxy group, a hexyloxy group or an octyloxy group A preferred alkoxy group is one having a carbon number of from 3 to 5

The C_{7 19} aralkyl (aryl-d ₁₃-alkyl) group may, for example, be a benzyl group, a 2- phenylethyl group, or a 3-phenylpropyl group

The C_{3 9} cycloalkyl group may, for example, be a cyclohexyl group, a cycloheptyl group, a cyclooctyl group or a cyclononyl group

The aryl group may, for example, be a phenyl group or a naphthyl group

It is currently envisaged that the promising properties of the novel antifouhng paints of the invention at least in part resides in the fact that the silylated sulfonate groups will tend to hydrolyse upon contact with the aqueous environment The rate of hydrolysis of the individual silylated sulfonate monomers will in part depend on the nature of the silyl substituents, in particular on the substituents on the silicon atom bound directly to the sulfonate group, i e the substituents R¹, R² and R³ where n is 0 and substituents R⁴ and R⁵ (in particular those neighbouring the sulfonate group, where n>0 It is generally believed - and also supported by the literature - that larger substituents and in particular branched substituents will lead to a decrease in hydrolysis rate) Preferred meanings of the symbols R¹, R², R³, R⁴ and R⁵ in the formulae above are d ₈ alkyl, benzyl and phenyl In a presently particularly interesting embodiment where n is 0, at least one, preferably two, in particular all three, of R¹ , R², and R³ are a branched alkyl group such as isopropyl, isobutyl, tert-butyl and thexyl (2,3-dιmethyl-but-2-yl) In a presently particularly interesting embodiment where n>0, at least one, preferably both, of R⁴ and R⁵ are a branched alkyl group such as isopropyl, isobutyl, tert-butyl and thexyl (2,3-dιmethyl-but-2-yl) In these embodiments, it is preferred that the substituents on the silyl group which is attached to the sulfonate group, are bound to the silicon atom via a secondary or, preferably, a tertiary carbon atom

The organosilyl compound of the formula (2a) may, for example, be tπmethylsilane, tnethylsilane, tπ-n-propylsilane, tn-iso-propylsilane, tn-n-butylsilane, tn-iso-butylsilane, dimethylhexylsilane, tπphenylsilane, dibutylhexylsilane, dibutylphenylsilane, di-tert- butylphenylsilane, diphenyl-tert-butylsilane, dimethyloctylsilane, di-tert-butylmethylsilane, tri-tert-butylsilane, tert-butyl-di-isobutylsilane, tert-butyl-di-isopropylsilane, thexyl-di- isobutylsilane or thexyl-di-isopropylsilane

Further, the organosilyl compound of the formula (3a) may, for example, be tnmethyl- chlorosilane, tnethylchlorosilane, tπ-n-propylchlorosilane, tnisopropylchlorosilane, tri-n- butylchlorosilane, tnisobutylchlorosilane, tri-tert-butylchlorosilane, dibutylhexylchloro- silane, dimetyl n-propylchlorosilane, di-tert-butylmetylchlorosilane, dimethylbutylchloro- silane, dimethyloctylchlorosilane, dimethyldodecylchlorosilane, di-iso-propyloctylchloro- silane, dimetyloctadecylchlorosilane, tnphenylchlorosilane, tπbenzylchlorosilane, ditert- butylphenylchlorosilane, diphenylmetylchlorosilane, dipheyltert butylchlorosilane, di- metyl(3,3-dιmetylbutyl)chlorosιlane, tnbutoxychlorosilane, dibutylphenylchlorosilane, di- tert-butylmethylchlorosilane, tri-tert-butylchlorosilane, tert-butyl-di-isobutylchlorosilane, tert-butyl-di-isopropylchlorosilane, thexyl-di-isobutylchlorosilane or thexyl-di-isopropyl- chlorosilane as well as the corresponding bromo compounds

The polymensable unsaturated monomer (a) having such a silylated sulfonate group, may, for example, be tnmethylsilylsulfoethyl (meth)acrylate, tπethylsilylsulfoethyl (meth)acrylate, dibutylphenylsilylsulfoethyl (meth)acrylate, di-tert-butylmethylsilylsulfoethyl (meth)acrylate, trι-tert-butylsιlylsulfoethyl(meth)acrylate, tert-butyl-di-isobutylsilylsulfoethyl- (meth)acrylate, tert-butyl-dι-ιsopropylsιlylsulfoethyl(meth)acrylate, thexyl-dusobutylsilyl- sulfoethyl(meth)acrylate, thexyl-di-isopropylsilylsulfoethyl(meth)acrylate, triisopropylsilyl- sulfopropyl(meth)acrylate, di-tert-butylmethylsilylsulfopropyl (meth)acrylate, tritertbutyl- silylsulfopropyl(meth)acrylate, tert-butyl-di-isobutylsilylsulfopropyl(meth)acrylate, tert-butyl- di-isopropylsilylsulfopropyl(meth)acrylate, thexyl-di-isobutylsilylsulfopropyl(meth)acrylate, thexyl-di-isopropylsilylsulfopropyl(meth)acrylate, triisopropylsilylsulfobutyl (meth)acrylate, triisobutylsilylsulfobutyl (meth)acrylate, triphenylsilylsulfobutyl(meth)acrylate, tertbutyldi- phenylsilylsulfobutyl(meth)acrylate, dimethyl tertbutyisilylsulfobutyl (meth)acrylate, ditert- butylmethylsilylsulfobutyl (meth)acrylate, tri-tert-butylsilylsulfobutyl(meth)acrylate, tert- butyl-di-isobutylsilylsulfobutyl(meth)acrylate, tert-butyl-di-isopropylsilylsulfobutyl(meth)- acrylate, thexyl-di-isobutylsilylsulfobutyl(meth)acrylate, thexyl-diisopropylsilylsulfobutyl- (meth)acrylate, trimethylsilylsulfostyrene, triisopropylsilylsulfostyrene, triisobutylsilyl- sulfostyrene, dibutylphenylsilylsulfostyrene, dimethyl tert-butylsilylsulfostyrene, di- tertbutylmethylsilylsulfostyrene, tri-tert-butylsilylsulfostyrene, tert-butyl-di-isobutylsilyl- sulfostyrene, tert-butyl-di-isopropylsilylsulfostyrene, thexyl-diisobutylsilylsulfostyrene, thexyl-di-isopropylsilylsulfostyrene, triethylsilylsulfovinyl, di-tertbutylmethylsilyl-sulfovinyl, t -tert-butylsilylsulfovinyl, tert-butyl-di-isobutylsilylsulfovinyl, tert-butyl-di-isopropylsilyl- sulfovinyl, thexyl-di-isobutylsilylsulfovinyl, thexyl-di-isopropylsilylsulfovinyl trimethyl- silylsulfoallyl, triisopropylsilylsulfoallyl, triisobutylsilylsulfoallyl, dibutylphenylsilylsulfoallyl, dimethyl tertbutylsilylsulfoallyl, ditertbutylmethylsilylsulfoallyl, t tertbutylsilylsulfoallyl, tertbutyldiisobutylsilylsulfoallyl, tertbutyldiisopropylsilylsulfoallyl, thexyl-di-isobutylsilyl- sulfoallyl, thexyl-di-isopropylsilylsulfoallyl triisopropylsilylsulfo-allylbenzene, triisobutyl- silylsulfoallylbenzene, dibutylphenylsilylsulfoallylbenzene, dimethyl tert-butylsilylsulfo- allylbenzene, di-tert-butylmethylsilylsulfoallylbenzene, tri-tert-butylsilylsulfoallylbenzene, tert-butyl-di-isobutylsilylsulfoallylbenzene, tert-butyl-di-isopropylsilylsulfoallylbenzene, thexyl-di-isobutylsilylsulfoallylbenzene or thexyi-di-isopropylsilylsulfoallylbenzene.

It should be understood that more than one type of the polymensable unsaturated monomer(a) may be included in one polymer.

As the above-mentioned other polymensable unsaturated monomer(s) (b) copolyme sable with the polymensable unsaturated monomer (a) having a silylated sulfonate group, various polymerisable unsaturated monomers commonly used for acrylic resins or vinyl resins, may be used without any particular restrictions. Specifically, they may, for example, be (meth)acrylate type monomers such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, iso-propyl (meth)acrylate, n-butyl (meth)acrylate, iso-butyl (meth)acrylate, pentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)- acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, α-chloroethyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxy- ethyl (meth)acrylate, methoxypropyl (meth)acrylate, ethoxypropyl (meth)acrylate; styrene type monomers such as styrene, methylstyrene, chlorostyrene and methoxystyrene; carboxyl group-containing monomers such as (meth)acrylic acid, crotonic acid, itaconic acid, itaconic acid half ester, maleic acid and maleic acid half ester; hydroxyl group- containing monomers such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)- acrylate and 4-hydroxybutyl acrylate; amide group-containing monomers such as (meth)- arylamide, N-methylolacrylamide and maleinamide; a ino group-containing monomers such as 2-aminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, 3-aminopropyl (meth)acrylate and 2-butylaminoethyl (meth)acrylate; epoxy group-containing monomers such as glycidyl (meth)acrylate; vinyl type monomers such as vinyl acetate, vinyl chloride, vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl isobutyl ether, vinylpyrrolidone and vinylpyridine; and ethylene, butadiene and (meth)acrylonitrile; and organosilyl monomers such as tri-n-butyl silyi(meth)acrylate, t-butyl dimethylsilyl(meth)acrylate, thexyl dimethylsilyl(meth)acrylate, tri-iso-propylsilyl(meth)acrylate. These monomers may be used alone or in combination as a mixture of two or more of them.

As the solvent for dissolving or dispersing the organic solvent type resin which will be a binder, various organic solvents which have been commonly used for paints can be used without any particular restrictions so long as they are capable of dissolving the resin.

Specifically, it may, for example, be a hydrocarbon type solvent such as toluene or xylene; a ketone type solvent such as methyl ethyl ketone or acetone; an ester type solvent such as ethyl acetate, propyl acetate or butyl acetate; or an ether type solvent such as ethylene glycol monoethyl ether or ethyl ether. These solvents may be used alone or in combination as a mixture of two or more of them.

Examples of solvents in which the components of the antifouhng paint are dissolved or dispersed are alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol and benzyl alcohol; alcohol/water mixtures such as ethanol/water mixtures; aliphatic, cycloaliphatic and aromatic hydrocarbons such as white spirit, cyclohexane, toluene, xylene and naphtha solvent; ketones such as methyl ethyl ketone, acetone, methyl isobutyl ketone, methyl isoamyl ketone, diacetone alcohol and cyclohexanone; ether alcohols such as 2-butoxyethanol, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethyl ether and butyl diglycol, esters such as ethyl acetate, propyl acetate, methoxypropyl acetate, n-butyl acetate and 2-ethoxyethyl acetate, chlorinated hydrocarbons such as methylene chloride, tetrachloroethane and tπchloroethylene, and mixtures thereof

In the present invention, the resin for the binder may be of a non-aqueous dispersion type The non-aqueous dispersion type resm is a non-aqueous dispersion resin composed of a core component dispersed in a hydrocarbon type solvent and substantially insoluble in the solvent and a shell component (a dispersion stabiliser) which dissolves or swells in the solvent, wherein at least one of the core and shell components contains silylated sulfonate groups of the formula (1) or (1a)

The above hydrocarbon type solvent includes aliphatic, ahcychc and aromatic solvents In the present invention, it is preferred to employ an aliphatic hydrocarbon solvent and/or an ahcychc hydrocarbon solvent, or such a solvent in the major amount

Such aliphatic and ahcychc hydrocarbon solvents include, for example, n-hexane, iso- hexane, n-heptane, n-octane, iso-octane, n-decane, n-dodecane, cyclohexane, methyl- cyclohexane and cycloheptane Commercial products include, for example, mineral spirit ec, vm&p naphtha and shellzole 72 (manufactured by Shell Chemical Co ), naphtha no 3, naphtha no 5, naphtha no 6 and solvent no 7 (manufactured by Exxon Chemical Co ), ip solvent 1016, ip solvent 1620 and ip solvent 2835 (manufactured by idemitsu Petrochemical co , ltd ), and pengazole an-45 and pengazole 3040 (manufactured by Mobile Oil Co )

Further, the aromatic solvents include, for example, benzene, toluene, xylene and decalin Commercial products include, for example, SOLVESSO 100 and SOLVESSO 150 (manufactured by Exxon Chemical Co ), and SWAZOLE (manufactured by Maruzen Oil Co , Ltd )

These hydrocarbon type solvents may be used alone or in combination as a mixture of two or more of them The non-aqueous dispersion resin may be prepared by a method wherein a polymerisable unsaturated monomer which is soluble in a hydrocarbon solvent and which is polymerisable to form a polymer (the core component) which is insoluble in the hydrocarbon solvent, is subjected to dispersion polymerisation in accordance with a conventional method in the hydrocarbon solvent in the presence of a shell component (the dispersion stabiliser) made of a polymer which dissolves or swells in the solvent.

The monomer for forming the polymer for the shell component is not particularly limited so long as it dissolves in a hydrocarbon solvent to be used, and the polymer formed after the polymerisation will dissolve or swell therein, and the above-mentioned various polymerisable unsaturated monomers may be used. However, it is preferred to use a mixture of polymerisable unsaturated monomers containing from 30 to 100 weight % , preferably from 50 to 98 weight %, of a (meth)acrylate type monomer.

As the monomer for forming the polymer for the core component, the above-mentioned various polymerisable unsaturated monomers can be used so long as they are soluble in a hydrocarbon solvent to be used, and the polymers formed after the polymerisation will be insoluble in the solvent. Preferred is a monomer whereby the polymer will be hydrophilic.

The polymerisable unsaturated monomer which imparts hydrophilicity, may, for example, be the above-mentioned carboxyl group-containing monomer, the hydroxyl group- containing monomer or the amino group-containing monomer.

In the present invention, it is important that the above-described polymerisable unsaturated monomer (a) is used as an essential component for at least one of the polymer for the shell component and the polymer for the core component constituting the non-aqueous dispersion resin, to incorporate silylated sulfonate groups of the formula (1).

The weight ratio of the core component to the shell component (core component/shell component) is not particularly limited. However, it is usually from 90/10 to 10/90, preferably from 80/20 to 25/75.

In the non-aqueous dispersion type resin, fine particles of the core component insoluble in an organic solvent are present as a part of the resin, and accordingly, the paint viscosity is relatively low as compared with an organic solvent-soluble resm, whereby it is possible to reduce the amount of the organic solvent to have a high solid content Further, by changing the amount of silylated sulfonate groups contained in the core component and the shell component, it is possible to adjust the hydrolysmg rate, i e a higher ratio of silylated sulfonate groups will increase the hydrolysmg rate for the polymer

In the present invention, from the viewpoint of the storage stability, an antifouhng paint composition is particularly preferred wherein a non-aqueous dispersion type resm containing silylated sulfonate groups, is used as the core component

In the description of the resins of an organic solvent-soluble type and a non-aqueous dispersion type having silylated sulfonate groups of the formula (1) to be used in the present invention, a silylated sulfonate group-containing monomer is used as a starting material in the synthesis of each of the resins However, it is possible to prepare a resm from the above-mentioned monomer (i) having a sulfonic acid group and a polymensable unsaturated monomer (b), and then a tπorganosilyl compound (n) of the formula (2) or (3) is reacted to impart silylated sulfonate groups to the resin

Typically, the resm as the binder to be used in the present invention, is prepared by the above-described method, wherein the amount of the silylated sulfonate group-containing polymensable unsaturated monomer (a) of the formula (1) is usually from 1-90, e g 3-90 such as 3-80 weight %, preferably from 3-60, e g 5-60 such as 5-30, e g 10-20 weight %, in the total monomer

If the amount of the silylated sulfonate group-containing polymensable unsaturated monomer (a) of the formula (1) is smaller than the above range, the long term antifouhng property tends to deteriorate On the other hand, if it is too large, the coating film strength tends to deteriorate

It should be noted that the percentage amounts of unsaturated monomer (a) indicated above relates to the synthesised polymer A certain fraction of the silylated sulfonate groups in the polymer may undergo hydrolysis in the preparation step due to presence of moisture A certain degree of hydrolysis is normally acceptable As mentioned herein, the general rate of hydrolysis of the silylated sulfonate groups may be adjusted by appropriate selection of the silyl substituents Further, the number average molecular weight of the resin as the binder is usually from 1 ,000 to 300,000, preferably from 5,000 to 100,000.

As the antifouhng agent which can be used in the present invention, various antifouhng agents which have been commonly used in antifouhng paints, can be used without any particular restriction. Typical examples include metallo-dithiocarbamates such as bis(dimethyldithiocarbamato)zinc, ethylene-bis(dithiocarbamato)zinc, ethylene-bis(dithio- carbamato)manganese, and complexes between these; bis(1-hydroxy-2(1 H)-pyridine- thionato-0,S)-copper; copper acrylate; bis(1-hydroxy-2(1 H)-pyridinethionato-0,S)-zinc; phenyl(bispyridyl)-bismuth dichloride; metal biocides such as copper, copper metal alloys such as copper-nickel alloys; metal oxides such as cuprous oxide and cupric oxide (even though e.g. cuprous oxide and cupric oxide may have pigment charac-teristics, it is understood that in the present context such agents are only considered as "antifouhng agents"); metal salts such as cuprous thiocyanate, basic copper carbonate, copper hydroxide, barium metaborate, and copper sulfide; heterocychc nitrogen compounds such as 3a,4,7,7a-tetrahydro-2-((trichloromethyl)-thio)-1 H-isoindole-1 ,3(2H)-dione, pyridine- triphenylborane, 1-(2,4,6-trichlorophenyl)-1 H-pyrrole-2,5-dione, 2,3,5,6-tetrachloro-4- (methylsulfonyl)-pyridine, 2-methylthio-4-tert-butylamino-6-cyclopropylamine-s-triazin, and quinoline derivatives; heterocychc sulfur compounds such as 2-(4-thiazolyl)benzimidazole, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 4,5-dichloro-2-octyl-3(2H)-isothiazoline, 1 ,2- benzisothiazolin-3-one, and 2-(thiocyanatomethylthio)-benzothiazole; urea derivatives such as N-(1 ,3-bis(hydroxymethyl)-2,5-dioxo-4-imidazolidinyl)-N,N'-bis(hydroxymethyl)- urea, and N-(3,4-dichlorophenyl)-N,N-dimethylurea, N,N-dimethylchlorophenylurea; amides or imides of carboxylic acids; sulfonic acids and of sulfenic acids such as 2,4,6- trichlorophenyl maleimide, 1 , 1 -dichloro-N-((dimethylamino)sulfonyl)-1 -fluoro-N-(4-methyl- phenyl)-methanesulfenamide, 2,2-dibromo-3-nitrilo-propionamide, N-(fluorodichloro- methylthio)-phthalimide, N,N-dimethyl-N'-phenyl-N'-(fluorodichloromethylthio)-sulfamide, and N-methylol formamide; salts or esters of carboxylic acids such as 2-((3-iodo-2- propynyl)oxy)-ethanol phenylcarbamate and N,N-didecyl-N-methyl-poly(oxyethyl)- ammonium propionate; amines such as dehydroabiethylamines and cocodimethylamine; substituted methane such as di(2-hydroxy-ethoxy)methane, 5,5'-dichloro-2,2'-dihydroxy- diphenylmethane, and methylene-bisthiocyanate; substituted benzene such as 2,4,5,6- tetrachloro-1 ,3-benzenedicarbonitrile, 1 , 1 -dichloro-N-((dimethylamino)-sulfonyl)-1 -fluoro- N-phenylmethanesulfenamide, and 1-((diiodomethyl)sulfonyl)-4-methyl-benzene; tetraalkyl phosphonium halogenides such as tπ-n-butyltetradecyl phosphonium chloride, guanidme derivatives such as n-dodecylguanidme hydrochloπde, disulfides such as bis- (dιmethylthιocarbamoyl)-dιsulfιde, tetramethylthiuram disulfide, and mixtures thereof

In the antifouhng paint, the total amount of the antifouhng agent(s) may be in the range of 0-80%, such as 2-75%, by wet weight of the paint, preferably 5-75%, such as 5-70%, by wet weight of the paint Depending upon the type and specific activity of the antifouhng agent, the total amount of the agent may, e g , be 5-60% or 10-50% by wet weight of the paint Alternatively the total amount of the antifouhng agent(s) may be expressed as being in the range of 0-70%, e g 2-50%, such as 3-50%, by solids volume of the paint, preferably 5-50%, such as 5-40%, by solids volume of the paint Depending upon the type and specific activity of the antifouhng agent, the total amount of the agent may, e g , be 5- 15% or 10-25% by solids volume of the paint

In the present invention, especially a dehydrating agent is preferably incorporated, so that hydrolysis will not proceed by an influence of moisture during the storage of the antifouhng paint

The dehydrating agent may, for example, be synthetic zeolite, sepiohte, anhydrous gypsum, orthopropionic acid ester, orthoformic acid ester, orthoacetic acid ester alkoxysilane, alkyl silicates like tetra ethyl ortosihcate, or isocyanates It is used preferably in an amount of from 0 1 to 20% wet weight in the paint

The blend proportions of the respective components constituting the antifouhng paint composition of the present invention are usually such that the binder resm is from 5-60 such as 5-40% by wet weight, preferably from 15 to 40% by wet weight, the antifouhng agent is from 0 to 80%, preferably from 2-75% such as 5-60% by wet weight, and the solvent is from 10 to 60% such as 10-50%, preferably from 10 to 40 such as 15-40% by wet weight

Alternatively the blend proportions of the respective components constituting the antifouhng paint composition of the present invention is such that the binder resm is from 5-70%, preferably from 10-65% by solids volume of the paint the antifouhng agent is from 0 to 70%, preferably from 5-50% such as 5-40% by solids volume Pigments, further binder components e.g., rosin or modifying rosins .fibres and various additives are not essential constituting components. However, such pigments, plasticizers, further binder components e.g., rosin or modifying rosins, fibres and the additives may be incorporated in a total amount of up to 40% such as 30% by wet weight.

Examples of pigments are grades of titanium dioxide, red iron oxide, zinc oxide, carbon black, graphite, yellow iron oxide, red molybdate, yellow molybdate, zinc sulfide, antimony oxide, sodium aluminium sulfosilicates, quinacridones, phthalocyanine blue, phthalocyanine green, titaniumdioxide, black iron oxide, graphite, indanthrone blue, cobalt aluminium oxide, carbazole dioxazine, chromium oxide, isoindoline orange, bis-acetoacet- o-tolidiole, benzimidazolon, quinaphtalone yellow, isoindoline yellow, tetrachloro- isoindolinone, quinophthalone yellow. Such materials are characterised in that they render the final paint coating non-transparent and non-translucent. The pigments may further be selected from pigment-like ingredients such as fillers. Examples of fillers are calcium carbonate, dolomite, talc, mica, barium sulfate, kaolin, silica, perlite, magnesium oxide, calcite and quartz flour, etc. These materials are characterised in that they do not render the paint non-translucent and therefore do not contribute significantly to hide any material below the coating of the paint of the invention.

In a preferred embodiment of the present invention, the paint has a total pigment content (pigment and pigment-like ingredients) in the range of 1-60%, preferably 1-50%, such as 5-40% in particular 1-25% such as 1-15%, of the wet weight of the paint.

Alternatively the total pigment content (pigment and pigment-like ingredients) can be expressed as being in the range of 1-60%, preferably 1-50%, in particular 1-25% such as 1-15%, of the solids volume of the paint.

Examples of dyes are 1,4-bis(butylamino)anthraquinone and other anthraquinone derivatives; toluidine dyes etc.

Examples of additives are plasticizers such as chlorinated paraffin; phthalates such as dibutyl phthalate, benzylbutyl phthalate, dioctyl phthalate, diisononyl phthalate and diisodecyl phthalate; phosphate esters such as tricresyl phosphate, nonylphenol phosphate, octyloxipoly(ethyleneoxy)ethyl phosphate, t butoxyethyl phosphate, iso- octylphosphate and 2-ethylhexyl diphenyl phosphate; sulfonamides such as N-ethyl-p- toluensulfonamide, alkyl-p-toluene sulfonamide, adipates such as bιs(2-ethylhexyl)- adipate), dnsobutyl adipate and dioctyladipate, phosphoric acid tnethyl ester, butyl stearate, sorbitan tnoleate, and epoxidised soybean oil, surfactants such as derivatives of propylene oxide or ethylene oxide such as alkylphenol-ethylene oxide condensates, ethoxylated monoethanolamides of unsaturated fatty acids such as ethoxylated mono- ethanolamides of Imoleic acid, sodium dodecyl sulfate, alkylphenol ethoxylates, and soya lecithin, wetting agents and dispersants such as those described in M Ash and I Ash, "Handbook of Paint and Coating Raw Materials, Vol 1", 1996, Gower Publ Ltd , Great Britain, pp 821-823 and 849-851 , defoaming agents such as sihcone oils, stabilisers such as stabilisers against light and heat, e g hindered amine light stabilisers (HALS), 2- hydroxy-4-methoxybenzophenone, 2-(5-chloro-(2H)-benzotrιazol-2-yl)-4-methyl-6-(tert- butyl)phenol, and 2,4-dιtert-butyl-6-(5-chlorobenzotπazol-2-yl)phenol, stabilisers against moisture such as molecular sieves or water scavengers such as synthetic zeolites, substituted isocyanates, substituted silanes and ortho formic acid tnethyl ester, stabilisers against oxidation such as butylated hydroxyanisole, butylated hydroxytoluene, propyl- gallate, tocopherols, 2,5-dι-tert-butyl-hydroquιnone, L-ascorbyl palmitate, carotenes, vitamin A, inhibitors against corrosion such as aminocarboxylates, calcium silico- phosphate, ammonium benzoate, baπum/calcium/zinc/magnesium salts of alkyl- naphthalene sulfonic acids, zinc phosphate, zinc metaborate, coalescing agents such as glycols, 2-butoxy ethanol, and 2,2,4-tπmethyl-1 ,3-pentanedιol monoisobutyrate, and thickeners and anti-settling agents such as colloidal silica, hydrated aluminium silicate (bentonite), aluminiumtπstearate, aluminiummonostearate, πcinus oil, xanthan gum, salicylic acid, chrysotile, pyrogenic silica, hydrogenated castor oil, organo-modified clays, polyamide waxes and polyethylene waxes

It is preferred that the paints according to the present invention comprises dyes and additives in a cumulative content of 0-10% by wet weight Alternatively the cumulative content of dyes and additives can be expressed as being 0-15% by solids volume

As will be understood by the person skilled in the art, one or several further binder components may be present in the binder system Examples of such further binder components are

oils such as linseed oil and derivatives thereof, castor oil and derivatives thereof, soy bean oil and derivatives thereof, other polymeric binder components such as saturated polyester resins; polyvinylacetate, polyvinylbutyrate, polyvinylchloride-acetate, copolymers of vinyl acetate and vinyl isobutyl ether; vinylchloride; copolymers of vinyl chloride and vinyl isobutyl ether; alkyd resins or modified alkyd resins; hydrocarbon resins such as petroleum fraction condensates; chlorinated polyolefines such as chlorinated rubber, chlorinated polyethylene, chlorinated polypropylene; styrene copolymers such as styrene/butadiene copolymers, styrene/methacrylate and styrene/acrylate copolymers; acrylic resins such as homopolymers and copolymers of methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate and isobutyl methacrylate; hydroxy-acrylate copolymers; polyamide resins such as polyamide based on dimerised fatty acids, such as dimerised tall oil fatty acids; cyclised rubbers; epoxy esters; epoxy urethanes; polyurethanes; epoxy polymers; hydroxy-polyether resins; polyamine resins; etc., as well as copolymers thereof; rosin or rosin equivalents (e.g. those generally and specifically described in

WO 97/44401 which is hereby incorporated by reference).

It should be understood that the group of other polymeric binder components may include polymeric flexibilisers such as those generally and specifically defined in WO 97/44401 which is hereby incorporated by reference.

In the present context the term "% by wet weight" is intended to mean the weight/weight percentage of the wet matter of the paint. It should be understood that solvents are included.

In the present context the term "% by solids volume" is intended to mean the volume/volume percentage of the dry matter of the paint. It should be understood that any solvents are not included in the contents stated as "% by solids volume". Instead, the content of solvent(s) is expressed as "solids volume ratio" or SVR which indicates the volume of the dry matter in relation to the total volume of the paint including the solvent.

Apart from the above constituents, the antifouhng paint composition may also comprise fibres (e.g. those generally and specifically described in WO 00/77102 which is hereby incorporated by reference). At present, especially preferred are mineral fibres such as mineral-glass fibres, wollastonite fibres, montmoπllonite fibres, tobermoπte fibres, atapulgite fibres, calcined bauxite fibres, volcanic rock fibres, bauxite fibres, rockwool fibres, and processed mineral fibres from mineral wool

It is however also presently believed that some organic fibres can be especially advantageous within the present invention Particularly preferred examples of such fibres are aromatic polyamide fibres, aromatic polyester fibres, aromatic polyimide fibres, cellulose fibres, cotton fibres, wood fibres, rubber fibres and fibres of derivatives of rubber, polyolefm fibres, polyacetylene fibres, polyester fibres, acrylic fibres and modified acrylic fibres, acrylonitnle fibres (e g preoxidised acrylonitπle fibres), elastomeπc fibres, protein fibres, algmate fibres, poly(ethylene terephthalate) fibres, polyvmyl alcohol fibres, aliphatic polyamide fibres, polyvinylchloπde fibres, polyurethane fibres, vinyl polymeric fibres, and viscose fibres Presently even more preferred examples of such fibres are polyethylene fibres, polypropylene fibres, cotton fibres, cellulose fibres, polyacrylonitπle fibres, preoxidised polyacrylonitπle fibres, and polyester fibres

In view of the above, it is presently believe that a particularly interesting group of fibres (including inorganic as well as organic fibres) is mineral fibres such as mineral-glass fibres, wollastonite fibres, montmoπllonite fibres, tobermoπte fibres, atapulgite fibres, calcined bauxite fibres, volcanic rock fibres, bauxite fibres, rockwool fibres, processed mineral fibres from mineral wool, polyethylene fibres, polypropylene fibres, cotton fibres, cellulose fibres, polyacrylonitnle fibres, preoxidised polyacrylonitrile fibres, and polyester fibres

The concentration of the fibres is normally in the range of 0 1-50%,e g 0 1-25% by wet weight of the paint, such as 0 5-10% by wet weight of the paint Especially relevant concentrations of fibres, depending upon the type and size of the fibres, may be 2-10%, such as 2-7%, or 3-10%, such as 3-8% by wet weight of the paint

Alternatively the concentration of the fibres is in the range of 0 1-25% by solids volume of the paint, such as 0 5-10% by solids volume of the paint Especially relevant concentrations of fibres, depending upon the type and size of the fibres, may be 2-10%, such as 2- 7%, or 3-10%, such as 3-8% by solids volume of the paint It should be understood that the above ranges refer to the total amount of fibres, thus, in the case where two or more fibre types are utilised, the combined amounts should fall within the above ranges.

The antifouhng paint composition of the present invention is prepared usually by mixing and dispersing the above components all at once or in a divided fashion by a conventional apparatus for producing paints, such as a ball mill, a pearl mill, a three-roll mill, a high speed disperser. The antifouhng paints according to the invention, optionally containing fibres, may be filtrated using bag filters, patron filters, wire gap filters, wedge wire filters, metal edge filters, EGLM turnoclean filters (ex Cuno), DELTA strain filters (ex Cuno), and Jenag Strainer filters (ex Jenag), or by vibration filtration. The antifouhng paint composition of the present invention thus prepared may be coated as it is or after having the viscosity adjusted by a diluting solvent, on a ship or a maritime structure having a rust preventive coating material coated thereon, by e.g. airless spray coating, air spray coating, roller coating or brush coating. . The exact technique chosen depends upon the object to be protected and also upon the particular composition (such as its viscosity etc.) and upon the particular situation. Preferred applications techniques are spraying and by means of a brush or a roller.

Depending on the application technique, it is desirable that the paint comprises solvent(s) so that the SVR is in the range of 30-100%, such as 30-70%.

The antifouhng paint according to the invention may be applied to the marine structure to be protected in one or several successive layers, typically 1 to 5 layers, preferably 1 to 3 layers. The dry film thickness (DFT) of the coating applied per layer will typically be 10 to 300 μm, preferably 20 to 250 μm, such as 40 to 200 μm. Thus, the total dry film thickness of the coating will typically be 10 to 900 μ , preferably 20 to 750 μm, in particular 40 to 600 μm, such as 80 to 400μm.

The marine structure to which the paint according to the invention may be applied to may be any of a wide variety of solid objects that come into contact with water, for example vessels (including but not limited to boats, yachts, motorboats, motor launches, ocean liners, tugboats, tankers, container ships and other cargo ships, submarines (both nuclear and conventional), and naval vessels of all types); pipes; shore and off-shore machinery, constructions and objects of all types such as piers, pilings, bridge substructures, floatation devices, underwater oil well structures etc, nets and other manculture installations, cooling plants, and buoys, and is especially applicable to the hulls of ships and boats and to pipes

Prior to the application of a paint of the invention to a marine structure, the marine structure may first be coated with a primer-system which may comprise several layers and may be any of the conventional primer systems used in connection with application of antifouhng paints to marine structures Thus, the primer system may include an anti- corrosive primer optionally followed by a layer of an adhesion-promoting primer In a preferred embodiment, the primer-system is a composition having a polishing rate of less than 1 μm per 10,000 Nautical miles, i e the primer is a non-self-pohshing coating

The above-mentioned primer system may, for example, be a combination of an epoxy resin having an epoxy equivalent of from 160 to 600 with its curing agent (such as an am o type, a carboxylic acid type or an acid anhydride type), a combination of a polyol resm with a polyisocyanate type curing agent, or a coating material containing a vinyl ester resin, an unsaturated polyester resm or the like, as a binder, and, if required, further containing a thermoplastic resm (such as chlorinated rubber, an acrylic resm or a vinyl chloride resm), a curing accelerator, a rust preventive pigment, a coloring pigment, an extender pigment, a solvent, a trialkoxysilane compound, a plasticizer, an additive (such as an antisaggmg agent or a precipitation preventive agent), or a tar epoxy resin type coating material, as a typical example

As mentioned herein, the coating resulting from the paint according to the present invention is preferably self-polishing Thus, the antifouhng paint (actually the coating) should have a polishing rate of at least 1 μ per 10,000 Nautical miles (18,520 km) Preferably the polishing rate is in the range of 1-50 μm, in particular in the range of 1-30 μm per 10,000 Nautical miles (18,520 km)

In one embodiment, the present invention relates of a composition comprising

a binder resm in an amount of from 5-75%, preferably from 5 to 60% by wet weight, one or more antifouhng agent(s) in a total amount of from 0 to 80%, preferably from 5-75%, such as 5-60% by wet weight In another embodiment, the present invention relates to a composition comprising:

5-40% by wet weight of a resin, as a binder, having groups of the formula (1) 2-75% by wet weight of an antifouhng agent 0-30% by wet weight of additional binder components

0-40% by wet weight of additives (including dehydrating agents, fibres, pigments, etc.) 10-40% by wet weight of a solvent

In another embodiment, the present invention relates of a composition comprising:

10-65% by solids volume of a resin, as a binder, having groups of the formula (1) 0-70% by solids volume of an antifouhng agent 0-55% by solids volume of further binder components.

0-45% by solids weight of additives (including dehydrating agents, fibres, pigments, etc.) SVR 30-100%

EXPERIMENTAL

The respective tests were carried out in accordance with the following methods.

Polishing Rate Test

An stainless steel test panel (13.5 x 7 cm²) with a curvature corresponding to that of a cylindrical drum with a diameter of 1 m is first coated with 40 μm of an epoxy primer (Hempadur Primer 15300 ex Hempel's Marine Paints A/S). After 24 hours, the panel is coated with 80 μm (DFT) of a commercial vinyl primer (Hempanyl Tar 16280 ex Hempel's Marine Paints A/S) applied by air spraying. After minimum 24 hours drying in the laboratory at room temperature the test paint is applied by air spraying in two coats in a DFT of approximately 100 μm per coat (total test paint DFT: 200 μm). Recoating interval between two coats of test paint: 24 hours. The initial thickness of the coat of the test paint is measured using an ISOSCOPE MP-3. The panel is dried for at least 1 week in the laboratory at room temperature before testing.

The test panel is fixed onto the convex surface of a cylindrical drum of 1 m in diameter and is rotated in sea water with a salinity in the range of 37-38 parts per thousand at an average temperature of 17-18°C at a test site in the harbour of Villanova y La Geltru in Northeastern Spam which is situated at longitude 41 2°N (see also Morale, E & Anas, E , Rev Iber Corros y Prot , vol XIX(2), 1988, pp 91-96) The rotor is rotated at a peripheral speed of 15 knots for a relative distance of 33 100 Nautical miles The thickness is controlled with periodic inspections using the ISOSCOPE MP-3 The polishing is the difference between the film thickness measures at a given inspection and the initial film thickness The polishing rate is expressed as the polishing measured in μm per 10,000 Nm

Blister Box Test

Preparation of panels

Acrylic panels (155x100x5 mm) are first coated with 80 μm (dry film thickness, DFT) of a commercial vinyl tar primer (Hempanyl 16280, from Hempel^'s Marine Paints) applied by air spraying After 12-36 hours of drying in the laboratory at room temperature antifouhng paints (model paints or commercial paints) are applied in the following way A template (acrylic panel (155x100x5) with 4 holes (diameter = 41 mm)) is placed and fixed on top of the above mentioned panel coated with the primer The antifouhng paint adjusted to an viscosity of 70-75 KU (25°C) is weighed into one of the holes The amount of antifouhng paint weighed into the whole correspond to a final DFT of 500 μm The paint is spread through the hole surface through circular movements of the panel Four paints may be applied to each panel (one in each hole) The template is removed 1-1 hours after the application The panels are dried for 4-5 days in the laboratory at room temperature before testing

Testing

Tests panels are tested in a Cleveland Condensation Tester (QCT from Q-Panel) in condensation and dry-off mode CCT equipment is described in standard method ASTM D 1735-92 Testing water resistance of coatings using water fog apparatus Coated specimens are placed in an enclosed chamber where cycles of water fog (10 hours)/dryιng (2 hours) are applied The temperature in the chamber is maintained at 50°C During the water fog cycle water penetrates into the film while during the drying cycle water "escapes" from the paint film The test is operated for two months and the paints are evaluated every week for film defects as described below.

Every week the paints are evaluated with respect to the degree of cracking and the degree of flaking in accordance with the guidelines set forth in ISO standard 4628, parts 4 and 5.

Evaluation of the degree of cracking is based on the below ranking (ISO standard 4628, part 4):

Density of cracking Ranking Value

None 0

Less than few 1 Few 2

Medium 3

Medium - dense 4

Dense 5

Size of cracks Ranking Value

Not visible under x 10 magnification 0

Only visible under magnification up to x 10 1

Just visible with normal corrected vision 2

Clearly visible with normal corrected vision 3 Large cracks generally up to 1 mm wide 4

Very large cracks generally more than 1 mm wide 5

Hydrolysis test

In order to have a self-polishing antifouhng technology, it is a requirement that the polymer through controlled hydrolysis transforms from a hydrophobic state to a hydrophilic state. By hydrolysis of tri-alkyl silylated sulfonate polymers in aqueous solution, tri-alkylsilanols are liberated. The hydrolysis method describes how to measure the rate of dissociation of trialkylsilanols from trialkylsilylated sulfonate polymers. The amount of triisopropyl silanol liberated by hydrolysis was determined by gas chromatography (GC). Procedure

A solution of polymer is applied to a filter paper and the solvent is allowed to evaporate overnight. The dry film is immersed in media and left for hydrolysis. The amount of tri- alkylsilanol liberated by hydrolysis as a function of time can be determined by gas chromatography (GC).

Sample preparation

Place a piece of filter paper on top of a plastic beaker. Weigh (4 decimals) approximately 0.2 g of polymer solution on the middle of the filter paper. Make sure that all the polymer is kept on the filter paper. Leave overnight in own at 50°C for evaporation of solvents. Cut excess filter paper away from the dry polymer film and put sample into a 8 ml test tube. Fill 4 ml of hydrolysis medium into tube. Close and shake. Leave the capped tube on shaking table for hydrolysis.

Measurement

Add (4 decimals) 0.02 g of dodecane (C₁₂ - internal GC standard) to the sample (containing the tri-alkyl silylated sulfonate polymer) in test tube and shake. Add approximately 2 ml of toluene to the sample and shake. Centrifuge the sample (15000 rpm, 10 min.). Transfer the toluene phase (top phase) to a 2 ml GC vial. Inject 1.0 μl of the toluene phase into the GC. Run the sample on GC with the following conditions:

Column temperature program

Temp, °C Time, min Rate , °C/min

Step l 75 0 1

Step 2 80 0 15

Step 3 305 0 0

Injection port temperature, °C 150

Detector temperature, °C 320

Carrier gas Helium

Pressure, psi 12

Linear gas velocity, m/min 25

Split 1 :30

Gas chromatography equipped with a 25QC3/BPX 5-1.0 column from SGE, Australia (25 m, 0.33 mm i.d., 1 μm 5% diphenyl dimethyl polysiloxane, bonded phase), a split injector, a flame ionisation detector and an integrating and recording device.

Calibration standards were made by dissolving 0.02 g of internal standard and 0.02 g of triisopropylsilanol in 2 mL of toluene.

Antifouhng property test

Antifouling property test, static panel variant

An acrylic test panel (15 x 20 cm²), sandblasted on one side to facilitate adhesion of the coating., is first coated with 80 μm (DFT) of a commercial chlorinated rubber primer (Hempatex HI-BUILD 46330 ex Hempel's Marine Paints A/S) applied by air spraying. After a minimum drying time of 24 hours in the laboratory at room temperature the test paint is applied with a four sided "Bar" type applicator, with four gap sizes with a film width of 80 mm. One coat in a DFT of 90-100 μm. After at least 72 hours drying the test panels are fixed on a rack and immersed in sea water. Vilanova test variant

Vilanova i la Geltrύ in Northeastern Spain In this test site the panels are immersed in sea water with a salinity in the range of 37-38 parts per thousand at an average temperature of 17-18°C.

Singapore variant

In this test site the panels are immersed in sea water with a salinity in the range of 29-31 parts per thousand at a temperature in the range of 29-31 °C Every 5-8 weeks, inspection of the panels are made and the antifouhng performance is evaluated according to the following scale

Antifouhng property test, rotor variant

Preparation and inspection intervals as for the "Polishing rate test" Evaluation according to the scale above

Compositions illustrating the invention were prepared as described in the following-

Preparation of resin solutions (A) to (C)

Synthesis of Triisopropylsilylsulfobutyl methacrylate (TIPSS-BMA) monomers

CH₂=C(CH₃)-C(0)-0-(CH₂)₄-S(0)₂-0-Sι[CH(CH₃)₂]3 TIPSS-BMA monomer can be synthesised by reacting triisopropylsilane (TIPS) and a monomer having a polymerisable unsaturated double bond and a sulfonic acid group, such as sodium butylmethacrylate sulfonate (SBMAS), in a two-stage reaction.

Stage 1 : De-saltlation

Sodium is removed from SBMAS by adding hydrochloric acid to form butylmethacrylate sulfonic acid (SBMA). The resulting NaCI is removed from the system before the stage 2.

CH₂=C(CH₃)COO(CH₂)₄S0₂0^"Na⁺ + HCI — > (SBMAS)

CH₂=C(CH₃)COO(CH₂)₄S0₂OH + NaCI (SBMA)

Stage 2: Silylation

SBMA is reacted with triisopropylsilane (TIPS) to form a TIPSS-BMA monomer. A catalyst is required to promote silylation. A detail description can be found herein above.

CH₂=C(CH₃)COO(CH₂)₄S0₂OH + H-Si(i-Pr)₃ (+ catalyst) — > (SBMA) (TIPS)

CH₂=C(CH₃)COO(CH₂)₄S0₂0-Si(i-Pr)3 + H₂ (g) (TIPSS BMA)

Polymerisation

Into a reactor equipped with a stirrer, a thermometer and a condenser, 80 parts of xylene were charged, and while maintaining the temperature at 100°C, a dropping monomer mixture containing a polymerisation initiator (2,2'-azobis(2-methylbutyronitrile)) (ABN-E), as shown in Table 1 , was drop wise added over a period of 3 hours with stirring. Then, at the same temperature, the mixture was reacted for 1 hour while adding 0.5 part of the above polymerisation initiator in 3 parts of xylene. The resin is then held at the same temperature for a further 1 hour. The resin is adjusted to approximately 50% NV (nonvolatile) contents with xylene. In this manner, resin solutions (A) to (C) were prepared.

Preparation of non-aqueous dispersions (D)

Into a reactor equipped with a stirrer, a thermometer and a condenser, 22 5 parts of turpentine was charged, and while maintaining the temperature at 100°C, a dropping monomer mixture containing a polymerisation initiator (tert-butylperoxy 2-ethyl hexanoate) KE-0 ex Kayaku Akzo Corporation, Japan, as shown in Table 2, was drop wise added over a period of 3 hours with stirring Then, at the same temperature, a mixture comprising 0 25 parts of the above-mentioned polymerisation initiator and 11 0 parts of turpentine, was drop wise added over a period of one hour, with stirring Thereafter, the mixture was reacted at the same temperature for 3 hours, and further 16 1 parts of turpentine was added to obtain shell component solution a

Then, into a reactor equipped with a stirrer, a thermometer and a condenser, the above shell component solution was charged, and while maintaining the temperature at 105°C, a dropping monomer mixture containing a polymerisation initiator (a xylene solution containing 40% of benzoyl peroxide) BMT-K40 Nippon Oil & Fats Co , Ltd, Japan, as shown in Table 3, was drop wise added over a period of 3 hours with stirring Then, at the same temperature, a mixture comprising 0 42 parts of the above-mentioned polymerisation initiator and 5 0 parts of turpentine, was drop wise added over a period of 1 5 hours Thereafter, the mixture was reacted at the same temperature for 2 5 hours, and 28 05 parts of turpentine was further added, to obtain non-aqueous dispersions (D)

Table 3 (unit: parts)

Charaterisation

Non-volatile contents (NV) was measured by drying 1 g resin at 150°C for 60 minutes. Acid value (AV) was measured by titration of 0.5 g resin in MEK with 0.1 M KOH in methanol. Model Paint Composition A

The following model paints were prepared Model Paint Composition A (with the co- polymer A or B or C as described herein, and the references trιιsopropylsιlyl(meth) 5 acrylate based copolymer or tnbutyltin methacrylate methyl methacrylate co-polymer (Cutmox 1000/60 He ex Acima AG, Switzerland))

47%, by solids volume of a binder

1 8% by solids volume thixotropic agent HDK N20 (ex Wacker Chemie, Germany) 10 1 7% by solids volume thixotropic agent Aditix M60 (ex Supercoloπ, Italy)

1 7% by solids volume wetting agent Disperbyk 164 (ex Byk Chemie, Germany)

23% by solids volume of Cuprous Thiocyanate (ex Bardyke Chemicals LT, UK ) or 23% by solids volume of Cuprous oxide, low tint (LoLo Tint CDC ex American Chemet Export

Corporation, USA ) 15 4% by solids volume of titanium dioxide Cπstal 121 (ex Cπstal, Saudi Arabia)

10% by solids volume of Copper Omadme (ex Arch Chemicals, Ireland)

54% by solids volume of 4,5-dιchloro-2-n-octyl-n-ιsothιazohne-3-on (Sea-Nine 211 ex

Rohm and Haas, USA )

5% by solids volume of water Scavanger Si kat TES 40 (ex Wacker Chemie, Germany) 20

Solids volume ratio (SVR) 43-48, Solvent xylene

1) tnbutyltin methacrylate methyl methacrylate co-polymer (Cutmox 1000/60 He ex Acima AG, Switzerland) (non-volatile matter 60% weight)

2) Trιιsopropylsιlyl(meth)acrylate based copolymer (non-volatile matter 50% weight) 3) HDK N20 (ex Wacker Chemie, Germany)

4) Aditix M60 (ex Supercolon, Italy)

5) Disperbyk 164 (ex Byk Chemie, Germany) 6) TES 40 (ex Wacker Chemie, Germany)

7) Cπstal 121 (ex Cπstal, Saudi Arabia)

8) Copper Omadme (ex Arch Chemicals Ireland)

9) 4,5-dιchloro-2-n-octyl-n-ιsothιazohne-3-on (Sea-Nine 211 ex Rohm and Haas, USA ) 5 10) Cuprous Thiocyanate (ex Bardyke Chemicals LT, UK )

11 ) LoLo Tint CDC (ex American Chemet Export Corporation, USA )

It should be noted that the differences in the "% wet weight" for the compositions "A" primarily are caused by the fact that the density of the 10 antifouhng agents, Cuprous oxide low tint and Cuprous thiocyanate, respectively, are quite different

Model Paint Composition B

15 49%, by solids volume of a binder

1 8% by solids volume thixotropic agent HDK N20 (ex Wacker Chemie, Germany)

1 8% by solids volume thixotropic agent Aditix M60 (ex Supercoloπ, Italy)

1 8% by solids volume wetting agent Disperbyk 164 (ex Byk Chemie, Germany)

24 1% by solids volume of cuprous oxide (Nordox Cuprous oxide Paint Grade, Red, micro

20 milled ex Nordox Industπer A/S, Norway)

4 3% by solids volume of titanium dioxide Cπstal 121 (ex Cπstal, Saudi Arabia) 10,5% by solids volume of Copper Omadme (ex Arch Chemicals, Ireland)

5 7% by solids volume of 4,5-dιchloro-2-n-octyl-n-ιsothιazohne-3-on (Sea-Nine 211 ex Rohm and Haas, USA )

25 1 % by solids volume of water Scavanger Silikat TES 40 (ex Wacker Chemie, Germany)

Solids volume ratio (SVR) 49, Solvent xylene

1 ) Tributyltm methacrylate methyl methacrylate co-polymer (Cutmox 1000/60 He ex Acima AG, Switzerland)

2) Trιιsopropylsιlyl(meth) acrylate based copolymer 3) HDK N20 (ex Wacker Chemie, Germany)

4) Aditix M60 (ex Supercoloπ, Italy)

5) Disperbyk 164 (ex. Byk Chemie, Germany)

6) TES 40 (ex Wacker Chemie, Germany)

7) Cristal 121 (ex Cπstal, Saudi Arabia) 8) Copper Omadme (ex Arch Chemicals, Ireland)

9) 4,5-dιchloro-2-n-octyl-n-ιsothιazohne-3-one (Sea-Nine 211 ex Rohm and Haas, USA )

10) Nordox Cuprous oxide Paint Grade, Red, micro milled ex Nordox Industner A/S, Norway) Test results

Blister box test

Test results are provided in the format "3S1" where the first number, 3, indicates the density of cracking and the last number, 1 , indicates the size of cracking, cf the above description

Polishing rate test

1)Metal carboxylate/rosm type 1) Copper acrylate type 2) Silylated acrylate type Antifouling performance on the rotor

Antifouling performance

Tests based on the non-aqueous dispersions (D)

The non-aqueous dispersion (D) was mixed with above "other raw materals (RM)" as indicated in the below tables

Blister Box Test

Test results are provided in the format "3S1" where the first number, 3, indicates the density of cracking and the last number, 1 , indicates the size of cracking, cf the above description

Antifouling performance

Polishing results

Claims

1 An antifouhng paint composition containing, as a binder, a resin having groups of the formula (1)

-S(0)₂-0-(Sι(R⁴)(R⁵)-0)_n-Sι(R¹)(R²)R³ (1 )

wherein n is 0-200, preferably 0-10, and each of R , R² R³ R⁴ and R⁵ which are independent of one another, is a hydrocarbon group selected from the group consisting of d ₁8 alkyl groups, d is alkoxy groups, C₇ 19 aralkyl groups, C_{3 9} cycloalkyl groups and C₆ ι₈ aryl groups, in its molecule

2 An antifouhng paint composition according to Claim 1 , wherein said resm is a copolymer comprising from 5 to 60 weight % of a polymensable unsaturated monomer (a) having a group of the formula (1) as defined in claim 1 , and from 95 to 40 weight % of other polymensable unsaturated monomer(s) (b) copolymeπsable with said polymensable unsaturated monomer (a), said copolymer having a number-average molecular weight of from 1 ,000 to 300,000

3 An antifouhng paint composition according to Claim 1 or 2, wherein said resm is an organic solvent-soluble type or a non-aqueous dispersion type

4 An antifouhng paint composition according to any one of Claims 1 to 3, which further contains a dehydrating agent

5 An antifouhng paint composition according to any of the preceding claims, wherein n

6 An antifouhng paint composition according to any of the preceding claims, wherein the number average molecular weight of the resm as the binder is in the range of from 1 ,000 to 300,000

7 An antifouhng paint composition according to any of the preceding claims, comprising one or more antifouling agent(s) in a total amount of in the range of 0-80% by wet weight of the paint 8 An antifouhng paint composition according to any of the preceding claims, comprising a binder resin in an amount of from 5-75% by wet weight, one or more antifouhng agent(s) in a total amount of from 0 to 80% by wet weight

5

9 An antifouhng paint composition according to any of the preceding claims, said composition comprising

5-40% by wet weight of a resm, as a binder, having groups of the formula (1) 10 2-75% by wet weight of an antifouhng agent

0-30% by wet weight of additional binder components

0-40% by wet weight of additives (including dehydrating agents, fibres, pigments, etc )

10-40% by wet weight of a solvent

15 10 An antifouhng paint composition according to any of the preceding claims, wherein the binder of the paint is prepared by copolymeπsation of a polymensable unsaturated monomer (a) having a silylated sulfonate group of the above formula (1) with other polymensable unsaturated monomer(s) (b) copolymeπsable with the monomer (a)

20 11 An antifouhng paint composition according to Claim 10, wherein the polymerisable unsaturated monomer (a) is obtainable by reacting (i) a monomer having a polymerisable unsaturated double bond and a sulfonic acid group with (n) an organosilyl compound of the formula

25 H-(Sι(R⁴)(R⁵)-0)_n-Sι(R )(R²)R³ (2) or X-(Sι(R⁴)(R⁵)-0)_n-Sι(R¹)(R²)R³ (3)

wherein n, R¹, R² R³ R⁴ and R⁵ have the same meanings as n, R¹, R² R³ R⁴ and R⁵ in the formula (1) and X designates a halogen atom such as chlorine or bromine, preferably 30 chlorine

12 An antifouhng paint composition according to Claim 11 , wherein the monomers (i) are of the formula CH₂=CR-(C(0)-0)_k-(Q)-S(0)₂0H wherein k is 0 or 1 , or of the formula CH₂=CR-C(0)-NH-(Q)-S(0)₂OH, wherein R is hydrogen or methyl and Q is selected from 35 linear or branched Ci ₈-alkylene and C₆ is arylene, and the alkali metal salt thereof 13 An antifouhng paint composition according to Claim 12, wherein the monomers (i) are selected from (meth)acrylsulfonιc acid, 2-sulfoethyl (meth)acrylate, sulfopropyl(meth)- acrylate, 4-sulfobutyl (meth)acrylate, styrenesulfonic acid, vmylsulfonic acid, allylsulfonic acid, and 2-(meth)acrylamιde-2-methylpropanesulfoπιc acid, and the alkali metal salt thereof, e g the sodium salt

14 An antifouling paint composition according to Claim 11 , wherein the organosilyl compound of the formula (2) is selected from trimethylsilane, tπethylsilane, tn-n-propyl- silane, tn-iso-propylsilane, tπ-n-butylsilane, t -iso-butylsilane, dimethylhexylsilane, tnphenylsilane, dibutylhexylsilane, dibutylphenylsilane, di-tert-butylphenylsilane, diphenyl- tert-butylsilane, dimethyloctylsilane, di-tert-butylmethylsilane, tri-tert-butylsilane, tert-butyl- di-isobutylsilane, tert-butyl-di-isopropylsilane, thexyl-di-isobutylsilane, and thexyl-di- isopropylsilane and organosilyl compound of the formula (3) is selected from tnmethyl- chlorosilane, tnethylchlorosilane, tn-n-propylchlorosilane, tπ-iso-propylchlorosilane, tn-n- butylchlorosilane, tn-iso-butylchlorosilane, tri-tert-butylchlorosilane, dibutylhexylchloro- silane, dimetyl n-propylchlorosilane, di-tert-butylmetylchlorosilane, dimethylbutylchloro- siiane, dimethyloctylchlorosilane, dimethyldodecylchlorosilane, di-iso-propyloctylchloro- silane, dimetyloctadecylchlorosilane, tnphenylchlorosilane, tπbenzylchlorosilane, di-tert- butylphenylchlorosilane, diphenylmetylchlorosilane, diphenyl-tert-butylchlorosilane, di- metyl(3,3-dιmetylbutyl)chlorosιlane, tnbutoxychlorosilane, dibutylphenylchlorosilane, di- tert-butylmethylchlorosilane, tri-tert-butylchlorosilane, tert-butyl-di-isobutylchlorosilane, tert-butyl-di-isopropylchlorosilane, thexyl-di-isobutylchlorosilane, and thexyl-di-isopropyl- chlorosilane, as well as the corresponding bromo compounds

15 An antifouhng paint composition according to Claim 10, wherein the polymerisable unsaturated monomer (a) is selected from trimethylsilylsulfoethyl (meth)acrylate, tπethylsilylsulfoethyl (meth)acrylate, dibutylphenylsilylsulfoethyl (meth)acrylate, di-tert- butylmethylsilylsulfoethyl (meth)acrylate, trι-tert-butylsιlylsulfoethyl(meth)acrylate, tert- butyl-dι-ιsobutylsιlylsulfoethyl(meth)acrylate, tert-butyl-dι-ιsopropylsιlylsulfoethyl(meth)- acrylate, thexyl-dι-ιsobutylsιlylsulfoehtyl(meth)acrylate, thexyl-di-isopropylsilylsulfoethyl- (meth)acrylate, trιιsopropylsιlylsulfopropyl(meth)acrylate, di-tert-butylmethylsilylsulfopropyl (meth)acrylate, trι-tert-butylsιlylsulfopropyl(meth)acrylate, tert-butyl-di-isobutylsilylsulfo- propyl(meth)acrylate, tert-butyl-dι-ιsopropylsιlylsulfopropyl(meth)acrylate, thexyl-di-iso- butylsιlylsulfopropyl(meth)acrylate, thexyl-dι-ιsopropylsιlylsulfopropyl(meth)acrylate, tπiso- propylsilylsulfobutyl (meth)acrylate, trusobutylsilylsulfobutyl (meth)acrylate, tnphenylsilyl- sulfobutyl(meth)acrylate, tert-butyldιphenylsιlylsulfobutyl(meth)acrylate, dimethyl tert- butylsilylsulfobutyl (meth)acrylate, di-tert-butylmethylsilylsulfobutyl (meth)acrylate, tπ-tert- butylsιlylsulfobutyl(meth)acrylate, tert-butyl-dι-ιsobutylsιlylsulfobutyl(meth)acrylate, tert- butyl-dι-ιsopropylsιlylsulfobutyl(meth)acrylate, thexyl-dι-ιsobutylsιlylsulfobutyl-(meth)- acrylate, thexyl-dι-ιsopropylsιlylsulfobutyl(meth)acrylate, tnmethylsilylsulfostyrene, trnso- propylsilylsulfostyrene, trnsobutylsilylsulfostyrene, dibutylphenylsilylsulfostyrene, dimethyl tert-butylsilylsulfostyrene, di-tert-butylmethylsilylsulfostyrene, tri-tert-butylsilylsulfostyrene, tert-butyl-di-isobutylsilylsulfostyrene, tert-butyl-di-isopropylsilylsulfostyrene, thexyl-di- isobutylsilylsulfostyrene, thexyl-di-isopropylsilylsulfostyrene, triethylsilylsulfovinyl, di-tert- butylmethylsilylsulfovmyl, tri-tert-butylsilylsulfovmyl, tert-butyl-di-isobutylsilylsulfovinyl, tert- butyl-di-isopropylsilylsulfov yl, thexyl-di-isobutylsilylsulfovmyl, thexyl-di-isopropyisilyl- sulfovmyl, trimethylsilylsulfoallyl, tnisopropylsilylsulfoallyl, tπisobutylsilylsulfoallyl, dibutyl- phenylsilylsulfoallyl, dimethyl tert-butylsilylsulfoallyl, di-tert-butylmethylsilylsulfoallyl, tri- tert-butylsilylsulfoallyl, tert-butyl-di-isobutylsiiylsulfoallyl, tert-butyl-di-isopropylsilylsulfoallyl, thexyl-di-isobutylsilylsulfoallyl, thexyl-di-isopropylsilylsulfoallyl trnsopropylsilylsulfoallyl- benzene, t isobutylsilylsulfoallylbenzene, dibutyiphenylsilylsulfoallylbenzene, dimethyl tert-butylsilylsulfoallylbenzene, di-tert-butylmethylsilylsulfoallylbenzene, tn-tert-butylsilyl- sulfoallylbenzene, tert-butyl-di-isobutylsilylsulfoallylbenzene, tert-butyl-di-isopropylsilyl- sulfoallylbenzene, thexyl-di-isobutylsilylsulfoallylbenzene, and thexyl-di-isopropylsilyl- sulfoallylbenzene

16 A process for the preparation of an antifou ng paint composition, the method comprising mixing a resin having groups of the formula (1)

-S(0)₂-0-(Sι(R⁴)(R⁵)-0)_n-Sι(R¹)(R²)R³ (1 )

wherein n is 0-200, preferably 0-10, and each of R¹, R², and R³, R⁴ and R⁵ which are independent of one another, is a hydrocarbon group selected from the group consisting of Ci is alkyl groups, Ci _i8 alkoxy groups, C_{7 1}9 aralkyl groups, C_{3 9} cycloalkyl groups and C_{6 18} aryl groups, in its molecule, with other paint constituents optionally including further binder components, and a solvent

17 A process according to Claim 16, wherein the resm and other paint constituents are essentially as defined in any of the Claims 1-15