(19)

*EP003571251B1*
(11) EP 3 571 251 B1
(12) EUROPEAN PATENT SPECIFICATION

(45) Date of publication and mention (51) Int Cl.:

of the grant of the patent: C09D 5/00 (2006.01) C09D 5/16 (2006.01)
16.12.2020 Bulletin 2020/51
(86) International application number:
(21) Application number: 18701274.5 PCT/EP2018/050711

(22) Date of filing: 12.01.2018 (87) International publication number:

WO 2018/134124 (26.07.2018 Gazette 2018/30)

(54) FOUL RELEASE COATING COMPOSITION, SUBSTRATE COATED WITH SUCH COATING
COMPOSITION, AND USE OF SUCH COATING COMPOSITION
ANTIFÄULNISAGENTIEN FREISETZENDE BESCHICHTUNGSZUSAMMENSETZUNG
COMPOSITION DE REVÊTEMENT ANTI-SALISSURE

(84) Designated Contracting States: • PARRY, Alison Louise

AL AT BE BG CH CY CZ DE DK EE ES FI FR GB Durham DH1 2DS (GB)
GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO • DUNFORD, Graeme
PL PT RO RS SE SI SK SM TR South Shields
Tyne and Wear NE34 6NQ (GB)
(30) Priority: 17.01.2017 EP 17151859 • PRICE, Clayton
Whitley Bay,
(43) Date of publication of application: Tyne and Wear NE25 9JY (GB)
27.11.2019 Bulletin 2019/48 • HEATH, Robin Alexander
Tyne and Wear NE10 0JY (GB)
(73) Proprietor: Akzo Nobel Coatings International B.V.
6824 BM Arnhem (NL) (74) Representative: Akzo Nobel IP Department
Velperweg 76
(72) Inventors: 6824 BM Arnhem (NL)
• MOORE, David
Durham DH3 2EB (GB) (56) References cited:
• SCHEIM, Uwe EP-A1- 2 161 318 WO-A1-2014/096572
01612 Nünchritz (DE) FR-A1- 2 761 367 US-A1- 2013 172 193
• REYNOLDS, Kevin John
Tyne and Wear NE10 8BU (GB)
EP 3 571 251 B1

Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent
Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the
Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been
paid. (Art. 99(1) European Patent Convention).

Printed by Jouve, 75001 PARIS (FR)

 EP 3 571 251 B1

Description

Field of the Invention

5 [0001] The invention relates to a non-aqueous liquid foul release coating composition for controlling aquatic biofouling
on man-made objects, to a substrate coated with the coating composition, and to the use of the coating composition to
control aquatic biofouling on man-made objects.

Background of the Invention

10
[0002] Man-made structures such as ship and boat hulls, buoys, drilling platforms, dry dock equipment, oil production
rigs, aquaculture equipment and netting and pipes which are immersed in water, or have water running through them,
are prone to fouling by aquatic organisms such as green and brown algae, barnacles, mussels, and the like. Such
structures are commonly of metal, but may also comprise other structural materials such as concrete, glass reenforced
15 plastic or wood. This fouling is a nuisance on boat hulls, because it increases frictional resistance during movement
through the water, the consequence being reduced speeds and increased fuel consumption. It is a nuisance on static
structures such as the legs of drilling platforms and oil and gas production, refining and storage rigs, firstly because the
resistance of thick layers of fouling to waves and currents can cause unpredictable and potentially dangerous stresses
in the structure, and, secondly, because fouling makes it difficult to inspect the structure for defects such as stress
20 cracking and corrosion. It is a nuisance in pipes such as cooling water intakes and outlets, because the effective cross-
sectional area is reduced by fouling, with the consequence that flow rates are reduced.
[0003] It is known, for example as disclosed in GB 1307001 and US 3702778 that silicone rubber coatings resist fouling
by aquatic organisms. It is believed that such coatings present a surface to which the organisms cannot easily adhere,
and they can accordingly be called fouling release or fouling resistant rather than anti-fouling coatings. Silicone rubbers
25 and silicone compounds generally have very low toxicity. The disadvantage of this anti-fouling system when applied to
boat hulls is that although accumulation of marine organisms is reduced, there is the need for relatively high vessel
speeds to remove all fouling species. Thus, in some instances, it has been shown that for effective release from a hull
that has been treated with such a polymer it is necessary to sail with a speed of at least 14 knots.
[0004] WO 2014/131695 describes anti-fouling compositions comprising an organosiloxane-containing polymer and
30 a fluorinated oxyalkylene-containing polymer or oligomer. The compositions typically comprise a tin-based curing catalyst.
[0005] Commercially available foul release coating systems based on polysiloxanes require a cure catalyst, which is
typically a tin-based catalyst. Tin-based catalysts are faced with increasing disfavor due to toxicity issues associated
with tin compounds. Other, less hazardous, catalysts are available; however they typically have a detrimental impact
upon key coating attributes such as drying time, pot life or anti-fouling performance.
35 [0006] In US 2015/0329724 is described an anti-fouling coating composition comprising an organosiloxane-containing
polymer with hydrolysable and condensable groups, a crosslinking agent, and a zinc complex as curing catalyst.
[0007] EP2161318 describes an antifouling coating material comprising a triphenylboron compound as an antifouling
agent, and also optionally an oxyalkylene group-containing linear organopolysiloxane. US2013/172193 describes func-
tionalised ionic silicone compositions that can have utility in coating compositions. FR2761367 describes a process for
40 grafting at least one pendant chain having biocidal properties onto a polysiloxane.
[0008] There is a need for foul release coatings providing improved protection against fouling, in particular at low
vessel speed or under static conditions. There is also a need for foul release coatings having superior adhesion to
substrates, compositions having an improved balance of usability after opening (pot life) and drying time, in particular
when drying at low temperatures is required.
45
Summary of the Invention

[0009] The invention provides a foul release coating composition which removes or alleviates the above-mentioned
problems.
50 [0010] Accordingly the invention provides in a first aspect a non-aqueous liquid foul release coating composition for
controlling aquatic biofouling on man-made objects comprising

i) a moisture curable polysiloxane comprising repeating units of formula (I)

55

2
 EP 3 571 251 B1

10
and at least one terminal or pendant group of formula (II)

15

20
wherein R1 and R2 are, independently, organic groups having 1 to 20 carbon atoms; R3 and R4 are, independently,
organic groups having 1 to 20 carbon atoms; A is an organic group having 1 to 50 carbon groups; R5 is, independently,
selected from organic groups having 1 to 20 carbon atoms and groups of the formula O-R6 wherein R6 is an organic
group having 1 to 20 carbon atoms, with the proviso that at least one of R5 is a group of the formula O-R6, and
25 ii) at least one of a marine biocide or a non-volatile component comprising units selected from hydrocarbyl, hetero-
carbyl, halocarbyl, ether, ester, amide, ketone, siloxane, urethane or urea groups.

[0011] The foul release coating composition of the invention provides coatings having improved anti-fouling perform-
ance compared to known anti-fouling coatings. Organisms cannot easily adhere to such coatings, even at low vessel
30 speed or under static conditions. The coating compositions have an improved balance of usability (pot life) and drying
time, in particular when drying at low temperatures is required, and the coatings show improved adhesion to substrates.
The coating composition cures very well in the absence of a cure catalyst. Hence, tin-based cure catalysts or other
catalysts are not required and are preferably absent.
[0012] In a second aspect, the invention provides a substrate coated with a foul release coating composition according
35 to the first aspect of the invention.
[0013] After the coating composition has been applied to a substrate and dried, cured or crosslinked, the coated
substrate can be immersed and gives protection against fouling.
[0014] Therefore, in a third aspect, the invention provides a process of controlling aquatic biofouling of a man-made
object, comprising the steps of:
40
a) applying the foul release coating composition according to the first aspect of the invention to at least a part of the
surface of the man-made object;
b) curing the coating composition to form a cured coating layer; and
c) immersing the man-made object at least partly in water.
45
[0015] In a final aspect, the invention provides the use of the foul release coating composition according to the first
aspect of the invention to control aquatic biofouling on man-made objects.

Detailed Description of the Invention

50
[0016] The foul release coating composition of the invention is a liquid coating composition. This means that the
composition is liquid at ambient temperature and can be applied to a substrate by well-known techniques, such as
brushing, rolling, dipping, bar application or spraying.
[0017] In one embodiment, the coating composition comprises a volatile organic solvent to achieve the required
55 application viscosity. Alternatively, the coating composition may be essentially or entirely free of volatile organic solvent,
for example when the polysiloxane is liquid and has a sufficiently low viscosity, or when reactive diluents or liquid
plasticizers are included. The coating composition is a non-aqueous coating composition. This means that the composition
is supplied in a form which is essentially free or entirely free of water. By essentially free of water it is meant that the

3
 EP 3 571 251 B1

composition comprises between 0 and 5 % by weight, preferably between 0 and 2 % by weight of water, calculated on
the total weight of the composition. The mentioned amounts of water may be unintentionally introduced by components
included in the coating composition, for example by pigments or organic solvents which contain low amounts of water
as impurity.
5 [0018] An essential component of the coating composition is a moisture curable polysiloxane comprising repeating
units of formula (I)

10

15

and at least one terminal or pendant group of formula (II)

20

25

wherein R1, R2, R3, R4, R5, R6 and A are as specified hereinabove.
[0019] Organic groups are groups comprising at least one carbon atom. Generally, the organic groups R1, R2, R3, R4,
30 R5, R6 and A are linear, branched or cyclic organic groups, for example aliphatic or aromatic organic groups. The definition
of organic groups also encompasses oligo- or poly-siloxanes.
[0020] In one embodiment, R1, R 2, R3, R4, R5, R6, and A, are, independently, hydrocarbyl, heterocarbyl or halocarbyl
groups.
[0021] R3 and R4 are organic groups having 1 to 20 carbon atoms. In one embodiment, the organic groups R3 and
35 R4 are only indirectly linked to each other via the nitrogen atom in formula (II). In a further embodiment, the organic
groups R3 and R4 are also directly linked to each other by a further covalent bond, thus representing a cyclic amine
structure. By way of example, R3 and R4, together with the nitrogen atom of formula (II), may represent a pyrrolidine or
a piperidine ring.
[0022] Preferably, R3 and R4 are, independently, a linear, cyclic or branched aliphatic hydrocarbyl radical without
40 hereoatoms, having 1 to 10 carbon groups, more preferably 1 to 8 carbon atoms. In one embodiment, R3 and R4 each
are a butyl group.
[0023] As used herein, the term ’hydrocarbyl’ means a univalent group formed by removing a hydrogen atom from a
hydrocarbon, such as a linear, branched, cyclic, aliphatic, aryl, aralkyl, or alkylaryl hydrocarbon,
[0024] As used herein, the term ’heterocarbyl’ means a hydrocarbyl group that comprises a heteroatom such as
45 oxygen, sulfur, nitrogen or silicon incorporated within the chain or ring.
[0025] As used herein, the term ’halocarbyl’ means a hydrocarbyl group wherein one or more hydrogen atoms have
been substituted by a halogen atom, such as a fluorine, chlorine or bromine atom.
[0026] In formula (I) R 1 and R2 are independently selected from linear, cyclic or branched organic groups having 1 to
20 carbon atoms. In one embodiment, the organic groups are hydrocarbyl groups without heteroatoms. Alternatively,
50 the organic groups may comprise heteroatoms atoms or groups comprising heroatoms, such as ether, ester, amide,
sulfide, haloalkyl, siloxane, urethane or urea groups. More preferably, each of R1 and R2 is, independently, a methyl
group or a phenyl group.
[0027] In formulae (II) and (III) the R5 groups are suitably selected from linear, cyclic or branched aromatic or aliphatic
organic groups having 1 to 20 carbon atoms and groups of the formula O-R6, wherein R6 is a linear, cyclic or branched
55 aliphatic organic group having 1 to 20 carbon atoms, with the proviso that at least one R5 group is a group of the formula
O-R6. The linear, cyclic or branched aromatic or aliphatic organic groups are preferably alkyl groups having 1 to 6 carbon
atoms.
[0028] The presence of groups of the formula O-R 6 provides moisture curability to the polysiloxane. It is preferred that

4
 EP 3 571 251 B1

at least two of the R5 groups are groups of the formula O-R6. In a further preferred embodiment R5 groups are selected
from C1 to C4 alkoxy groups, particularly ethoxy groups.
[0029] Suitable moisture curable polysiloxanes can be prepared by reaction of hydroxyl functional polysiloxanes having
repeating units of formula (I) as defined above, and an aminosilane of formula (III)
5

10

wherein R3 to R5 and A are as defined above, and wherein at least one R5 group is a group of the formula O-R6. Such
15 a reaction is described in Chinese patent publication CN 101134887, which is herein incorporated by reference. This
document describes the reaction of an α,ω-dihydroxy polydimethyl siloxane with an α-aminomethyl trialkoxysilane. In
order to ensure a sufficient degree of conversion of the hydroxyl groups of the hydroxyl functional polysiloxanes having
repeating units of formula (I) and the aminosilane of formula (III), it may be advantageous to employ a molar excess of
aminosilane of formula (III) during the reaction. Any unreacted excess of aminosilane may be removed after the reaction.
20 However, it is also possible to retain any excess of unreacted aminosilane in the moisture curable polysiloxane. Any
excess of aminosilane can participate as curing agent in the curing reaction once the coating composition is applied to
a substrate. Furthermore, the aminosilane can lower the viscosity of the coating composition and reduce the need for
volatile organic solvent as diluent. Therefore, it is preferred that the coating composition of the invention further comprises
an aminosilane of formula (III). The aminosilane of formula (III) may be used in any suitable amount, typically up to 10
25 wt% based on the weight of moisture curable polysiloxane, preferably in the range of from 0.5 to 7 wt%, even more
preferably of from 1 to 5 wt%.
[0030] In one embodiment, group A in formulae (II) and (III) is a linear, cyclic or branched aliphatic organic group
having 1 to 10 carbon atoms, preferably a hydrocarbyl group without heteroatoms having 1 to 10 carbon atoms, more
preferably 1 to 8 carbon atoms, even more preferably 1 to 6 carbon atoms. Very good results have been obtained in
30 embodiments wherein A is a methylene group (-CH2-). Therefore, in a preferred embodiment, A is a methylene group.
[0031] The moisture curable polysiloxane may be linear or branched. In one embodiment, the moisture curable polysi-
loxane is essentially linear and has two terminal groups of formula (II).
[0032] In one embodiment the moisture curable polysiloxane essentially consists of repeating units of formula (I) and
terminal or pendant groups of formula (II). In an alternative embodiment, the moisture curable polysiloxane comprises
35 other groups, which may form part of the main polymer chain or may be pendant from the main polymer chain. Examples
of other groups include ether moieties, polyether moieties and fluorinated alkyl groups.
[0033] One of the advantages of the foul release coating composition of the invention is that a curing catalyst is not
required for the curing reaction of the moisture-curable polysiloxane to proceed after application of the composition to
a substrate. Therefore, it is generally preferred not to include a curing catalyst in the coating composition.
40 [0034] In a particularly preferred embodiment, the coating composition comprises an aminosilane of formula (III); group
A in formulae (II) and (III) is a methylene group; and the coating composition does not comprise a curing catalyst. It has
been found that in this embodiment, the aminosilane of formula (III) acts as a crosslinking agent (curing agent) to the
extent that the coating composition cures within an acceptable time, also in the absence of a curing catalyst.
[0035] Nevertheless, it may be desirable under specific circumstances to further increase the curing rate by addition
45 of curing catalysts to the coating composition.
[0036] Examples of suitable catalysts include carboxylic acid salts of various metals, such as tin, zinc, iron, lead,
barium, and zirconium. Such salts preferably are salts of long- chain carboxylic acids, for example dibutyltin dilaurate,
dibutyltin dioctoate, iron stearate, tin (II) octoate, and lead octoate. Further examples of suitable catalysts include orga-
nobismuth and organotitanium compounds and organo- phosphates such as bis(2-ethyl-hexyl) hydrogen phosphate.
50 Other possible catalysts include chelates, for example dibutyltin acetoacetonate. Further, the catalyst may comprise a
halogenated organic acid which has at least one halogen substituent on a carbon atom which is in the [alpha]-position
relative to the acid group and/or at least one halogen substituent on a carbon atom which is in the [beta]-position relative
to the acid group, or a derivative which is hydrolysable to form such an acid under the conditions of the condensation
reaction. Alternatively, the catalyst may be as described in any of WO2007122325 A1, WO2008055985 A1,
55 WO2009106717 A2, WO2009106718 A2. It is also possible to use combinations of the above materials.
[0037] In addition to the moisture curable polysiloxane the coating composition comprises a second component to
provide enhanced protection against fouling. The second component is a marine biocide or a non-volatile component
comprising units selected from hydrocarbyl, heterocarbyl, halocarbyl, ether, ester, amide, ketone, siloxane, urethane or

5
 EP 3 571 251 B1

urea groups.
[0038] The biocide may be one or more of an inorganic, organometallic, metal-organic or organic biocide for marine
or freshwater organisms. Examples of inorganic biocides include copper salts such as copper oxide, copper thiocyanate,
copper bronze, copper carbonate, copper chloride, copper nickel alloys, and silver salts such as silver chloride or nitrate;
5 organometallic and metal-organic biocides include zinc pyrithione (the zinc salt of 2-pyridinethiol-1-oxide), copper py-
rithione, bis (N-cyclohexyl-diazenium dioxy) copper, zinc ethylene-bis(dithiocarbamate) (i.e. zineb), zinc dimethyl dithi-
ocarbamate (ziram), and manganese ethylene-bis(dithiocarbamate) complexed with zinc salt (i.e. mancozeb); and or-
ganic biocides include formaldehyde, dodecylguanidine monohydrochloride, thiabendazole, N-trihalomethyl thioph-
thalimides, trihalomethyl thiosulphamides, N-aryl maleimides such as N-(2,4,6-trichlorophenyl) maleimide, 3-(3,4-dichlo-
10 rophenyl)-1,1-dimethylurea (diuron), 2,3,5,6-tetrachloro-4-(methylsulphonyl) pyridine, 2-methylthio-4-butylamino-6-cy-
clopopylamino-s-triazine, 3-benzo[b]thien-yl-5,6-dihydro-1,4,2-oxathiazine 4-oxide, 4,5-dichloro-2-(n-octyl)-3(2H)-iso-
thiazolone, 2,4,5,6-tetrachloroisophthalonitrile, tolylfluanid, dichlofluanid, diiodomethyl-p-tosylsulphone, capsciacin or a
substituted capsciacin, N-cyclopropyl-N’-(1,1-dimethylethyl)-6-(methylthio)-1,3,5-triazine-2,4-diamine, 3-iodo-2-propy-
nylbutyl carbamate, medetomidine, 1,4-dithiaanthraquinone-2,3-dicarbonitrile (dithianon), boranes such as pyridine
15 triphenylborane, a 2-trihalogenomethyl-3-halogeno-4-cyano pyrrole derivative substituted in position 5 and optionally in
position 1, such as 2-(p-chlorophenyl)-3-cyano-4-bromo-5-trifluoromethyl pyrrole (tralopyril), and a furanone, such as
3-butyl-5-(dibromomethylidene)-2(5H)-furanone, and mixtures thereof, macrocyclic lactones such as avermectins, for
example avermectin B1, ivermectin, doramectin, abamectin, amamectin and selamectin, and quaternary ammonium
salts such as didecyldimethylammonium chloride and an alkyldimethylbenzylammonium chloride.
20 [0039] Optionally, the biocide is wholly or partially encapsulated, adsorbed, entrapped, supported or bound. Certain
biocides are difficult or hazardous to handle and are advantageously used in an encapsulated, entrapped, absorbed,
supported, or bound form. Encapsulation, entrapment, absorption, support or binding of the biocide can provide a
secondary mechanism for controlling biocide leaching from the coating system in order to achieve an even more gradual
release and long lasting effect.
25 [0040] The method of encapsulation, entrapment, adsorption, support or binding of the biocide is not particularly limiting
for the present invention. Examples of ways in which an encapsulated biocide may be prepared for use in the present
invention include mono and dual walled amino-formaldehyde or hydrolysed polyvinyl acetate-phenolic resin capsules
or microcapsules as described in EP 1791424. An example of a suitable encapsulated biocide is encapsulated 4,5-
dichloro-2-(n-octyl)-3(2H)-isothiazolone marketed by Dow Microbial Control as Sea-Nine CR2 Marine Antifoulant Agent.
30 [0041] Examples of ways in which an absorbed or supported or bound biocide may be prepared include the use of
host-guest complexes such as clathrates as described in EP0709358, phenolic resins as described in EP0880892,
carbon-based adsorbents such as those described in EP1142477, or inorganic microporous carriers such as the amor-
phous silicas, amorphous aluminas, pseudoboehmites or zeolites described in EP1115282.
[0042] In view of environmental and health concerns linked to the use of biocides in coatings for the prevention of
35 aquatic biofouling, the second component is preferably not a marine biocide. In that case, the coating composition may
be essentially or entirely free of a marine biocide. In a preferred embodiment, enhanced protection against fouling is
provided by a non-biocidal component, said non-biocidal component being a non-volatile component comprising units
selected from hydrocarbyl, heterocarbyl, halocarbyl, ether, ester, amide, ketone, siloxane, urethane or urea groups.
[0043] A component is considered non-volatile if it does not boil at a temperature below 250 °C, at atmospheric
40 pressure. Preferably, this component is an incompatible fluid or grease. Examples include a silicone, organic or inorganic
molecule or polymer, usually a liquid, but optionally also an organosoluble grease or wax, which is immiscible (either
wholly or partly) with the cured moisture-curable polysiloxane. It is believed that the non-volatile second component will
become enriched at the surface of the cured coating layer and augment its foul release properties.
[0044] Suitable examples of the non-volatile second component of the coating composition include fluorinated polymers
45 or oligomers, such as linear and branched trifluoromethyl fluorine end-capped perfluoropolyethers (e.g. Fomblin Y®,
Krytox K® fluids, or Demnum S® oils); linear di-organo (OH) end-capped perfluoropolyethers (eg Fomblin Z DOL®,
Fluorolink E®); low molecular weight polychlorotrifluoroethylenes (eg Daifloil CTFE® fluids). Other mono- and diorgano-
functional end-capped fluorinated alkyl- or alkoxy- containing polymers or oligomers can also be used, such as carboxy-
or ester-functional fluorinated alkyl- or alkoxy-containing polymers or oligomers.
50 [0045] Further examples of the second component of the coating composition include silicone oils, for example of the
formula:

Q3Si-O-(SiQ2-O-)nSiQ3

55 wherein each group Q represents a hydrocarbon radical having 1 -10 carbon atoms and n is an integer such that the
silicone oil has a viscosity of 20 to 5000 m Pa s. At least 10% of the groups Q are generally methyl groups and at least
2% of the groups Q are phenyl groups. Most preferably, at least 10% of the - S1Q2-O- units are methyl-phenylsiloxane
units. Most preferably the silicone oil is a methyl terminated poly(methylphenylsiloxane). The oil preferably has a viscosity

6
 EP 3 571 251 B1

of 20 to 1000 m Pa s. Examples of suitable silicone oils are sold under the trademarks Rhodorsil Huile 510V100 and
Rhodorsil Huile 550 by Bluestar Silicones.
[0046] Still further examples of the second component of the coating composition include sterol(s) and/or sterol de-
rivative(s). Sterols and sterol esters are triterpenoids, which is a class of organic molecule derived from triterpene
5 molecules. Sterols and sterol derivatives may be derived from natural sources, such as animals and plants. Examples
of sterols include cholesterol, lanosterol, agnosterol, 7-dehydrocholesterol, cholecalciferol, desmosterol, lathosterol,
cholestanol, coprastanol, campesterol, stigmasterol, sitosterol, avenasterol, stigmastenol, brassicasterol, 4-desmethyl
sterols (i.e. with no substituent on carbon-4), 4α-monomethyl sterols and 4,4-dimethyl sterols, phytostanols (fully satu-
rated), ergosterol, amyrin and cylcoartenol. Suitable mixtures comprising sterols and sterol derivatives are lanolin, acylat-
10 ed lanolin, alkoxylated lanolin, and lanolin oil.
[0047] Yet further examples of the second component of the coating include hydrophilic-modified polysiloxanes such
as poly(oxyalkylene)-modified polysiloxane, for example a polysiloxane having grafted thereto poly(oxyalkylene) chains,
a polysiloxane having incorporated in the backbone thereof poly(oxyalkylene) chains, or a polysiloxane having incorpo-
rated in the backbone thereof polyoxyalkylene chains and having grafted thereto polyoxyalkylene chains. Commercially
15 available hydrophilic-modified polysiloxane oils of this type include DC5103, DC Q2-5097, DC193, DC Q4-3669, DC
Q4-3667, DC57 and DC2-8692 (all Dow Corning) and BYK333.
[0048] In one embodiment, the second component ii) of the coating composition may become covalently linked to the
moisture-curable polysiloxane i) when the coating is cured.
[0049] However, it is preferred that the second component of the coating composition does not participate in the
20 moisture induced curing reaction of the polysiloxane. Therefore, in a preferred embodiment, this component does not
contain groups of formula (II).
[0050] In an alternative embodiment, a non-biocidal, non-volatile second component is combined with a marine biocide.
[0051] The foul release coating composition may also comprise further ingredients, such as fillers, pigments, wetting
agents, dispersing agents, flow additives, rheology control agents, adhesion promoters, antioxidants, UV stabilizers,
25 organic solvents, organic polymers, reactive diluents, plasticizers and catalysts.
[0052] Examples of suitable fillers are barium sulphate, calcium sulphate, calcium carbonate, silicas or silicates (such
as talc, feldspar, and china clay), including pyrogenic silica, bentonite and other clays, and solid silicone resins, which
are generally condensed branched polysiloxanes, such as a silicone resin comprising Q units of the formula SiO 4/2 and
M units of the formula Rm3SiO1/2, wherein the Rm substituents are selected from alkyl groups having 1 to 6 carbon atoms
30 and the ratio of M units to Q units is in the range of 0.4:1 to 1:1. Some fillers such as fumed silica may have a thixotropic
effect on the coating composition. The proportion of fillers may be in the range of from 0 to 25 wt%, based on the total
weight of the coating composition. Preferably the clay is present in an amount of 0 to 1 wt% and preferably the thixotrope
is present in an amount of 0 to 5 wt%, based on the total weight of the coating composition.
[0053] Examples of pigments include black iron oxide, red iron oxide, yellow iron oxide, titanium dioxide, zinc oxide,
35 carbon black, graphite, red molybdate, yellow molybdate, zinc sulfide, antimony oxide, sodium aluminium sulfosilicates,
quinacridones, phthalocyanine blue, phthalocyanine green, indanthrone blue, cobalt aluminium oxide, carbazolediox-
azine, chromium oxide, isoindoline orange, bis-acetoaceto-tolidiole, benzimidazolone, quinaphthalone yellow, isoindoline
yellow, tetrachloroisoindolinone, and quinophthalone yellow, metallic flake materials (e.g. aluminium flakes), or other
so-called barrier pigments or anticorrosive pigments such as zinc dust or zinc alloys; or other so-called lubricant pigments
40 such as graphite, molybdenum disulfide, tungsten disulphide or boron nitride. The pigment volume concentration pref-
erably is in the range of 0.5-25%. The proportion of pigments may be in the range of from 0 to 25 weight %, based on
the total weight of the coating composition.
[0054] Suitable solvents for use in the coating composition include aromatic hydrocarbons, alcohols, ketones, esters,
and mixtures of the above with one another or an aliphatic hydrocarbon. Preferable solvents include ketones such as
45 methyl isopentyl ketone and/or hydrocarbon solvents, such as xylene, trimethyl benzene, or aliphatic cyclic or acyclic
hydrocarbons, as well as mixture thereof.
[0055] The coating composition preferably has a non-volatile content, defined as the weight percentage of non-volatile
material in the coating composition, of at least 35 weight %, more preferably at least 50 weight %, even more preferably
at least 70 weight %. The non-volatile content can range up to 80 weight %, 90 weight %, 95 weight % and preferably
50 up to 100 weight %. The non-volatile content may be determined in accordance with ASTM method D2697.
[0056] In a second aspect, the invention relates to a substrate coated with a foul release coating composition according
to the first aspect of the invention. The coating composition can be applied to a substrate by techniques known in the
art, such as brush, roller, dipping, bar application or spray (airless and conventional).
[0057] The coating composition according to the first aspect of the invention provides coatings with very good fouling-
55 resistant and foul release properties. This makes these coating compositions very suitable for coating objects that are
immersed in an aquatic environment, such as marine and aquaculture applications. The coating can be used for both
dynamic and static structures, such as ship and boat hulls, buoys, drilling platforms, oil production rigs, a floating pro-
duction storage and offloading vessel (FPSO), a floating storage and regasification unit (FSRU), a cooling water intake

7
 EP 3 571 251 B1

in a power plant, a fish net or a fish cage and pipes which are immersed in water.
[0058] The substrate suitably is a surface of any of these structures, such as a metal, concrete, wood, organic polymer,
such as polyvinyl chloride or fiber-reinforced resin, substrate. Metal substrates, in particular steel, aluminium or bronze
substrates, are particularly suitable substrates. In an alternative embodiment, the substrate is a surface of a flexible
5 polymeric carrier foil. The coating composition is then applied to one surface of a flexible polymeric carrier foil, for example
a polyvinyl chloride carrier foil, and cured, and subsequently the non-coated surface of the carrier foil is laminated to a
surface of a structure to be provided with fouling-resistant and/or foul release properties, for example by use of an
adhesive.
[0059] To achieve good adhesion to the substrate it is preferred to apply the fouling-release coating composition to a
10 substrate that is provided with a primer layer and/or a tie-coat layer. The primer layer may be deposited from any primer
composition known in the art, for example an epoxy resin-based or polyurethane based primer composition. More
preferably, the substrate is provided with a tie-coat layer deposited from a tie-coat composition, before applying a foul
release coating layer deposited from the fouling-release coating composition according to the invention. The tie-coat
composition may be applied to the bare substrate surface, to a substrate surface still containing an aged layer of coating
15 composition, or to a primed substrate surface.
[0060] Tie-coat compositions are known in the art. In a preferred embodiment, the tie-coat layer is deposited from a
tie-coat composition comprising a binder polymer with alkoxysilane functional groups capable of reacting with pendant
alkoxy group(s) of moisture curable polysiloxane (i), in particular alkoxy groups O-R6. Such tie-coat compositions are
known in the art and for example described in WO99/33927. The binder polymer with curable alkoxysilane functional
20 groups in the tie-coat composition may be any suitable binder polymer, for example polyurethane, polyurea, polyester,
polyether, polyepoxy, or a binder polymer derived from ethylenically unsaturated monomers such as a polyacrylate.
[0061] In one embodiment, the substrate is coated with a multi-layer coating system comprising:

- optionally a primer layer applied to the substrate and deposited from a primer coating composition;
25 - a tie-coat layer applied to the substrate or to the optional primer layer, deposited from a tie-coat composition com-
prising an binder polymer with curable alkoxysilane functional groups; and
- a topcoat layer applied to the tie-coat layer, the topcoat layer deposited from a liquid foul release coating composition
according to the first aspect of the invention.

30 [0062] The substrate to which the primer layer or, in case no primer layer is applied, the tie-coat layer is applied may
be a bare substrate surface or a substrate surface still containing an aged layer of coating composition.
[0063] Preferably, the binder polymer in the tie-coat composition is a polyacrylate with curable alkoxysilane functional
groups. The curable alkoxysilane functional groups preferably have the following general formula:

35 -(CmH2m)-Si(R7)(3-n)(OR8)n

wherein n is 1, 2, or 3, preferably 2 or 3; R7, R8 are, independently, an alkyl radical having 1 to 6 carbon atoms, preferably
1 to 4 carbon atoms, more preferably are ethyl or methyl; m is an integer with a value in the range of from 1 to 20,
preferably in the range of from 1 to 6. More preferably, m is 1 or 3, even more preferably m is 1. It has been found that
40 if m is 1, adhesion between the tie-coat layer and the fouling-release coating deposited from the fouling-release coating
composition according to the invention is obtained quicker than if m has a value larger than 1.
[0064] Preferably, the binder polymer in the tie-coat composition does not have crosslinkable functional groups other
than the alkoxysilane functional groups.
[0065] In one embodiment, the binder polymer in the tie-coat composition is prepared by radical polymerisation of a
45 mixture of acrylate and/or (meth)acrylate monomers of which at least one has alkoxysilane functionality, such as for
example 3-(trimethoxysilylpropyl) methacrylate or trimethoxysilylmethyl methacrylate, preferably trimethoxysilylmethyl
methacrylate. An example of such monomer mixture is a mixture of methyl methacrylate, lauryl methacrylate and tri-
methoxysilylmethyl methacrylate.
[0066] Accordingly, in a third aspect, the invention provides a process of controlling aquatic biofouling of a man-made
50 object, comprising the steps of:

a) applying the foul release coating composition according to the first aspect of the invention to at least a part of the
surface of the man-made object;
b) curing the coating composition to form a cured coating layer; and
55 c) immersing the man-made object at least partly in water.

[0067] Preferably, the process further comprises the step of applying a tie-coat layer deposited from a tie-coat com-
position as specified hereinabove on the at least part of the surface of the man-made object before applying the foul

8
 EP 3 571 251 B1

release coating composition. Before applying the tie-coat, the surface provided with a primer layer deposited from a
primer coating composition as hereinbefore described.
[0068] The tie-coat composition is preferably a tie-coat composition as described above for the second aspect of the
invention.
5 [0069] In a final aspect, the invention provides the use of the foul release coating composition according to the first
aspect of the invention to control aquatic biofouling on man-made objects.

Examples

10 Preparation of Resin A

[0070] Resin A is the reaction product of an α,ω-dihydroxy polydimethylsiloxane and an excess of (N,N-dibutylamino
methyl)triethoxysilane The preparation of such resins is described in Chinese patent application CN 101134887 A.

15 Preparation of coating compositions

[0071] Coating compositions were prepared by high speed dispersion of the components mentioned below, wherein
pbw means parts by weight.

20 Example 1 (Foul release coating composition according to the invention)

Component pbw Function
Resin A 57.7 Resin / Cross-linker
Solvent naphtha (petroleum), light aromatic 34.6 Solvent
25
Black Iron Oxide 0.4 Colouring Pigment
Titanium dioxide 1.7 Colouring Pigment
Hydrophobic Fumed Silica 1.0 Thixotrope
30 Ethoxylated perfluoropolyether 4.6 Non-volatile fluid

[0072] The composition could be used for at least 6 months after mixing when stored without access of atmospheric
moisture.
35
Example 2 (Foul release coating composition according to the invention)
Component pbw Function
Resin A 62.0 Resin / Cross-linker

40 Solvent naphtha (petroleum), light aromatic 30.2 Solvent

Black Iron Oxide 0.4 Colouring Pigment
Titanium dioxide 1.8 Colouring Pigment
Hydrophobic Fumed Silica 1.0 Thixotrope
45
Ethoxylated perfluoropolyether 4.6 Non-volatile fluid

[0073] The composition could be used for at least 6 months after mixing when stored without access of atmospheric
moisture.
50
Example 3 (Foul release coating composition according to the invention)
Component pbw Function
Resin A 57.1 Resin / Cross-linker
55
Solvent naphtha (petroleum), light aromatic 18.0 Solvent
Dearomatised white spirit D40 12.0 Solvent

9
 EP 3 571 251 B1

(continued)

Component pbw Function

Titanium dioxide 7.8 Colouring Pigment
5
Hydrophobic Fumed Silica 1.0 Thixotrope
Dimethyl, methyl(propyl(polyethylene oxide) acetate-capped) siloxane 3.1 Non-volatile fluid

10
[0074] The composition could be used for at least 6 months after mixing when stored without access of atmospheric
moisture.

Examples A and B (Comparative foul release coating compositions)

Component pbw pbw Function
15
A B
Hydroxy terminated organosiloxane polymer 60.0 64.9 Resin
Hydrophobic Fumed Silica 1.7 3.1 Thixotrope

20 Titanium dioxide 5.3 2.7 Colouring Pigment

Black iron oxide 1.1 0.6 Thixotrope
Tetraethoxy silane 2.7 4.4 Curing agent
Xylene 19.2 20.6 Solvent
25
Diocyltin dilaurate 0.5 0.5 Catalyst
2,4-pentanedione 4.3 3.2 Cure inhibitor
Ethoxylated perfluoropolyether 5.2 - Non-volatile fluid

30
[0075] The compositions could be used for a maximum of 1 hour after mixing. After this time the viscosity of the
composition increased to a level that negatively impacted the application and the flow and leveling characteristics of the
paint.

35 Preparation of tie-coat compositions

Preparation of tie-coat composition 1

[0076] A siloxane functional polyacrylate was prepared by copolymerizing a mixture of methyl methacrylate, lauryl
40 methacrylate and trimethoxysilylpropyl methacrylate in the presence of mercaptopropyl trimethoxysilane as chain transfer
agent and 2,2’azobis(2-methylbutyronitrile (AMBN) as initiator in methyl n-amyl ketone (MAK) as solvent at 100 °C. The
methyl methacrylate/lauryl methacrylate/trimethoxysilylpropyl methacrylate/ mercaptopropyl trimethoxysilane molar ratio
was 70/12/15/3. A solution of 70 wt% polymer in MAK was obtained.

45 Preparation of tie-coat composition 2

[0077] A siloxane functional polyacrylate was prepared as described above for acrylic tie-coat composition 1, but with
trimethoxysilylmethyl methacrylate instead of trimethoxysilylpropyl methacrylate.

50 Biofouling testing

[0078] Marine grade plywood test panels were primed with Intershield 300 (International Paints Ltd) to give an average
dry film thickness of about 100 mm. Intersleek 731 silicone elastomer tie-coat (International Paints Ltd) was then applied
to give an average dry film thickness of about 100mm and the tie-coat was allowed to dry. The coating compositions of
55 Example 1, Example 2 and the Comparative Example A were then applied to the pre-treated panels in an average dry
film thickness of about 150 mm.
[0079] The panels were then immersed in Singapore, at Changi Marina, an aquatic environment where heavy marine
fouling growth is known to occur. After 74 weeks immersion an assessment was made of the board to quantify severity

10
 EP 3 571 251 B1

of animal fouling that was present. The results are shown in Table 1.

Table 1 - Coverage of animal fouling on test coatings after 74 weeks immersion

Coating Average % animal fouling coverage
5
Example 1 9
Example 2 10
Example A 36
10

Adhesion testing 1

[0080] 12x6" steel panels were degreased with solvent and then grit-blasted to SA2.5. Panels were then coated on
both sides with Intersleek 717 Link Coat (International Paint Ltd) as a primer coating by airless spray, dried under ambient
15
indoor conditions for 7 hours, and then coated on both sides with Intersleek 737 silicone elastomer tie-coat (International
Paint Ltd) by airless spray. After drying for 1 day under ambient indoor conditions, one set of panels was coated on both
sides by airless spray with the coating composition of Example 1, and a second set of panels was coated on both sides
by airless spray with the composition of comparative Example A. The test panels were then immediately removed to an
outside area and exposed to the ambient outdoor conditions in the winter of north east England for 48 hours.
20
[0081] The adhesion of the final coating to the previous coatings was qualitatively assessed by using a penknife blade
to make a first 5 cm cut through the coatings to the steel substrate, followed by a second 5 cm cut across the first cut
to make an ’X’ shape. The intersection of the cuts was rubbed with a finger and the relative difficulty of delaminating the
final coat from the previously applied coatings was noted. This allows the adhesion of different final coating layers to be
ranked.
25
[0082] The coating layer prepared from Comparative Composition A was more easily delaminated from the previously
applied coating layers than the coating prepared from Coating Composition 1 according to the invention. This demon-
strated that the coating composition of Example 1 provides better adhesion than the comparative composition A.

Adhesion testing 2
30

[0083] 6x4" aluminium Q-panels were surface roughened using sandpaper and then degreased with solvent. Panels
were then brush coated on both sides with tie-coat composition 1 or tie-coat composition 2. After drying for 1 day under
ambient indoor conditions, one set of panels was brush coated on both sides with the coating composition of Example
3, and a second set of panels was brush coated on both sides with the comparative coating composition of Example B.
35
The test panels were then immediately removed to an outside area and exposed to the ambient outdoor conditions in
the winter of north east England for 96 hours.
[0084] After 5, 24, and 96 hours of exposure, adhesion of the final coating to the tie-coating was qualitatively assessed
by using a penknife blade to cut through and remove a small section of the coatings down to the substrate. The exposed
section was rubbed by a finger and the adhesion between tie-coat and topcoat was given a rating between 0 (poor
40
adhesion) - 5 (very good adhesion).

Table 2 Adhesion between tie-coat and foul-release coat

Tie-coat Top-coat adhesion
45 5h 24h 96h
Tie-coat composition 1 Coating composition 3 0 3.5 3
Tie-coat composition 1 Comparative composition B 0 3 3.5
Tie-coat composition 2 Coating composition 3 4 5 5
50
Tie-coat composition 2 Comparative composition B 3.5 5 5

[0085] It can be summarized that the foul release coating compositions according to the invention can be used for a
longer time after mixing (longer pot-life), provide coatings having improved anti-fouling properties and better adhesion
55
than the comparative coating compositions.

11
 EP 3 571 251 B1

Claims

1. A non-aqueous liquid foul release coating composition for controlling aqueous biofouling on man-made objects
comprising:
5
i) a moisture curable polysiloxane comprising repeating units of formula (I)

10

15

and at least one terminal or pendant group of formula (II)

20

25

wherein R1 and R2 are, independently, organic groups having 1 to 20 carbon atoms; R3 and R4 are, independently,
organic groups having 1 to 20 carbon atoms; A is an organic group having 1 to 50 carbon groups; R5 is,
30 independently, selected from organic groups having 1 to 20 carbon atoms and groups of the formula O-R6
wherein R6 is an organic group having 1 to 20 carbon atoms, with the proviso that at least one R5 is a group of
the formula O-R6; and
ii) at least one of a marine biocide or a non-volatile component comprising units selected from hydrocarbyl,
heterocarbyl, halocarbyl, ether, ester, amide, ketone, siloxane, urethane or urea groups.
35
2. The foul release coating composition according to claim 1, wherein the coating composition further comprises an
aminosilane of formula (III)

40

45

wherein R3 to R5 and A are defined as in claim 1, and wherein at least one R5 is a group of the formula O-R6, wherein
R6 is an organic group having 1 to 20 carbon atoms.

50 3. The foul release coating composition according to claim 1 or 2, wherein component ii) does not contain groups of
formula (II).

4. The foul release coating composition according to any one of the preceding claims, wherein A is a methylene group.

55 5. The foul release coating composition according to any one of the preceding claims, wherein each of R1 and R2 is,
independently, a methyl group or a phenyl group.

6. The foul release coating composition according to any one of the preceding claims, wherein R5 is selected from C1

12
 EP 3 571 251 B1

to C4 alkoxy groups, preferably ethoxy groups.

7. The foul release coating composition according to any one of the preceding claims, wherein the coating composition
is essentially free or entirely free of a marine biocide.
5
8. The foul release coating composition according to any one of the preceding claims, wherein the coating composition
comprises a volatile organic solvent.

9. The foul release coating composition according to any one of the preceding claims, wherein the non-volatile content
10 is in the range of 70 to 100 % by weight.

10. A substrate coated with a foul release coating composition according to any one of the preceding claims.

11. A substrate according to claim 10, wherein the substrate is coated with a multi-layer coating system comprising:
15
- optionally a primer layer applied to the substrate and deposited from a primer coating composition;
- a tie-coat layer applied to the substrate or to the optional primer layer, deposited from a tie-coat composition
comprising an binder polymer with curable alkoxysilane functional groups; and
- a topcoat layer applied to the tie-coat layer, the topcoat layer deposited from a liquid foul release coating
20 composition according to any one of claims 1 to 9.

12. A substrate according to claim 10 or 11, wherein the tie-coat composition comprises a polyacrylate with curable
alkoxysilane functional groups.

25 13. A process for controlling aquatic biofouling of a man-made object, comprising the steps of:

a) applying the foul release coating composition according to anyone of the preceding claims 1 to 9 to at least
a part of the surface of the man-made object;
b) curing the coating composition to form a cured coating layer; and
30 c) immersing the man-made object at least partly in water.

14. A process according to claim 13, further comprising the step of applying a tie-coat layer deposited from a tie-coat
composition as specified in claim 11 or 12 on the at least part of the surface of the man-made object before applying
the foul release coating composition.
35
15. Use of the foul release coating composition according to any one the preceding claims 1 to 9 to control aquatic
biofouling on man-made objects.

40 Patentansprüche

1. Nichtwässrige flüssige Beschichtungszusammensetzung mit fäulnisgesteuerter Freisetzung zur Bekämpfung von

mit Wasser verbundener biologisch hervorgerufener Fäulnis auf künstlich geschaffenen Objekten, die Folgendes
umfasst:
45
i) ein feuchtigkeitshärtendes Polysiloxan, das Wiederholungseinheiten der Formel (I)

50

55

13
 EP 3 571 251 B1

und mindestens eine end- oder seitenständige Gruppe der Formel (II)

10

umfasst, wobei R1 und R2 unabhängig für organische Gruppen mit 1 bis 20 Kohlenstoffatomen stehen; R3 und
R4 unabhängig für organische Gruppen mit 1 bis 20 Kohlenstoffatomen stehen; A für eine organische Gruppe
15 mit 1 bis 50 Kohlenstoffatomen steht; R 5 unabhängig aus organischen Gruppen mit 1 bis 20 Kohlenstoffatomen
und Gruppen der Formel O-R6 ausgewählt ist, wobei R 6 für eine organische Gruppe mit 1 bis 20 Kohlenstoff-
atomen steht, mit der Maßgabe, dass mindestens ein R5 für eine Gruppe der Formel O-R6 steht, und
ii) mindestens ein Marinebiozid und/oder eine nichtflüchtige Komponente, umfassend aus Hydrocarbyl-, Hete-
rocarbyl-, Halogencarbyl-, Ether-, Ester-, Amid-, Keton-, Siloxan-, Urethan- oder Harnstoffgruppen ausgewählte
20 Einheiten.

2. Beschichtungszusammensetzung mit fäulnisgesteuerter Freisetzung nach Anspruch 1, wobei die Beschichtungs-

zusammensetzung ferner ein Aminosilan der Formel (III)

25

30

35 umfasst, wobei R 3 bis R5 und A wie in Anspruch 1 definiert sind und wobei mindestens ein R5 für eine Gruppe der
Formel O-R 6 steht, wobei R6 für eine organische Gruppe mit 1 bis 20 Kohlenstoffatomen steht.

3. Beschichtungszusammensetzung mit fäulnisgesteuerter Freisetzung nach Anspruch 1 oder 2, wobei Komponente

ii) keine Gruppen der Formel (II) enthält.
40
4. Beschichtungszusammensetzung mit fäulnisgesteuerter Freisetzung nach einem der vorhergehenden Ansprüche,
wobei A für eine Methylengruppe steht.

5. Beschichtungszusammensetzung mit fäulnisgesteuerter Freisetzung nach einem der vorhergehenden Ansprüche,

45 wobei R1 und R2 jeweils unabhängig für eine Methylgruppe oder eine Phenylgruppe stehen.

6. Beschichtungszusammensetzung mit fäulnisgesteuerter Freisetzung nach einem der vorhergehenden Ansprüche,

wobei R5 aus C1-C4-Alkoxygruppen, vorzugsweise Ethoxygruppen, ausgewählt ist.

50 7. Beschichtungszusammensetzung mit fäulnisgesteuerter Freisetzung nach einem der vorhergehenden Ansprüche,

wobei die Beschichtungszusammensetzung im Wesentlichen frei oder gänzlich frei von einem Marinebiozid ist.

8. Beschichtungszusammensetzung mit fäulnisgesteuerter Freisetzung nach einem der vorhergehenden Ansprüche,

wobei die Beschichtungszusammensetzung ein flüchtiges organisches Lösungsmittel umfasst.
55
9. Beschichtungszusammensetzung mit fäulnisgesteuerter Freisetzung nach einem der vorhergehenden Ansprüche,
wobei der nichtflüchtige Anteil im Bereich von 70 bis 100 Gew.-% liegt.

14
 EP 3 571 251 B1

10. Substrat, beschichtet mit einer Beschichtungszusammensetzung mit fäulnisgesteuerter Freisetzung nach einem
der vorhergehenden Ansprüche.

11. Substrat nach Anspruch 10, wobei das Substrat mit einem mehrschichtigen Beschichtungssystem beschichtet ist,
5 das Folgendes umfasst:

- gegebenenfalls eine auf das Substrat aufgetragene und aus einer Grundierungsbeschichtungszusammenset-
zung abgeschiedene Grundierungsschicht;
- eine auf das Substrat oder die fakultative Grundierungsschicht aufgetragene Haftbeschichtungsschicht, die
10 aus einer ein polymeres Bindemittel mit härtbaren funktionellen Alkoxysilangruppen umfassenden Haftbeschich-
tungszusammensetzung abgeschieden wird, und
- eine auf die Haftbeschichtungsschicht aufgetragene Deckschicht, wobei die Deckschicht aus einer flüssigen
Beschichtungszusammensetzung mit fäulnisgesteuerter Freisetzung nach einem der Ansprüche 1 bis 9 abge-
schieden wird.
15
12. Substrat nach Anspruch 10 oder 11, wobei die Haftbeschichtungszusammensetzung ein Polyacrylat mit härtbaren
funktionellen Alkoxysilangruppen umfasst.

13. Verfahren zur Bekämpfung von aquatischer biologisch hervorgerufener Fäulnis von einem künstlich geschaffenen
20 Objekt, das die folgenden Schritte umfasst:

a) Auftragen der Beschichtungszusammensetzung mit fäulnisgesteuerter Freisetzung nach einem der vorher-
gehenden Ansprüche 1 bis 9 auf zumindest einer Teiloberfläche des künstlich geschaffenen Objekts;
b) Härten der Beschichtungszusammensetzung zur Bildung einer gehärteten Beschichtungsschicht; und
25 c) zumindest teilweises Eintauchen des künstlich geschaffenen Objekts in Wasser.

14. Verfahren nach Anspruch 13, das ferner vor dem Auftragen der Beschichtungszusammensetzung mit fäulnisge-
steuerter Freisetzung den Schritt des Auftragens einer Haftbeschichtungsschicht, die aus einer wie in Anspruch 11
oder 12 angegebenen Haftbeschichtungszusammensetzung abgeschieden wird, auf zumindest der Teiloberfläche
30 des künstlich geschaffenen Objekts umfasst.

15. Verwendung der Beschichtungszusammensetzung mit fäulnisgesteuerter Freisetzung nach einem der vorherge-
henden Ansprüche 1 bis 9 zur Bekämpfung von aquatischer biologisch hervorgerufener Fäulnis auf künstlich ge-
schaffenen Objekten.
35

Revendications

1. Composition de revêtement antisalissure liquide non aqueuse destinée à contrôler le bio-encrassement aqueux sur
40 des objets fabriqués par l’homme comprenant :

i) un polysiloxane durcissable à l’humidité comprenant des motifs répétitifs de formule (I)

45

50

55 et au moins un groupe terminal ou pendant de formule (II)

15
 EP 3 571 251 B1

10 dans lesquelles R1 et R2 sont indépendamment des groupes organiques ayant 1 à 20 atomes de carbone ; R3
et R 4 sont indépendamment des groupes organiques ayant 1 à 20 atomes de carbone ; A est un groupe
organique ayant 1 à 50 atomes de carbone ; les R5 sont indépendamment choisis parmi les groupes organiques
ayant 1 à 20 atomes de carbone et les groupes de la formule O-R6 dans laquelle R6 est un groupe organique
ayant 1 à 20 atomes de carbone, à condition qu’au moins un R5 soit un groupe de la formule O-R6 ; et
15 ii) au moins un biocide marin et/ou un constituant non volatil comprenant des motifs choisis parmi les groupes
hydrocarbyle, hétérocarbyle, halogénocarbyle, éther, ester, amide, cétone, siloxane, uréthane et urée.

2. Composition de revêtement antisalissure selon la revendication 1, la composition de revêtement comprenant en

outre un aminosilane de formule (III)
20

25

dans laquelle les R3 à R5 et A sont définis comme dans la revendication 1, et dans laquelle au moins un R5 est un
30 groupe de la formule O-R6, dans laquelle R 6 est un groupe organique ayant 1 à 20 atomes de carbone.

3. Composition de revêtement antisalissure selon la revendication 1 ou 2, dans laquelle le constituant ii) ne contient
pas de groupes de formule (II).

35 4. Composition de revêtement antisalissure selon l’une quelconque des revendications précédentes, dans laquelle A
est un groupe méthylène.

5. Composition de revêtement antisalissure selon l’une quelconque des revendications précédentes, dans laquelle R1
et R2 sont chacun indépendamment un groupe méthyle ou un groupe phényle.
40
6. Composition de revêtement antisalissure selon l’une quelconque des revendications précédentes, dans laquelle R5
est choisi parmi les groupes alcoxy en C1 à C4, de préférence les groupes éthoxy.

7. Composition de revêtement antisalissure selon l’une quelconque des revendications précédentes, la composition
45 de revêtement étant quasiment dépourvue ou totalement dépourvue de biocide marin.

8. Composition de revêtement antisalissure selon l’une quelconque des revendications précédentes, la composition
de revêtement comprenant un solvant organique volatil.

50 9. Composition de revêtement antisalissure selon l’une quelconque des revendications précédentes, dans laquelle la
teneur en composés non volatils se situe dans la gamme de 70 à 100 % en poids.

10. Substrat revêtu d’une composition de revêtement antisalissure selon l’une quelconque des revendications précé-
dentes.
55
11. Substrat selon la revendication 10, le substrat étant revêtu d’un système de revêtement multicouche comprenant :

- éventuellement, une couche primaire appliquée au substrat et déposée à partir d’une composition de revête-

16
 EP 3 571 251 B1

ment primaire ;
- une couche d’accrochage appliquée au substrat ou à la couche primaire facultative, disposée à partir d’une
composition d’accrochage comprenant un polymère liant avec des groupes fonctionnels alcoxysilane
durcissables ; et
5 - une couche de finition appliquée à la couche d’accrochage, la couche de finition étant déposée à partir d’une
composition de revêtementantisalissure liquide selon l’une quelconque des revendications 1 à 9.

12. Substrat selon la revendication 10 ou 11, dans lequel la composition d’accrochage comprend un polyacrylate avec
des groupes fonctionnels alcoxysilane durcissables.
10
13. Procédé de contrôle du bio-encrassement aquatique d’un objet fabriqué par l’homme, comprenant les étapes
suivantes :

a) application de la composition de revêtement antisalissure selon l’une quelconque des revendications 1 à 9

15 à au moins une partie de la surface de l’objet fabriqué par l’homme ;
b) durcissement de la composition de revêtement pour former une couche de revêtement durcie ; et
c) immersion au moins partielle de l’objet fabriqué par l’homme dans l’eau.

14. Procédé selon la revendication 13, comprenant en outre l’étape d’application d’une couche d’accrochage déposée
20 partir d’une composition d’accrochage telle que spécifiée dans la revendication 11 ou 12 sur l’au moins une partie
de la surface de l’objet fabriqué par l’homme avant l’application de la composition de revêtement antisalissure.

15. Utilisation de la composition de revêtement antisalissure selon l’une quelconque des revendications 1 à 9 pour le
contrôle du bio-encrassement aquatique sur des objets fabriqués par l’homme.
25

30

35

40

45

50

55

17
 EP 3 571 251 B1

REFERENCES CITED IN THE DESCRIPTION

This list of references cited by the applicant is for the reader’s convenience only. It does not form part of the European
patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be
excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description

• GB 1307001 A [0003] • WO 2009106717 A2 [0036]

• US 3702778 A [0003] • WO 2009106718 A2 [0036]
• WO 2014131695 A [0004] • EP 1791424 A [0040]
• US 20150329724 A [0006] • EP 0709358 A [0041]
• EP 2161318 A [0007] • EP 0880892 A [0041]
• US 2013172193 A [0007] • EP 1142477 A [0041]
• FR 2761367 [0007] • EP 1115282 A [0041]
• CN 101134887 [0029] • WO 9933927 A [0060]
• WO 2007122325 A1 [0036] • CN 101134887 A [0070]
• WO 2008055985 A1 [0036]

18