WO2018158436A1 - Composition - Google Patents

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Publication number
WO2018158436A1
WO2018158436A1 PCT/EP2018/055193 EP2018055193W WO2018158436A1 WO 2018158436 A1 WO2018158436 A1 WO 2018158436A1 EP 2018055193 W EP2018055193 W EP 2018055193W WO 2018158436 A1 WO2018158436 A1 WO 2018158436A1
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WO
WIPO (PCT)
Prior art keywords
composition
polar solvent
meth
acrylate
silyl
Prior art date
Application number
PCT/EP2018/055193
Other languages
English (en)
Inventor
Marit Dahling
Cecilia Winander
Original Assignee
Jotun A/S
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jotun A/S filed Critical Jotun A/S
Priority to KR1020197028289A priority Critical patent/KR102610866B1/ko
Priority to DE112018001119.4T priority patent/DE112018001119T5/de
Priority to CN201880014854.1A priority patent/CN110382634B/zh
Priority to JP2019568810A priority patent/JP7145175B2/ja
Publication of WO2018158436A1 publication Critical patent/WO2018158436A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C09D5/1668—Vinyl-type polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents

Definitions

  • the present invention relates to an antifouling coating composition
  • an antifouling coating composition comprising a silyl (meth)acrylate polymer, tralopyril and a polar solvent, as well as to a method of preparing the composition.
  • the composition has excellent long term storage stability.
  • the invention also relates to paint comprising the composition and to a paint container containing the composition. Additionally the invention relates to an article comprising a coating on at least a part of a surface thereof and to a method of coating an article to prevent fouling thereon comprising coating at least a part of a surface of the article with the composition.
  • antifouling paints are used. These paints generally comprise polymers which form a film (sometimes referred to as film-forming binder), antifouling agents which deter or control the fouling, pigments and solvents. In many cases the paint also comprises one or more further compounds such as extenders, dehydrating agents and thixotropic agents.
  • Tralopyril is an antifouling agent having a broad-spectrum activity against hard- shelled and soft bodied animal organisms. It is therefore an attractive antifouling agent to incorporate into paint and especially paint designed for application to surfaces of submerged vessels such as ships.
  • tralopyril in paints, however, is that when it is combined with silyl (meth)acrylate polymer, the paint tends to thicken or even gel during storage and particularly during storage for >1 month, e.g. 6 months.
  • paints comprising silyl (meth)acrylate polymer and tralopyril tend to increase in viscosity during storage indicating that reactions are happening in the paint and it is not entirely stable. This is obviously a practical problem.
  • the viscosity of paint determines how it can be applied (e.g. whether it can be sprayed) and also impacts on the surface finish.
  • the paint is typically applied to very large surface areas and is most often applied by airless spray. The viscosity of the paint must therefore be in a range that enables application by state of the art equipment. A paint cannot be thinned and sprayed if it has gelled.
  • EP-A-3078715 recognises the stability problem encountered in paints comprising silyl (meth)acrylates and tralopyril. It confirms that such paints have a tendency to thicken during storage. EP-A-3078715 goes on to disclose that the problem can be overcome by the addition of a stabiliser selected from carbodiimides and/or silanes.
  • an antifouling composition comprising:
  • said polar solvent has an evaporation rate relative to n-butyl acetate of at least 0.1 and a Hansen solubility parameter, ⁇ of ⁇ 17.0 (J/cm 3 ) 1 ' 2
  • said composition comprises at least 2.5 wt% polar solvent, based on the total amount of solvent present in the composition, and said composition has a viscosity of less than 2000 cP.
  • the present invention provides a method for preparing a composition as hereinbefore described comprising mixing:
  • the present invention provides a paint comprising a composition as hereinbefore described.
  • the present invention provides a paint container containing a composition as hereinbefore described.
  • the present invention provides an article comprising (e.g. covered with or coated with) a coating on at least a part of a surface thereof, wherein said coating comprises the composition as hereinbefore described.
  • the present invention provides a method of coating an article to prevent fouling thereon, wherein said method comprises:
  • the present invention provides the use of a composition as hereinbefore described for coating at least a part of a surface of an article to prevent fouling thereon.
  • anti-antifouling coating composition refers to a composition that, when applied to a surface, prevents or minimises growth of marine organisms on a surface.
  • the term "paint” refers to a composition comprising the antifouling coating composition as herein described and optionally solvent which is ready for use, e.g. for spraying.
  • the antifouling coating composition may itself be a paint or the antifouling coating composition may be a concentrate to which solvent is added to produce a paint.
  • Hansen solubility parameter, ⁇ provides a measure of the hydrogen bonds between molecules in a solvent.
  • Hansen solubility parameter, ⁇ provides a measure of the dispersion forces between molecules in a solvent.
  • Hansen solubility parameter, ⁇ provides a measure of the dipolar intermolecular forces between molecules in a solvent.
  • silyl (meth)acrylate polymer refers to a polymer comprising repeat units derived from silyl (meth)acrylate monomers. Generally a silyl (meth)acrylate polymer will comprise at least 5 wt%, more preferably at least 20 wt% and still more preferably at least 40 wt% repeat units derived from silyl (meth)acrylate monomers, i.e. silyl acrylate and/or silyl methacrylate monomers.
  • alkyl refers to saturated, straight chained, branched or cyclic groups. Alkyl groups may be substituted or unsubstituted.
  • cycloalkyl refers to a saturated or partially saturated mono- or bicyclic alkyl ring system containing 3 to 10 carbon atoms. Cycloalkyl groups may be substituted or unsubstituted.
  • alkylene refers to a bivalent alkyl group.
  • aryl refers to a group comprising at least one aromatic ring.
  • the term aryl encompasses heteroaryl as well as fused ring systems wherein one or more aromatic ring is fused to a cycloalkyl ring.
  • Aryl groups may be substituted or unsubstituted.
  • An example of an aryl group is phenyl, i.e. C 6 H 5 . Phenyl groups may be substituted or unsubstituted.
  • substituted refers to a group wherein one or more, for example up to 6, more especially 1 , 2, 3, 4, 5 or 6, of the hydrogen atoms in the group are replaced independently of each other by the corresponding number of the described substituents.
  • optionally substituted as used herein means substituted or unsubstituted.
  • molecular weight refers to weight average molecular weight (Mw), unless otherwise specified.
  • PDI polymer dispersity index refers to the ratio Mw/Mn, wherein Mn refers to number average molecular weight.
  • volatile organic compound refers to a compound having a boiling point of 250 °C or less at a standard atmospheric pressure of 101 .3 kPa.
  • rosin refers to rosin and rosin derivatives.
  • anti-antifouling agent refers to a compound or mixture of compounds that prevents the settlement of marine organisms on a surface, and/or prevents the growth of marine organisms on a surface and/or encourages the dislodgement of marine organisms from a surface.
  • the term “extender” is used interchangeably with “filler” and refers to a compound which increases the volume or bulk of a coating composition.
  • the present invention relates to an antifouling coating composition
  • an antifouling coating composition comprising:
  • composition further comprises one or more of: (v) additional antifouling agent; (vi) carboxylic acid compound and/or derivative thereof; (vii) a binder; (viii) a pigment and/or extender; (ix) a dehydrating agent; and (x) an additive.
  • the combination of a silyl (meth)acrylate polymer, tralopyril and polar solvent advantageously provides a composition which has long term storage stability as well as excellent application properties.
  • the antifouling coating composition can be stored for an extended period of time (e.g. at least 1 month in uncontrolled temperature conditions) and still have a viscosity of less than 2000 cP which enables it to be applied to a surface, e.g. by spraying.
  • the polar solvent may replace some or all of the conventional solvents (e.g. aromatic hydrocarbon solvents) present in antifouling coating compositions.
  • the antifouling coating composition comprises a non-polar solvent.
  • the polar solvent present in the antifouling coating composition preferably has an evaporation rate relative to n-butyl acetate of at least 0.15.
  • the polar solvent has an evaporation rate relative to n-butyl acetate of 0.15 to 5.0, more preferably 0.2 to 2.5 and still more preferably 0.3 to 2.0.
  • the evaporation rate is determined according to ASTM D3539 in an evaporometer at a temperature of 25 °C and at a relative humidity below 5 %.
  • the polar solvent present in the antifouling coating composition preferably has a Hansen solubility parameter, ⁇ of ⁇ 15.0 (J/cm 3 ) 1 ' 2 .
  • the Hansen solubility parameter, ⁇ is 2.0 to 14.5 (J/cm 3 ) 1 ' 2 , more preferably 3.0 to 12.0 (J/cm 3 ) 1 ' 2 and still more preferably 3.5 to 10.0 (J/cm 3 ) 1 ' 2 .
  • the polar solvent present in the antifouling coating composition preferably has a Hansen solubility parameter, ⁇ of ⁇ 10.0 (J/cm 3 ) 1 ' 2 .
  • the Hansen solubility parameter, ⁇ is 1 .5 to 8.5 (J/cm 3 ) 1 ' 2 , more preferably 2.0 to 8.0 (J/cm 3 ) 1 ' 2 and still more preferably 2.5 to 7.5 (J/cm 3 ) 1 ' 2 .
  • the polar solvent present in the antifouling coating composition preferably has a Hansen solubility parameter, ⁇ of ⁇ 20.0 (J/cm 3 ) 1 ' 2 .
  • the Hansen solubility parameter, ⁇ is 10.0 to 20.0 (J/cm 3 ) 1 ' 2 , more preferably 12.0 to 18.0 (J/cm 3 ) 1 ' 2 and still more preferably 14.0 to 16.5 (J/cm 3 ) 1 ' 2 .
  • Hansen solubility parameters, ⁇ , ⁇ and ⁇ are available for a wide range of solvents, e.g. in HSPiP (Hansen Solubility Parameters in Practice) software 4th Edition 4.1 .07.
  • HSPiP Hanesen Solubility Parameters in Practice
  • the Hansen solubility parameters for some polar solvents suitable for use in the antifouling coating composition of the invention are provided below.
  • the polar solvent present in the antifouling coating composition preferably has a boiling point of 75°C to 250°C and more preferably a boiling point of 1 10°C to 180°C.
  • the polar solvent present in the antifouling coating composition of the invention preferably comprises at least one heteroatom selected from O, N, P and S and preferably O. More preferably the polar solvent present in the composition comprises one or two heteroatoms and still more preferably one or two O atoms.
  • the polar solvent present in the antifouling coating composition of the invention preferably comprises one or more functional groups selected from -O- (ether), -OC(O)- (ester), -C(O)- (ketone) and -C(OH)- (secondary alcohol).
  • the polar solvent comprises one or more -OC(O)-, -(CO)- and -C(OH)- functional groups.
  • the polar solvent present in the composition does not comprise a primary alcohol functional group.
  • the polar solvent present in the antifouling coating composition of the present invention is preferably selected from formulae (la)-(lc) and more preferably from formulae (lb) or (Ic):
  • each R is independently selected from linear or branched Ci -8 alkyl groups
  • R 1 is selected from linear or branched Ci -8 alkyl groups, optionally interrupted by
  • R 2 is selected from H or linear or branched Ci -8 alkyl groups, optionally interrupted by one -O- group.
  • R is linear or branched Ci -6 alkyl, more preferably Ci -4 alkyl and still more preferably methyl.
  • R is linear.
  • R 1 is linear or branched C 2-8 alkyl and more preferably C 4-5 alkyl.
  • Representative examples of preferred R 1 groups include n- butyl, n-pentyl, i-butyl and i-pentyl.
  • R 1 is linear or branched Ci -8 alkyl groups, interrupted by one -O- group.
  • R 1 is preferably linear or branched C 2-4 alkyl.
  • Representative examples of preferred R 1 groups include - CH 2 OCH 3 and -CH(CH 3 )CH 2 OCH 3 .
  • R 2 is H.
  • solvents of formula (la) along with their evaporation rate relative to n-BuAc and their Hansen solubility parameters are provided in the table below. These are preferred solvents of formula (la) for the antifouling coating composition of the present invention. 1 -methoxy-2-propanol is a preferred solvent of formula (la).
  • solvents of formula (lb) along with their evaporation rate relative to n-BuAc and their Hansen solubility parameters are provided in the table below. These are preferred solvents of formula (lb) for the antifouling coating composition of the present invention. n-Butyl acetate, isoamyl acetate and 1 - methoxy-2-propyl acetate are preferred solvents of formula (lb). Name Evaporation ⁇ ⁇ ⁇
  • solvents of formula (lc), along with their evaporation rate relative to n-BuAc and their Hansen solubility parameters are provided in the table below. These are preferred solvents of formula (lc) for the antifouling coating composition of the present invention. Methyl isoamyl ketone, methyl amyl ketone and methyl isobutyl ketone are preferred solvents of formula (lc).
  • the antifouling coating composition of the present invention comprises a polar solvent selected from 1 -methoxy-2-propanol, n-butyl acetate, isoamyl acetate, 1 -methoxy-2-propyl acetate, methyl isoamyl ketone, methyl amyl ketone, and methyl isobutyl ketone.
  • a polar solvent selected from 1 -methoxy-2-propanol, n-butyl acetate, isoamyl acetate, 1 -methoxy-2-propyl acetate, methyl isoamyl ketone, methyl amyl ketone, and methyl isobutyl ketone.
  • the antifouling coating composition of the present invention preferably comprises at least 3 wt% polar solvent, based on the total amount of solvent present in the composition.
  • the composition comprises at least 4 wt% polar solvent, more preferably 5 to 60 wt% and still more preferably 7 to 55 wt% polar solvent, based on the total amount of solvent present in the composition.
  • the amount of polar solvent present in the overall antifouling coating composition is preferably 0.5 to 30 wt%, more preferably 1 to 25 wt% and still more preferably 2 to 20 wt% based on the total weight of the composition.
  • the antifouling coating composition comprises a non-polar solvent.
  • the non-polar solvent is organic.
  • non-polar organic solvents examples include aromatic hydrocarbons such as xylenes, toluene, mesitylene and aliphatic hydrocarbons such as white spirit and limonene. Combinations of different non-polar solvents may also be used.
  • the non-polar solvent is an aromatic hydrocarbon and particularly preferably the non-polar solvent is xylene.
  • Suitable non-polar organic solvents are commercially available.
  • the amount of solvent, and particularly non-polar solvent, present in the antifouling coating compositions of the present invention is preferably as low as possible as this minimizes the VOC content.
  • the composition comprises up to to 98 wt% non-polar solvent or up to 97.5 wt% non-polar solvent, more preferably 40 to 90 wt% and still more preferably 45 to 85 wt% non-polar solvent, based on the total amount of solvent present in the composition.
  • non-polar solvent is present in the compositions of the invention in an amount of 0-35 wt%, more preferably 1 -30 wt% and still more preferably 1 -25 wt% based on the total weight of the composition.
  • compositions of the present invention comprise 2.5-60 wt% polar solvent and 40 to 97.5 wt% non-polar solvent, more preferably 5-60 wt% polar solvent and 40 to 95 wt% non-polar solvent and still more preferably 7-55 wt% polar solvent and 45-93 wt% non-polar solvent, based on the total amount of solvent present in the composition.
  • solvent content will vary depending on the other components present.
  • the silyl (meth)acrylate polymer present in the antifouling coating composition of the present invention is preferably a copolymer.
  • the silyl (meth)acrylate polymer present in the antifouling coating composition of the present invention comprises a residue of at least one silyl (meth)acrylate monomer and preferably a residue of at least one silyl (meth)acrylate monomer of formula (II):
  • R 4 is H or CH 3 ;
  • R 5 are each independently selected from linear or branched Ci -4 alkyl groups
  • R 6 are each independently selected from the group consisting of linear or branched Ci. 20 alkyl groups, C3-12 cycloalkyl groups, optionally substituted C 6- 2o aryl groups and -OSi(R 7 ) 3 groups;
  • each R 7 is independently a linear or branched Ci -4 alkyl group
  • Z is a Ci-C 4 alkylene
  • n is an integer from 0 to 1 ;
  • n is an interger from 0 to 5.
  • substituted aryl groups include aryl groups substituted with at least one substituent selected from halogens, alkyl groups having 1 to about 8 carbon atoms, acyl groups, or a nitro group.
  • Particularly preferred aryl groups include substituted and unsubstituted phenyl, benzyl, phenalkyl or naphthyl.
  • R 5 and R 7 groups include methyl, ethyl, n-propyl, i- propyl, n-butyl, i-butyl and t-butyl.
  • Z include -CH 2 -, -CH 2 CH 2 -, -(CH 2 )3- and -(CH 2 ) 4 .
  • Branched C 3-4 alkylene groups are also envisaged, e.g. -CH 2 CH(CH3)CI-l2-.
  • n 0.
  • R 6 are each independently selected from linear or branched Ci -2 o alkyl groups. Still more R 6 are each independently selected from linear or branched Ci -8 alkyl groups and still more preferably from C 2- 6 alkyl groups.
  • silyl (meth) acrylate monomers e.g. as defined by the general formula (II) include:
  • (meth)acrylates such as triisopropylsilyl (meth)acrylate, tri-n-butylsilyl (meth)acrylate, triisobutylsilyl (meth)acrylate, tri-sec-butylsilyl (meth)acrylate, butyldiisopropylsilyl (meth)acrylate, tert-butyldimethylsilyl (meth)acrylate, thexyldimethylsilyl (meth)acrylate, tert-butyldiphenylsilyl (meth)acrylate, triisopropylsiloxycarbonylmethyl (meth)acrylate, triisopropylsiloxycarbonylethyl (meth)acrylate, tert-butyldiphenylsiloxycarbonylmethyl (meth)acrylate, nonamethyltetrasiloxy (meth)acrylate, bis(trimethylsiloxy)methylsilyl (meth)acrylate and
  • Preferred monomers are alkylsilyl (meth)acrylates and more preferably trialkylsilyl (meth)acrylates, wherein one or more of the alkyl group(s) is branched.
  • Particularly preferred monomers include triisopropylsilyl (meth)acrylate, tri-n-butylsilyl (meth)acrylate, thexyldimethylsilyl (meth)acrylate and tert-butyldiphenylsilyl (meth)acrylate. Triisopropylsilyl acrylate and triisopropylsilyl methacrylate are particularly preferred.
  • the silyl (meth)acrylate polymer present in the antifouling coating composition of the present invention preferably comprises 1 -3 different monomers of formula (II) and more preferably 1 or 2 different monomers of formula (II).
  • the silyl (meth)acrylate polymer present in the antifouling coating composition of the present invention further comprises a residue of one or more (meth)acrylate monomers.
  • Preferred meth(acrylate) monomers present in the silyl (meth)acrylate polymer are those of formulae (llla)-(lllc):
  • R is hydrogen or methyl, R is a cyclic ether and X is a Ci-C 4 alkylene;
  • R 8 is hydrogen or methyl
  • R 10 is a C 3 -Ci 8 substituent with at least one oxygen or nitrogen atom, preferably at least one oxygen atom;
  • R 8 is hydrogen or methyl
  • R 11 is a CrC 8 hydrocarbyl
  • R 8 is hydrogen or methyl
  • R 9 is a cyclic ether (such as oxolane, oxane, dioxolane, dioxane optionally alkyl substituted)
  • X is a C-i-4 alkylene, preferably a Ci -2 alkylene.
  • the cyclic ether may contain a single oxygen atom in the ring or 2 or 3 oxygen atoms in the ring.
  • the cyclic ether may contain a ring comprising 2 to 8 carbon atoms, such as 3 to 5 carbon atoms. The whole ring might comprise 4 to 8 atoms, such as 5 or 6 atoms.
  • the cyclic ether ring may be substituted such as by one or more, such as one, C-i-6 alkyl group. That substituent group might be at any position on the ring including the position that binds to the X group.
  • Suitable monomers of formula (Ilia) include tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, isopropylideneglycerol methacrylate, glycerolformal methacrylate and cyclic trimethylolpropane formal acrylate.
  • Formula (Ilia) most preferably represents tetrahydrofurfuryl acrylate having the structure below:
  • R 8 is hydrogen or methyl
  • R 10 is a C3-18 substituent containing at least one oxygen or nitrogen atom, preferably at least one oxygen atom.
  • R 10 is of formula -(CH 2 CH 2 0) M -R 12 where R 12 is a CMO hydrocarbyl substituent, preferably a CMO alkyl or a C 6- io aryl substituent, and m is an integer in the range of 1 to 6, preferably 1 to 3.
  • R 10 is of formula -(CH 2 CH 2 0) M -R 12 where R 12 is an alkyl substituent, preferably methyl or ethyl, and m is an integer in the range of 1 to 3, preferably 1 or 2.
  • Preferred monomers of formula (1Mb) include one or more of 2-methoxyethyl methacrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl methacrylate, 2-(2- ethoxyethoxy)ethyl methacrylate and 2-(2-ethoxyethoxy)ethyl acrylate.
  • silyl (meth)acrylate polymers present in the antifouling coating composition of the present invention it is generally not preferred to have monomers of both formula (Ilia) and (1Mb) present.
  • R 8 is hydrogen or methyl
  • R 11 is a
  • C 1 -8 hydrocarbyl substituent preferably a Ci -8 alkyl substituent, most preferably methyl, ethyl, n-butyl or 2-ethylhexyl.
  • Preferred monomers of formula (lllc) include methyl methacrylate and n-butyl acrylate.
  • Preferred silyl (meth)acrylate polymers present in the antifouling coating composition of the invention comprise at least one monomer of formula (lllc).
  • the silyl (meth)acrylate polymer present in the antifouling coating composition of the present invention may optionally comprise other polymerizable monomers.
  • alkyl esters of acrylic acid and methacrylic acid such as 3,5,5- trimethylhexyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, dodecyl (meth)acrylate, isotridecyl (meth)acrylate, octadecyl (meth)acrylate
  • cyclic alkyl esters of acrylic acid and methacrylic acid such as cyclohexyl (meth)acrylate, 4-tert- butylcyclohexyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyl oxyethyl (meth)acrylate, isobornyl (meth)acrylate
  • aryl esters of acrylic acid and methacrylic acid such as
  • Preferred silyl (meth)acrylate polymers present in the antifouling coating composition of the present invention have a weight average molecular weight of 5000 to 80000, more preferably 10000 to 70000 and still more preferably 20000 to 60000.
  • Preferred silyl (meth)acrylate polymers present in the antifouling coating composition of the present invention have a number average molecular weight of 3000 to 20000, more preferably 5000 to 15000 and still more preferably 7000 to 12000.
  • Preferred silyl (meth)acrylate polymers present in the antifouling coating composition of the present invention have a Tg of 10 °C to 80 °C, more preferably 15 °C to 70 °C and still more preferably 20 °C to 60 °C.
  • the antifouling coating composition may comprise one or more (e.g. 1 , 2, 3, 4 or 5) silyl (meth)acrylate polymers as hereinbefore described.
  • Preferred antifouling coating compositions of the present invention comprise 1 , 2, 3 or 4 silyl (meth) acrylate polymers and still more preferably 1 or 2 silyl (meth)acrylate polymers.
  • the amount of monomers of formula (II) is preferably 5 to 80 wt%, more preferably 20 to 70 wt% and still more preferably 40 to 65 wt% based on the total weight of monomers.
  • the total amount of monomers of formula (Ilia) and (1Mb) is preferably 1 to 40 wt%, more preferably 2 to 30 wt% and still more preferably 5 to 25 wt% based on the total weight of monomers.
  • the amount of monomers of formula (III c) is preferably 1 to 50 wt%, more preferably 2 to 45 wt% and still more preferably 5 to 40 wt% based on the total weight of monomers.
  • the amount of other monomers is preferably 0 to 20 wt%, more preferably 0 to 15 wt% and still more preferably 0 to 10 wt% based on the total weight of monomers.
  • the total amount of silyl (meth)acrylate polymer present in the compositions of the invention is 1 -50 wt%, more preferably 2-40 wt% and still more preferably 5-35 wt%, based on the total weight of the composition.
  • Suitable silyl (meth)acrylate polymers may be prepared using polymerization techniques known in the art.
  • the silyl (meth)acrylate polymer may, for example, be obtained by polymerizing a monomer mixture in the presence of a polymerization initiator by any of various methods such as solution polymerization, bulk polymerization, emulsion polymerization, and suspension polymerization. Controlled polymerization techniques may, for example, be employed.
  • the polymer is preferably diluted with solvent to give a polymer solution having an appropriate viscosity.
  • Suitable polymerization initiators include azo compounds such as dimethyl 2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-methylbutyronitrile), 2,2'- azobis(isobutyronitrile) and 1 ,1 '-azobis(cyanocyclohexane) and peroxides such as tert- butyl peroxypivalate, tert- butyl peroxy-2-ethylhexanoate, tert-butyl peroxydiethylacetate, tert-butyl peroxyisobutyrate, di-tert-butyl peroxide, tert-butyl peroxybenozate, and tert-butyl peroxyisopropylcarbonate, tert-amyl peroxypivalate, tert-amyl peroxy-2- e
  • suitable solvents for polymerisation include aromatic hydrocarbons such as xylene, toluene, mesitylene; ketones such as methyl isobutyl ketone, methyl isoamyl ketone, cyclopentanone, cyclohexanone; esters such as butyl acetate, amyl acetate, isoamyl acetate, propylene glycol methyl ether acetate; ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dibutyl ether; alcohols such as 2-butanol, benzyl alcohol; ether alcohols such as 1 -methoxy-2-propanol; aliphatic hydrocarbons such as white spirit; and optionally a mixture of two or more solvents. These compounds are used alone or as a mixture of two or more thereof.
  • silyl (meth)acrylate polymers may be purchased commercially.
  • the antifouling coating composition of the present invention comprises tralopyril or a salt thereof.
  • This is an organic antifouling agent that is capable of preventing or removing marine fouling from a surface.
  • the organic biocide, tralopyril is sold by Janssen as Econea®.
  • Tralopyril is 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1 H- pyrrole-3-carbonitrile and has the structure shown below:
  • Tralopyril exhibits a broad spectrum of activity against various marine organisms including barnacles, mussels and tube worms. Salts thereof may also be used.
  • the term tralopyril is used below to discuss this biocide. The teaching equally applies to salts thereof.
  • Antifouling coating compositions of the present invention comprise tralopyril in an amount to ensure biocidal activity. Preferred amounts are 0.5 to 10 wt% (dry solids), preferably 1 to 7 wt%, preferably 2 to 6 wt%.
  • tralopyril exhibits greater biocidal efficacy towards marine organisms compared to metal biocides, meaning that the amount of metal biocide can be reduced or eliminated. In turn, unwanted effects such as discoloration due to the precipitation of copper salts is avoided or reduced.
  • a disadvantage of using tralopyril is that it causes instability in silyl (meth)acrylate containing compositions. This problem is, however, overcome in the antifouling coating compositions herein which comprises a polar solvent.
  • the antifouling coating composition comprises one or more additional antifouling agents.
  • antifouling agent biologically active compounds, antifoulant, biocide, toxicant are used in the industry to describe known compounds that act to prevent marine fouling on a surface.
  • the further antifouling agent present in the compositions of the invention is preferably a marine antifouling agent.
  • the antifouling agent may be inorganic, organometallic or organic. Suitable antifouling agents are commercially available.
  • inorganic antifouling agents include copper and copper compounds such as copper oxides, e.g. copper(l) oxide and copper(ll) oxide; copper alloys, e.g. copper-nickel alloys; copper salts, e.g. copper(l) thiocyanate and copper sulphide.
  • copper oxides e.g. copper(l) oxide and copper(ll) oxide
  • copper alloys e.g. copper-nickel alloys
  • copper salts e.g. copper(l) thiocyanate and copper sulphide.
  • organometallic antifouling agents include zinc pyrithione; organocopper compounds such as copper pyrithione, copper acetate, copper naphthenate, oxine copper, copper nonylphenolsulfonate, copper bis(ethylenediamine)bis(dodecylbenzensulfonate) and copper bis(pentachlorophenolate); dithiocarbamate compounds such as zinc bis(dimethyldithiocarbamate) [ziram], zinc ethylenebis(dithiocarbamate) [zineb], manganese ethylenebis(dithiocarbamate) [maneb] and manganese ethylene bis(dithiocarbamate) complexed with zinc salt [mancozeb].
  • organocopper compounds such as copper pyrithione, copper acetate, copper naphthenate, oxine copper, copper nonylphenolsulfonate, copper bis(ethylenediamine)bis(dodecylbenzensul
  • organic antifouling agents include heterocyclic compounds such as 2-(tert-butylamino)-4-(cyclopropylamino)-6-(methylthio)-1 ,3,5- triazine [cybutryne], 4,5- dichloro-2-n-octyl-4-isothiazolin-3-one [DCOIT], 1 ,2-benzisothiazolin-3-one, 2- (thiocyanatomethylthio)-1 ,3-benzothiazole [benthiazole] and 2,3,5,6-tetrachloro-4- (methylsulphonyl) pyridine; urea derivatives such as 3-(3,4-dichlorophenyl)-1 ,1 - dimethylurea [diuron]; amides and imides of carboxylic acids, sulphonic acids and sulphenic acids such as N-(dichlorofluoromethylthio)phthalimide, N- dichlorofluoromethylthio-
  • antifouling agents include tetraalkylphosphonium halogenides, guanidine derivatives, imidazole containing compounds such as 4-[1 -(2,3- dimethylphenyl)ethyl]-1 H-imidazole [medetomidine] and derivatives, macrocyclic lactones includes avermectins and derivatives thereof such as ivermectine and spinosyns and derivatives thereof such as spinosad, and enzymes such as oxidase, proteolytically, hemicellulolytically, cellulolytically, lipolytically and amylolytically active enzymes.
  • Preferred further antifouling agents are copper(l) oxide, copper thiocyanate, zinc pyrithione, copper pyrithione, zinc ethylenebis(dithiocarbamate) [zineb], 2-(tert- butylamino)-4-(cyclopropylamino)-6-(methylthio)-1 ,3,5-triazine [cybutryne], 4,5-dichloro- 2-n-octyl-4-isothiazolin-3-one [DCOIT], N-dichlorofluoromethylthio-N',N'-dimethyl-N- phenylsulfamide [dichlofluanid], N-dichlorofluoro methylthio-N',N'-dimethyl-N-p- tolylsulfamide [tolylfluanid] and 4-[1 -(2, 3-dimethylphenyl)ethyl]-1 H-imidazole [medetomidine].
  • Especially preferred further antifouling agents are copper(l) oxide, copper(l) thiocyanate, zinc pyrithione, copper pyrithione, zinc ethylenebis(dithiocarbamate) [zineb], 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one [DCOIT], and 4-[1 -(2,3- dimethylphenyl)ethyl]-1 H-imidazole [medetomidine].
  • the antifouling agents may be used alone or in mixtures as different antifouling agents operate against different marine fouling organisms. Mixtures of antifouling agents are generally preferred.
  • One preferred mixture of antifouling agents is active against marine invertebrates, such as barnacles, tubeworms, bryozoans and hydroids; and plants, such as algae (seaweed and diatoms); and bacteria
  • compositions of the present invention are free of an inorganic copper antifouling agent.
  • Such compositions preferably comprise a combination of tralopyril and one or more agents selected from zinc pyrithione, zineb and 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one.
  • compositions comprise tralopyril, copper(l) oxide and/or copper(l) thiocyanate and one or more selected from copper pyrithione, zineb and 4,5- dichloro-2-n-octyl-4-isothiazolin-3-one.
  • the combined amount of antifouling agents present in the antifouling composition may form up to 60 wt% of the coating composition, such as 0.1 to 50 wt%, e.g. 0.2 to 45 wt%, based on the total weight of the composition.
  • a suitable amount of antifouling agent might be 5 to 60 wt% in the coating composition.
  • lower amounts might be used such as 0.1 to 25 wt%, e.g. 0.2 to 20 wt%. It will be appreciated that the amount of antifouling agent will vary depending on the end use and the antifouling agent used.
  • antifouling agents are known in antifouling coatings and their use would be familiar to the skilled man.
  • the antifouling agent may be encapsulated or adsorbed on an inert carrier or bonded to other materials for controlled release. These percentages refer to the amount of active antifouling agent present and not therefore to any carrier used.
  • Preferred antifouling coating compositions of the invention comprise:
  • the antifouling coating composition of the present invention preferably comprises one or more compounds comprising a carboxylic acid group and/or derivatives thereof.
  • Derivatives include metal salts of compounds comprising a carboxylic acid group (also referred to as metal carboxylates) and esters of compounds comprising a carboxylic acid group, preferably methyl esters.
  • Preferred carboxylic acids compounds are rosins.
  • the antifouling coating composition of the present invention preferably comprises rosin and/or a rosin derivative.
  • Representative examples of rosins include wood rosin, tall oil rosin and gum rosin.
  • Representative examples of rosin derivatives include hydrogenated and partially hydrogenated rosin, disproportionated rosin, dimerised rosin, polymerised rosin, maleic acid esters, fumaric acid esters and other esters of rosin and hydrogenated rosin, copper rosinate, zinc rosinate, calcium rosinate, magnesium rosinate and other metal rosinates of rosin and polymerised rosin and others as described in WO 97/44401 .
  • the rosin or rosin derivative present in the antifouling coating composition of the present invention is a gum rosin.
  • the rosin present comprises rosin acids selected from abietic acid, neoabietic acid, dehydroabietic acid, dihydroabietic acid, tetrahydroabietic acid, secodehydroabietic acid, pimaric acid, isopimaric acid, levopimaric acid, palustric acid, sandaracopimaric acid, communic acid and derivatives thereof.
  • rosin acids selected from abietic acid, neoabietic acid, dehydroabietic acid, dihydroabietic acid, tetrahydroabietic acid, secodehydroabietic acid, pimaric acid, isopimaric acid, levopimaric acid, palustric acid, sandaracopimaric acid, communic acid and derivatives thereof.
  • carboxylic acid compounds examples include organic acid compounds such as VersaticTM acids, isononanoic acid, 2-ethylhexanoic acid, naphthenic acid, and other organic acids as described in EP1342756; cyclic carboxylic acid compounds such as 1 -methyl-3-(4-methyl-3-pentenyl)-3-cyclohexen-1 -yl-carboxylic acid, 1 -methyl-4-(4- methyl-3-pentenyl)-4-cyclohexen-1 -yl-carboxylic acid, 1 ,4,5-trimethyl-2-(2-methyl-1 - propenyl)-3-cyclohexen-1 -yl-carboxylic acid and 1 ,5,6-trimethyl-3-(2-methyl-1 - propenyl)-4-cyclohexen-1 -yl-carboxylic acid and others as described in EP 1695956 and JP2016216651A.
  • organic acid compounds such as VersaticTM acids, isononanoic acid
  • compounds comprising a carboxylic acid group and/or derivatives thereof is present in the compositions of the invention in an amount of 0-40 wt%, more preferably 1 -35 wt% and still more preferably 2-25 wt%, based on the total weight of the composition.
  • a mixture of one or more compounds comprising a carboxylic acid group and/or derivatives thereof may also be used.
  • Compounds comprising a carboxylic acid group and/or derivatives thereof including rosin and rosin derivatives are commercially available.
  • gum rosin which is preferably present in the coating compositions of the invention, is commercially available.
  • an additional binder may optionally be used to adjust the properties of the antifouling coating composition.
  • binders that can be used include:
  • (meth)acrylic polymers and copolymers in particular acrylate binders, such as poly(n-butyl acrylate), poly(n-butyl acrylate-co-isobutyl vinyl ether) and others as described in WO03/070832 and EP2128208;
  • acrylate binders such as poly(n-butyl acrylate), poly(n-butyl acrylate-co-isobutyl vinyl ether) and others as described in WO03/070832 and EP2128208;
  • hydrophilic copolymers for example (meth)acrylate copolymers as described in GB2152947 and poly(N-vinyl pyrrolidone) copolymers and other copolymers as described in EP0526441 ;
  • vinyl ether polymers and copolymers such as poly(methyl vinyl ether), poly(ethyl vinyl ether), poly(isobutyl vinyl ether), polyvinyl chloride-co-isobutyl vinyl ether);
  • aliphatic polyesters such as poly(lactic acid), poly(glycolic acid), poly(2- hydroxybutyric acid), poly(3-hydroxybutyric acid), poly(4-hydroxyvaleric acid), polycaprolactone and aliphatic polyester copolymer containing two or more of the units selected from the above mentioned units;
  • hydrocarbon resin e.g. as described in WO201 1/092143, such as hydrocarbon resin formed only from the polymerisation of at least one monomer selected from a C5 aliphatic monomer, a C9 aromatic monomer, an indene coumarone monomer, or a terpene or mixtures thereof.
  • Especially suitable additional binders are (meth)acrylic polymers and copolymers.
  • extender is used herein to encompass extenders as well as fillers. These compounds increase the bulk of the composition.
  • extenders and fillers are minerals such as dolomite, plastorite, calcite, quartz, barite, magnesite, aragonite, silica, wollastonite, talc, chlorite, mica, kaolin and feldspar; synthetic inorganic compounds such as zinc phosphates, calcium carbonate, magnesium carbonate, barium sulphate, calcium silicate and silica; polymeric and inorganic microspheres such as uncoated or coated hollow and solid glass beads, uncoated or coated hollow and solid ceramic beads, hollow, porous and compact beads of polymeric materials such as poly(methyl methacrylate), poly(methyl methacrylate-co- ethylene glycol dimethacrylate), poly(styrene-co-ethylene glycol dimethacrylate), poly(styrene-co-divinylbenzene), polystyrene and polyvinyl
  • the pigments may be inorganic pigments, organic pigments or a mixture thereof.
  • Inorganic pigments are preferred.
  • examples of inorganic pigments include titanium dioxide, iron oxides and zinc oxide.
  • Examples of organic pigments are naphthol red, phthalocyanine compounds, azo pigments and carbon black.
  • the total amount of extender, filler and/or pigment present in the compositions of the invention is 0-70 wt%, more preferably 1 -60 wt% and still more preferably 2-50 wt%, based on the total weight of the composition.
  • the skilled man will appreciate that the extender and pigment content will vary depending on the other components present and the end use of the coating composition.
  • the antifouling coating composition of the present invention optionally comprises a dehydrating agent, also refered to as water scavenger or drying agent.
  • a dehydrating agent is a compound which removes water from the composition in which it is present.
  • Dehydrating agents improve the storage stability of the antifouling coating composition by removing moisture introduced from raw materials, such as pigments and solvents, or water formed by reaction between carboxylic acid compounds and bivalent and trivalent metal compounds in the antifouling coating composition.
  • the dehydrating agents and desiccants that may be used in the antifouling coating compositions include organic and inorganic compounds.
  • the dehydrating agents can be hygroscopic materials that absorb water or binds water as crystal water, often refered to as desiccants.
  • desiccants include calcium sulphate hemihydrate, anhydrous calcium sulphate, anhydrous magnesium sulphate, anhydrous sodium sulphate, anhydrous zinc sulphate, molecular sieves and zeolites.
  • the dehydrating agent can be a compound that chemically reacts with water.
  • orthoesters such as trimethyl orthoformate, triethyl orthoformate, tripropyl orthoformate, triisopropy
  • Preferred dehydrating agents are those that chemically react with water.
  • Particularly preferred dehydrating agents are organosilanes.
  • Organosilanes are particularly preferred in antifouling coating compositions comprising inorganic copper antifouling agent.
  • the dehydrating agent is present in the compositions of the invention in an amount of 0-5 wt%, more preferably 0.5-2.5 wt% and still more preferably 1 .0-2.0 wt%, based on the total weight of the composition.
  • the antifouling coating compositions of the present invention do not comprise a carbodiimide compound.
  • the antifouling coating composition of the present invention preferably comprises one or more other components.
  • other components that can be added to the antifouling coating composition are reinforcing agents, thixotropic agents, thickening agents, anti-settling agents, dispersing agents, wetting agents and plasticizers.
  • Fibres include natural and synthetic inorganic fibres such as silicon-containing fibres, carbon fibres, oxide fibres, carbide fibres, nitride fibres, sulphide fibres, phosphate fibres, mineral fibres; metallic fibres; natural and synthetic organic fibres such as cellulose fibres, rubber fibres, acrylic fibres, polyamide fibres, polyimide fibres, polyester fibres, polyhydrazide fibres, polyvinylchloride fibres, polyethylene fibres and others as described in WO 00/77102.
  • the fibres have an average length of 25 to 2,000 ⁇ and an average thickness of 1 to 50 ⁇ with a ratio between the average length and the average thickness of at least 5.
  • reinforcing agents are present in the compositions of the invention in an amount of 0-20 wt%, more preferably 0.5-15 wt% and still more preferably 1 -10 wt%, based on the total weight of the composition.
  • thixotropic agents examples include silicas such as fumed silicas, organo-modified clays, amide waxes, polyamide waxes, amide derivatives, polyethylene waxes, oxidised polyethylene waxes, hydrogenated castor oil wax, ethyl cellulose, aluminium stearates and mixtures thereof.
  • thixotropic agents, thickening agents and anti-settling agents are each present in the composition of the invention in an amount of 0-10 wt%, more preferably 0.5-6 wt% and still more preferably 1.0-3.0 wt%, based on the total weight of the composition.
  • plasticizers are chlorinated paraffins, phthalates, phosphate esters, sulphonamides, adipates and epoxidised vegetable oils.
  • plasticizers are present in the compostions of the invention in an amount of 0-20 wt%, more preferably 1 -15 wt% and still more preferably 1 -10 wt%, based on the total weight of the composition.
  • the present invention also relates to a method of preparing the composition as hereinbefore described wherein the components present in the composition are mixed.
  • tralopyril is premixed with polar solvent and mixed with silyl (meth)acrylate polymer and non-polar solvent and other optional ingredients. Any conventional production method may be used.
  • silyl (meth)acrylate polymer and non-polar solvent and other optional ingredients are dispersed and milled and cooled prior to addition of tralopyril or a mixture comprising tralopyril and polar solvent.
  • composition as described herein may be prepared in a suitable concentration for use, e.g. in spray painting.
  • the composition is itself a paint.
  • the composition may be a concentrate for preparation of paint.
  • further solvent is added to the composition described herein to form paint.
  • Preferred solvents are as hereinbefore described in relation to the composition.
  • the antifouling coating composition or paint is preferably filled into a container. Suitable containers include cans, drums and tanks.
  • the antifouling coating composition is preferably supplied as a one-pack.
  • the composition is preferably supplied in a ready-mixed or ready to use form.
  • the one-pack product may be thinned with solvents prior to application.
  • the antifouling coating composition and paint of the invention preferably has a solids content of 40-80 vol%, more preferably 45-70 vol% and still more preferably 50- 65 vol%.
  • the antifouling coating composition and paint of the invention has a viscosity of 50 to 2000 cP, more preferably 50-1000 cP, still more preferably 100-900 cP and still more preferably 150-800 cP.
  • viscosity is measured using a Cone and Plate viscometer (ISO 2884-1 :1999) as described in the examples.
  • the antifouling coating composition and paint of the invention has a viscosity of 50 to 2000 cP, more preferably 50-1000 cP, still more preferably 100-900 cP and still more preferably 150-800 cP after storage for 1 week at 52°C according to ASTM D1849-95(2014).
  • the antifouling coating composition and paint of the invention has a viscosity of 50 to 2000 cP, more preferably 50-1000 cP, still more preferably 100-900 cP and still more preferably 150-800 cP after storage for 2 weeks at 52°C according to ASTM D1849-95(2014).
  • the antifouling coating composition and paint of the invention has a viscosity of 50 to 2000 cP, more preferably 50-1000 cP, still more preferably 100-900 cP and still more preferably 150- 800 cP after storage for 4 weeks at 52°C according to ASTM D1849-95(2014).
  • the antifouling coating composition of the invention does not form a gel during storage for 4 weeks at 52°C according to ASTM D1849-95(2014).
  • viscosity is measured using a Cone and Plate viscometer (ISO 2884-1 :1999) as described in the examples.
  • the antifouling coating composition and paint of the invention has a content of volatile organic compounds (VOC) of 50 to 500 g/L, preferably 50 to 420 g/L, e.g. 50 to 390 g/L.
  • VOC content can be calculated (ASTM D5201 -01 ) or measured (EPA, method 24).
  • the antifouling coating composition and paint of the invention has a viscosity of 50-1000 cP and a content of VOCs of 50 to 500 g/L, more preferably a viscosity of 100-900 cP and a content of VOCs of 50 to 420 g/L and more preferably a viscosity of 150-800 cP and a content of VOCs of 50 to 390 g/L.
  • the antifouling coating composition and paint of the invention can be applied to a whole or part of any article surface which is subject to fouling.
  • the surface may be permanently or intermittently underwater (e.g. through tide movement, different cargo loading or swell).
  • the article surface will typically be the hull of a vessel or surface of a fixed marine object such as an oil platform or buoy.
  • Application of the coating composition and paint can be accomplished by any convenient means, e.g. via painting (e.g. with brush or roller) or more preferably spraying the coating onto the article.
  • the surface will need to be separated from the seawater to allow coating.
  • the application of the coating can be achieved as conventionally known in the art. After the coating is applied, it is preferably dried.
  • the viscosity of the polymer solutions was determined in accordance with ASTM D2196-15 Test method A using a Brookfield DV-I viscometer with LV-2 or LV-4 spindle at 12 rpm. The polymers were tempered to 23.0°C ⁇ 0.5°C before the measurements.
  • the solids content of the polymer solutions was determined in accordance with ISO 3251 :2008.
  • a test sample of 0.4 g ⁇ 0.1 g was taken out and dried in a ventilated oven at 150°C for 30 minutes.
  • the weight of the residual material is considered to be the non-volatile matter (NVM).
  • the non-volatile matter content is expressed in weight percent. The result given is the average of three parallels.
  • the polymers were characterised by Gel Permeation Chromatography (GPC) measurement.
  • GPC Gel Permeation Chromatography
  • MWD molecular weight distribution
  • the analysis conditions were as set out in the table below.
  • Samples were prepared by dissolving an amount of polymer solution corresponding to 25 mg dry polymer in 5 ml. THF. The samples were kept for a minimum of 3 hours at room temperature prior to sampling for the GPC measurements. Before analysis the samples were filtered through 0.45 ⁇ Nylon filters. The weight- average molecular weight (Mw) and the polydispersity index (PDI), given as Mw/Mn, is reported.
  • Mw weight- average molecular weight
  • PDI polydispersity index
  • the glass transition temperature (Tg) was obtained by Differential Scanning
  • a quantity of solvent was charged to a temperature-controlled reaction vessel equipped with a stirrer, a condenser, a nitrogen inlet and a feed inlet.
  • the reaction vessel was heated and maintained at the reaction temperature of 85 °C.
  • a pre-mix of monomers, initiator and solvent was prepared. The pre-mix was charged to the reaction vessel at a constant rate over 2 hours under a nitrogen atmosphere. After a further 1 hour, post-addition of a boost initiator solution was added.
  • the reaction vessel was maintained at the reaction temperature of 85 °C for a further 2 hours. The temperature was then increased to 1 10 °C and maintained for a further 30 minutes.
  • the thinning solvent was added to the reactor and the copolymer solution was then cooled to room temperature.
  • the viscosity of the antifouling coating compositions were determined according to ISO 2884-1 :1999 using a Cone and Plate viscometer set at a temperature of 23 °C, working at a shear rate of 10000 s "1 and providing viscosity measurement range of 0-10 P. The result given is the average of three measurements.
  • the consistency of the antifouling paint compositions was determined according to ASTM D562-10(2014) Method B using a digital Stormer-type viscometer. The measurement was done on samples in 500 mL container at 23 °C.
  • VOC (g/L) of the antifouling coating compositions was calculated according to ASTM D5201 -01 .
  • the storage stability of the antifouling coating compositions were determined under the conditions described in ASTM D1849-95(2014).
  • the samples were stored in 250 mL containers at 52 °C. After storage, the samples were cooled to room temperature before the containers were opened. The consistency of the paints was evaluated. Liquid samples were stirred to homogenous quality and the viscosities were recorded using a Cone and Plate viscometer. Storage for 1 month at 52 °C simulates some of the effects of storage for 6 months to 1 year at 23 °C.
  • the components were mixed in the proportions given in Tables 3-1 to 3-3 and Table 4. The amounts are given in parts by weight. Table 4 describes comparative compositions.
  • the mixture was dispersed in the presence of an appropriate amount of glass beads (3-4 mm in diameter) in a 1 L container using a vibrational paint shaker for 15 minutes. The paint was transferred to 250 mL containers for storage stability testing.
  • the properties of the polar solvents employed in the antifouling coating compositions are summarised in Table 2 below.
  • the Hansen solubility properties were taken from HSPiP (Hansen Solubility Parameters in Practice) software 4th Edition 4.1 .07.
  • Antifouling coating compositions PA1 -PA17, PB1-13 and PC1 -4 all comprise a silyl (meth)acrylate, tralopyril and at least 2.5 wt% of polar solvent (either a ketone, ester or secondary alcohol). All of these coating compositions are stable to storage. Thus even after storage for 4 weeks in accelerated storage conditions, the compositions have not formed a gel which indicates that they are still applicable to a surface by spraying.
  • comparative example C-1 which comprises silyl (meth)acrylate and tralopyril, but lacks a polar solvent, forms a gel after 1 week of storage. This demonstrates that it is the addition of the polar solvent to the composition which provides the storage stability.
  • comparative example C-3 which comprises silyl (meth)acrylate, tralopyril and only 2 wt% polar solvent, based on the total weight of solvent, forms a gel after 1 week of storage in accelerated conditions.
  • PC-2 and PC-3 comprising 4 wt% and 9 wt% of polar solvent, based on the total weight of solvent, are stable to storage.
  • Comparative example C-2 which comprises silyl (meth)acrylate, but lacks tralopyril and polar solvent, is stable during storage. This shows that it is the combination of tralopyril and silyl (meth)acrylate which causes instability in antifouling compositions during storage.
  • An antifouling coating composition was prepared using a dissolver. 120 g copper pyrithione, 500 g silyl (meth)acrylate polymer solution S-2, 300 g gum rosin solution (60% in xylene) and 120 g methyl isoamyl ketone were mixed in a 3 L paint container. 1400 g copper(l) oxide, 240 g talc, 240 g zinc oxide, 80 g iron oxide red, 40 g titanium dioxide, 20 g oxidized polyether wax (25% in xylene) and 20 g tetraethoxysilane were added. The mixture was dispersed at high speed until the mill base had a fineness of grind of 40 ⁇ and a temperature of 55°C.
  • the paint composition had a calculated VOC of 403 g/L and a measured Stormer viscosity of 86 KU and a Cone and Plate viscosity of 369 cP.

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Abstract

La présente invention concerne une composition de revêtement antisalissure comprenant : (i) un polymère de (méth)acrylate de silyle ; (ii) du tralopyril ; (iii) un solvant polaire ; et (iv) un solvant non polaire ; ledit solvant polaire ayant un taux d'évaporation par rapport à l'acétate de n-butyle d'au moins 0,1 et un paramètre de solubilité de Hansen, δΗ de <17,0 (J/cm3)1/2, ladite composition comprenant au moins 2,5 % en poids de solvant polaire, sur la base de la quantité totale de solvant présent dans la composition, et ladite composition ayant une viscosité inférieure à 2000 cP.
PCT/EP2018/055193 2017-03-03 2018-03-02 Composition WO2018158436A1 (fr)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019081495A1 (fr) * 2017-10-23 2019-05-02 Hempel A/S Composition de revêtement antisalissure autopolissante comprenant un alcoxysilane
WO2020115323A1 (fr) * 2018-12-06 2020-06-11 Lonza Ltd Compositions complexes de chélate de cuivre pour protection antisalissure
WO2021191388A1 (fr) * 2020-03-27 2021-09-30 Jotun A/S Composition de revêtement antisalissure
CN114423830A (zh) * 2019-09-17 2022-04-29 克斯莫石油株式会社 环烷烃系溶剂
US11714361B2 (en) 2021-07-27 2023-08-01 Xerox Corporation Toner
US11834580B2 (en) 2021-07-27 2023-12-05 Xerox Corporation Ink composition with pH responsive resin particles
US11919982B2 (en) 2021-12-09 2024-03-05 Xerox Corporation Latexes with phosphoric acid functional resin particles
US11952448B2 (en) 2021-07-27 2024-04-09 Xerox Corporation Organic additives and compositions containing the same
US11952451B2 (en) 2021-07-27 2024-04-09 Xerox Corporation Latexes with pH responsive resin particles
EP4306599A4 (fr) * 2021-03-12 2024-06-19 Nitto Kasei Co., Ltd. Composition de revêtement antisalissure

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013025960A1 (fr) * 2011-08-17 2013-02-21 Arch Chemicals, Inc. Synthèse du cuivre pyrithione à partir du zinc pyrithione et d'un composé de cuivre
WO2015150249A1 (fr) * 2014-04-03 2015-10-08 Ppg Coatings Europe B.V. Composition de revêtement antisalissure érodable
EP3078715A1 (fr) * 2015-04-09 2016-10-12 Jotun A/S Composition antisalissure

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2790021B2 (ja) * 1993-09-30 1998-08-27 日本油脂株式会社 塗料組成物
JP2010150355A (ja) * 2008-12-25 2010-07-08 Nippon Paint Marine Kk 防汚塗料組成物、防汚塗膜、ならびに防汚塗膜の加水分解速度の制御方法
JP2016501951A (ja) * 2012-12-19 2016-01-21 ヨトゥン アーエス シリルエステルコポリマー
JP2016089167A (ja) * 2014-10-31 2016-05-23 中国塗料株式会社 防汚塗料組成物、防汚塗膜および防汚基材、ならびに防汚基材の製造方法
KR101991228B1 (ko) * 2015-09-25 2019-09-30 미쯔비시 케미컬 주식회사 (메트)아크릴계 공중합체, 중합체 용액, 중합체 함유 조성물, 방오 도료 조성물 및 (메트)아크릴계 공중합체의 제조 방법

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013025960A1 (fr) * 2011-08-17 2013-02-21 Arch Chemicals, Inc. Synthèse du cuivre pyrithione à partir du zinc pyrithione et d'un composé de cuivre
WO2015150249A1 (fr) * 2014-04-03 2015-10-08 Ppg Coatings Europe B.V. Composition de revêtement antisalissure érodable
EP3078715A1 (fr) * 2015-04-09 2016-10-12 Jotun A/S Composition antisalissure

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019081495A1 (fr) * 2017-10-23 2019-05-02 Hempel A/S Composition de revêtement antisalissure autopolissante comprenant un alcoxysilane
WO2020115323A1 (fr) * 2018-12-06 2020-06-11 Lonza Ltd Compositions complexes de chélate de cuivre pour protection antisalissure
US12041937B2 (en) 2018-12-06 2024-07-23 Arxada Ag Copper chelate complex compositions for antifouling protection
CN114423830A (zh) * 2019-09-17 2022-04-29 克斯莫石油株式会社 环烷烃系溶剂
WO2021191388A1 (fr) * 2020-03-27 2021-09-30 Jotun A/S Composition de revêtement antisalissure
EP4306599A4 (fr) * 2021-03-12 2024-06-19 Nitto Kasei Co., Ltd. Composition de revêtement antisalissure
US11714361B2 (en) 2021-07-27 2023-08-01 Xerox Corporation Toner
US11834580B2 (en) 2021-07-27 2023-12-05 Xerox Corporation Ink composition with pH responsive resin particles
US11952448B2 (en) 2021-07-27 2024-04-09 Xerox Corporation Organic additives and compositions containing the same
US11952451B2 (en) 2021-07-27 2024-04-09 Xerox Corporation Latexes with pH responsive resin particles
US11919982B2 (en) 2021-12-09 2024-03-05 Xerox Corporation Latexes with phosphoric acid functional resin particles

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JP7145175B2 (ja) 2022-09-30
KR102610866B1 (ko) 2023-12-06
CN110382634B (zh) 2022-01-11
JP2020511586A (ja) 2020-04-16
GB201703455D0 (en) 2017-04-19
DE112018001119T5 (de) 2019-11-21
CN110382634A (zh) 2019-10-25

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