WO2001060932A1 - Composition de peinture antisalissure - Google Patents

Composition de peinture antisalissure Download PDF

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Publication number
WO2001060932A1
WO2001060932A1 PCT/DK2001/000088 DK0100088W WO0160932A1 WO 2001060932 A1 WO2001060932 A1 WO 2001060932A1 DK 0100088 W DK0100088 W DK 0100088W WO 0160932 A1 WO0160932 A1 WO 0160932A1
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WO
WIPO (PCT)
Prior art keywords
tert
meth
acrylate
antifouhng
butyl
Prior art date
Application number
PCT/DK2001/000088
Other languages
English (en)
Inventor
Kazuyoshi Tuneta
Sadakazu Hokamura
Toshiya Takahashi
Hiroki Hayashi
Tomohiro Tanabe
Hiroyuki Tanabe
Yoshiyuki Iwase
Chugo Yokochi
Michael Stanley Pedersen
Frants Buchwald
Helle Simon Elbro
Santiago Arias Codolar
Tim Scott Gladwin
Peter Kwok Hing Lam
Original Assignee
J.C. Hempel's Skibsfarve-Fabrik A/S
Dai Nippon Toryo Co. Ltd.
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 J.C. Hempel's Skibsfarve-Fabrik A/S, Dai Nippon Toryo Co. Ltd. filed Critical J.C. Hempel's Skibsfarve-Fabrik A/S
Priority to AU31529/01A priority Critical patent/AU3152901A/en
Publication of WO2001060932A1 publication Critical patent/WO2001060932A1/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

Definitions

  • the present invention relates to an antifouhng paint composition for preventing attachment of marine organisms on the surface of objects in the sea for a long period of
  • Typical antifouhng paints which have heretofore been used, include insoluble matrix type antifouhng paints having an antifouhng agent incorporated to a binder comprising a resm insoluble in sea water, such as a vinyl type resm, an alkyd resm or chlorinated rubber, and rosin soluble in sea water, and soluble matrix type antifouhng paints containing as a binder a tin-containing resm which gradually hydrolyses in sea water and having an antifouhng agent incorporated as the case requires
  • the antifouhng agent will elute together with rosin into sea water, whereby a constant antifouhng effect for a long period of time can not be expected, and further, the insoluble resm component remaining in the coating film, will form a skeleton structure, whereby particularly when applied to ships or vessels, the f ⁇ ctional resistance between sea water and the coating film surface will increase, thus leading to drawbacks such as a decrease in the speed and an increase of the fuel costs
  • the above-mentioned soluble matrix type antifouhng paint containing a tin-containing resm as a binder component has an excellent antifouhng effect, but is problematic from the viewpoint of safety and sanitation, or environmental protection In Japan, its use is prohibited by regulations Under the circumstances, as antifouhng paints having the above-mentioned problems of the soluble matrix type antifouhng paint solved, there have been proposed an
  • antifouhng paints were all inferior in the long term antifouhng properties as compared with the conventional antifouhng paint using a tin-containing resin as a binder. Further, the antifouhng paints disclosed in the above-mentioned JP 9132736 A and WO 84/02915 were inferior in the storage stability when a metal-containing antifouhng agent was incorporated.
  • the present invention provides and possible improved solutions to these problems of the tin-free paint of the prior art, and it is an object of the present invention to provide an antifouhng paint composition which has little problem from the viewpoint of safety and sanitation, or environmental protection, and which is capable of preventing attachment of various marine organisms on the surface of objects such as fishing nets, maritime structures or bottom shell platings of ships or vessels located under the sea water surface for a long period of time.
  • the present inventors have conducted an extensive study to accomplish the above object and as a result, have found it possible to accomplish the object by using a resin having silylated sulfonate groups of a specific structure, as a binder for an antifouhng paint.
  • the present invention has been accomplished on the basis of this discovery.
  • the present invention provides an antifouhng paint composition containing, as a binder, a resin having groups of the formula (1):
  • n is 0-200, preferably 0-10 and each of R 1 , R 2 R 3 R 4 and R 5 which are independent of one another, is a hydrocarbon group selected from the group consisting of d 18 alkyl groups, Ci 18 alkoxy groups, C 7 19 aralkyl groups, C 3 9 cycloalkyl groups and C 6 18 aryl group, in its molecule
  • the antifouhng paint composition of the present invention comprises the above binder, optionally an antifouhng agent and a solvent as the main constituting components and may further contain various additives pigments, dyes, further binder components such as rosin or modified rosins and fibres as the case requires This will be explained in more detail below
  • the above-mentioned binder is a resm having silylated sulfonate groups of the formula (1)
  • silylated sulfonate groups of the formula (1) are those with the formula (1a)
  • R 1 , R 2 and R 3 have the same meanings as R 1 , R 2 and R 3 in the formula (1), corresponding to the formula (1) where n is 0
  • a typical example of the resin having such silylated sulfonate groups is an organic solvent-soluble type resm prepared by a copolyme ⁇ sation reaction of a polyme ⁇ sable unsaturated monomer (a) having a silylated sulfonate group of the above formula (1) with other polyme ⁇ sable unsaturated monomer(s) (b) copolyme ⁇ sable with the monomer (a), in an organic solvent in the presence of a polymerisation initiator in accordance with a usual method, for example, at a temperature of from 40 to 150°C such as 80 to 150°C for from 2 to 15 hours such as 3 to 15 hours
  • the above polymensable unsaturated monomer (a) is one which is obtainable by reacting (i) a monomer having a polymensable unsaturated double bond and a sulfonic acid group with (n) an organosilyl compound of the formula
  • n, R 1 , R 2 R 3 R 4 and R 5 have the same meanings as n, R 1 , R 2 R 3 R 4 and R 5 in the formula (1) and X designates a halogen atom such as chlorine or bromine, preferably chlorine, for example, in an organic solvent in the presence of a catalyst at a temperature of from 0 to 120°C for from 2 to 8 hours
  • a catalyst at a temperature of from 0 to 120°C for from 2 to 8 hours
  • platinum, palladium, aluminium, rhodium or ruthenium type is suitable as the catalyst mentioned above
  • a basic compound such as t ⁇ ethylamine or imidazole is suitable
  • organosilyl compounds leading to silylated sulfonates of the formula (1 a) are the tnorganosilyl compounds of formula
  • n is typically in the range of 1-200, preferably 1-10, particularly in the range of 1-4 such as 1 , 2 or 3
  • the monomers may also be present in the form of the alkali metal salt, e g the sodium salt
  • the organosilyl compound (u) is a compound of the formula (2) or (3), (2a) or (3a), respectively wherein each of R 1 , R 2 R 3 , R 4 and R 5 have the same meanings as n, R , R 2 R 3 R 4 and R 5 in the formula (1)
  • the d 18 alkyl group may be linear or branched
  • the alkyl group is typically a Ci 8 alkyl group and may, for example, be a methyl group, an ethyl group, a n-propyl group, an iso-propyl group, a n-butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group or an octyl group
  • a preferred alkyl group is one having a carbon number of from 3 to 6
  • the term "linear or branched C ⁇ 8 -alkylene" for Q is intended to mean any biradical of a Ci 8 -alkyl group
  • the Ci is alkoxy group may be linear or branched
  • the alkoxy group is typically a C-i 18 alkoxy group and may, for example, be a methoxy group, an ethoxy group, a n-propoxy group, an iso-propoxy group, an butoxy group, an iso-butoxy group, a sec-butoxy group, a tert-butoxy group, a pentoxy group, a hexyloxy group or an octyloxy group
  • a preferred alkoxy group is one having a carbon number of from 3 to 5
  • the C 7 19 aralkyl (aryl-d 13 -alkyl) group may, for example, be a benzyl group, a 2- phenylethyl group, or a 3-phenylpropyl group
  • the C 3 9 cycloalkyl group may, for example, be a cyclohexyl group, a cycloheptyl group, a cyclooctyl group or a cyclononyl group
  • the aryl group may, for example, be a phenyl group or a naphthyl group
  • the promising properties of the novel antifouhng paints of the invention at least in part resides in the fact that the silylated sulfonate groups will tend to hydrolyse upon contact with the aqueous environment
  • the rate of hydrolysis of the individual silylated sulfonate monomers will in part depend on the nature of the silyl substituents, in particular on the substituents on the silicon atom bound directly to the sulfonate group, i e the substituents R 1 , R 2 and R 3 where n is 0 and substituents R 4 and R 5 (in particular those neighbouring the sulfonate group, where n>0
  • Preferred meanings of the symbols R 1 , R 2 , R 3 , R 4 and R 5 in the formulae above are d 8 alkyl, benzyl and phen
  • the organosilyl compound of the formula (2a) may, for example, be t ⁇ methylsilane, tnethylsilane, t ⁇ -n-propylsilane, tn-iso-propylsilane, tn-n-butylsilane, tn-iso-butylsilane, dimethylhexylsilane, t ⁇ phenylsilane, dibutylhexylsilane, dibutylphenylsilane, di-tert- butylphenylsilane, diphenyl-tert-butylsilane, dimethyloctylsilane, di-tert-butylmethylsilane, tri-tert-butylsilane, tert-butyl-di-isobutylsilane, tert-butyl-di-isopropylsilane, thexyl-di- isobutyls
  • the organosilyl compound of the formula (3a) may, for example, be tnmethyl- chlorosilane, tnethylchlorosilane, t ⁇ -n-propylchlorosilane, tnisopropylchlorosilane, tri-n- butylchlorosilane, tnisobutylchlorosilane, tri-tert-butylchlorosilane, dibutylhexylchloro- silane, dimetyl n-propylchlorosilane, di-tert-butylmetylchlorosilane, dimethylbutylchloro- silane, dimethyloctylchlorosilane, dimethyldodecylchlorosilane, di-iso-propyloctylchloro- silane, dimetyloctadecylchlorosilane, tnphenylchloro
  • the polymensable unsaturated monomer (a) having such a silylated sulfonate group may, for example, be tnmethylsilylsulfoethyl (meth)acrylate, t ⁇ ethylsilylsulfoethyl (meth)acrylate, dibutylphenylsilylsulfoethyl (meth)acrylate, di-tert-butylmethylsilylsulfoethyl (meth)acrylate, tr ⁇ -tert-butyls ⁇ lylsulfoethyl(meth)acrylate, tert-butyl-di-isobutylsilylsulfoethyl- (meth)acrylate, tert-butyl-d ⁇ - ⁇ sopropyls ⁇ lylsulfoethyl(meth)acrylate, thexyl-dusobutylsilyl- sulfoe
  • polymensable unsaturated monomer(a) may be included in one polymer.
  • they may, for example, be (meth)acrylate type monomers such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, iso-propyl (meth)acrylate, n-butyl (meth)acrylate, iso-butyl (meth)acrylate, pentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)- acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, ⁇ -chloroethyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxy- ethyl (meth)acrylate, methoxypropyl (meth)acrylate, ethoxypropyl (meth)acrylate,
  • organic solvent type resin which will be a binder
  • various organic solvents which have been commonly used for paints can be used without any particular restrictions so long as they are capable of dissolving the resin.
  • it may, for example, be a hydrocarbon type solvent such as toluene or xylene; a ketone type solvent such as methyl ethyl ketone or acetone; an ester type solvent such as ethyl acetate, propyl acetate or butyl acetate; or an ether type solvent such as ethylene glycol monoethyl ether or ethyl ether.
  • a hydrocarbon type solvent such as toluene or xylene
  • a ketone type solvent such as methyl ethyl ketone or acetone
  • an ester type solvent such as ethyl acetate, propyl acetate or butyl acetate
  • an ether type solvent such as ethylene glycol monoethyl ether or ethyl ether.
  • solvents in which the components of the antifouhng paint are dissolved or dispersed are alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol and benzyl alcohol; alcohol/water mixtures such as ethanol/water mixtures; aliphatic, cycloaliphatic and aromatic hydrocarbons such as white spirit, cyclohexane, toluene, xylene and naphtha solvent; ketones such as methyl ethyl ketone, acetone, methyl isobutyl ketone, methyl isoamyl ketone, diacetone alcohol and cyclohexanone; ether alcohols such as 2-butoxyethanol, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethyl ether and butyl diglycol, esters such as ethyl acetate, propyl acetate, methoxypropyl a
  • the resin for the binder may be of a non-aqueous dispersion type
  • the non-aqueous dispersion type resm is a non-aqueous dispersion resin composed of a core component dispersed in a hydrocarbon type solvent and substantially insoluble in the solvent and a shell component (a dispersion stabiliser) which dissolves or swells in the solvent, wherein at least one of the core and shell components contains silylated sulfonate groups of the formula (1) or (1a)
  • the above hydrocarbon type solvent includes aliphatic, ahcychc and aromatic solvents
  • Such aliphatic and ahcychc hydrocarbon solvents include, for example, n-hexane, iso- hexane, n-heptane, n-octane, iso-octane, n-decane, n-dodecane, cyclohexane, methyl- cyclohexane and cycloheptane
  • Commercial products include, for example, mineral spirit ec, vm&p naphtha and shellzole 72 (manufactured by Shell Chemical Co ), naphtha no 3, naphtha no 5, naphtha no 6 and solvent no 7 (manufactured by Exxon Chemical Co ), ip solvent 1016, ip solvent 1620 and ip solvent 2835 (manufactured by idemitsu Petrochemical co , ltd ), and pengazole an-45 and pengazole 3040 (manufactured by Mobile Oil Co )
  • aromatic solvents include, for example, benzene, toluene, xylene and decalin
  • Commercial products include, for example, SOLVESSO 100 and SOLVESSO 150 (manufactured by Exxon Chemical Co ), and SWAZOLE (manufactured by Maruzen Oil Co , Ltd )
  • the non-aqueous dispersion resin may be prepared by a method wherein a polymerisable unsaturated monomer which is soluble in a hydrocarbon solvent and which is polymerisable to form a polymer (the core component) which is insoluble in the hydrocarbon solvent, is subjected to dispersion polymerisation in accordance with a conventional method in the hydrocarbon solvent in the presence of a shell component (the dispersion stabiliser) made of a polymer which dissolves or swells in the solvent.
  • a shell component the dispersion stabiliser
  • the monomer for forming the polymer for the shell component is not particularly limited so long as it dissolves in a hydrocarbon solvent to be used, and the polymer formed after the polymerisation will dissolve or swell therein, and the above-mentioned various polymerisable unsaturated monomers may be used. However, it is preferred to use a mixture of polymerisable unsaturated monomers containing from 30 to 100 weight % , preferably from 50 to 98 weight %, of a (meth)acrylate type monomer.
  • the above-mentioned various polymerisable unsaturated monomers can be used so long as they are soluble in a hydrocarbon solvent to be used, and the polymers formed after the polymerisation will be insoluble in the solvent.
  • Preferred is a monomer whereby the polymer will be hydrophilic.
  • the polymerisable unsaturated monomer which imparts hydrophilicity may, for example, be the above-mentioned carboxyl group-containing monomer, the hydroxyl group- containing monomer or the amino group-containing monomer.
  • the above-described polymerisable unsaturated monomer (a) is used as an essential component for at least one of the polymer for the shell component and the polymer for the core component constituting the non-aqueous dispersion resin, to incorporate silylated sulfonate groups of the formula (1).
  • the weight ratio of the core component to the shell component is not particularly limited. However, it is usually from 90/10 to 10/90, preferably from 80/20 to 25/75.
  • the non-aqueous dispersion type resin fine particles of the core component insoluble in an organic solvent are present as a part of the resin, and accordingly, the paint viscosity is relatively low as compared with an organic solvent-soluble resm, whereby it is possible to reduce the amount of the organic solvent to have a high solid content Further, by changing the amount of silylated sulfonate groups contained in the core component and the shell component, it is possible to adjust the hydrolysmg rate, i e a higher ratio of silylated sulfonate groups will increase the hydrolysmg rate for the polymer
  • an antifouhng paint composition is particularly preferred wherein a non-aqueous dispersion type resm containing silylated sulfonate groups, is used as the core component
  • a silylated sulfonate group-containing monomer is used as a starting material in the synthesis of each of the resins
  • a resm from the above-mentioned monomer (i) having a sulfonic acid group and a polymensable unsaturated monomer (b), and then a t ⁇ organosilyl compound (n) of the formula (2) or (3) is reacted to impart silylated sulfonate groups to the resin
  • the resm as the binder to be used in the present invention is prepared by the above-described method, wherein the amount of the silylated sulfonate group-containing polymensable unsaturated monomer (a) of the formula (1) is usually from 1-90, e g 3-90 such as 3-80 weight %, preferably from 3-60, e g 5-60 such as 5-30, e g 10-20 weight %, in the total monomer
  • the amount of the silylated sulfonate group-containing polymensable unsaturated monomer (a) of the formula (1) is smaller than the above range, the long term antifouhng property tends to deteriorate On the other hand, if it is too large, the coating film strength tends to deteriorate
  • the percentage amounts of unsaturated monomer (a) indicated above relates to the synthesised polymer
  • a certain fraction of the silylated sulfonate groups in the polymer may undergo hydrolysis in the preparation step due to presence of moisture
  • a certain degree of hydrolysis is normally acceptable
  • the general rate of hydrolysis of the silylated sulfonate groups may be adjusted by appropriate selection of the silyl substituents
  • the number average molecular weight of the resin as the binder is usually from 1 ,000 to 300,000, preferably from 5,000 to 100,000.
  • antifouhng agent which can be used in the present invention
  • various antifouhng agents which have been commonly used in antifouhng paints, can be used without any particular restriction.
  • Typical examples include metallo-dithiocarbamates such as bis(dimethyldithiocarbamato)zinc, ethylene-bis(dithiocarbamato)zinc, ethylene-bis(dithio- carbamato)manganese, and complexes between these; bis(1-hydroxy-2(1 H)-pyridine- thionato-0,S)-copper; copper acrylate; bis(1-hydroxy-2(1 H)-pyridinethionato-0,S)-zinc; phenyl(bispyridyl)-bismuth dichloride; metal biocides such as copper, copper metal alloys such as copper-nickel alloys; metal oxides such as cuprous oxide and cupric oxide (even though e.g.
  • cuprous oxide and cupric oxide may have pigment charac-teristics, it is understood that in the present context such agents are only considered as "antifouhng agents”); metal salts such as cuprous thiocyanate, basic copper carbonate, copper hydroxide, barium metaborate, and copper sulfide; heterocychc nitrogen compounds such as 3a,4,7,7a-tetrahydro-2-((trichloromethyl)-thio)-1 H-isoindole-1 ,3(2H)-dione, pyridine- triphenylborane, 1-(2,4,6-trichlorophenyl)-1 H-pyrrole-2,5-dione, 2,3,5,6-tetrachloro-4- (methylsulfonyl)-pyridine, 2-methylthio-4-tert-butylamino-6-cyclopropylamine-s-triazin, and quinoline derivatives; heterocychc sulfur compounds such as 2-(4-thiazolyl
  • the total amount of the antifouhng agent(s) may be in the range of 0-80%, such as 2-75%, by wet weight of the paint, preferably 5-75%, such as 5-70%, by wet weight of the paint
  • the total amount of the agent may, e g , be 5-60% or 10-50% by wet weight of the paint
  • the total amount of the antifouhng agent(s) may be expressed as being in the range of 0-70%, e g 2-50%, such as 3-50%, by solids volume of the paint, preferably 5-50%, such as 5-40%, by solids volume of the paint
  • the total amount of the agent may, e g , be 5- 15% or 10-25% by solids volume of the paint
  • a dehydrating agent is preferably incorporated, so that hydrolysis will not proceed by an influence of moisture during the storage of the antifouhng paint
  • the dehydrating agent may, for example, be synthetic zeolite, sepiohte, anhydrous gypsum, orthopropionic acid ester, orthoformic acid ester, orthoacetic acid ester alkoxysilane, alkyl silicates like tetra ethyl ortosihcate, or isocyanates It is used preferably in an amount of from 0 1 to 20% wet weight in the paint
  • the blend proportions of the respective components constituting the antifouhng paint composition of the present invention are usually such that the binder resm is from 5-60 such as 5-40% by wet weight, preferably from 15 to 40% by wet weight, the antifouhng agent is from 0 to 80%, preferably from 2-75% such as 5-60% by wet weight, and the solvent is from 10 to 60% such as 10-50%, preferably from 10 to 40 such as 15-40% by wet weight
  • the blend proportions of the respective components constituting the antifouhng paint composition of the present invention is such that the binder resm is from 5-70%, preferably from 10-65% by solids volume of the paint the antifouhng agent is from 0 to 70%, preferably from 5-50% such as 5-40% by solids volume
  • Pigments, further binder components e.g., rosin or modifying rosins .fibres and various additives are not essential constituting components.
  • pigments, plasticizers, further binder components e.g., rosin or modifying rosins, fibres and the additives may be incorporated in a total amount of up to 40% such as 30% by wet weight.
  • pigments are grades of titanium dioxide, red iron oxide, zinc oxide, carbon black, graphite, yellow iron oxide, red molybdate, yellow molybdate, zinc sulfide, antimony oxide, sodium aluminium sulfosilicates, quinacridones, phthalocyanine blue, phthalocyanine green, titaniumdioxide, black iron oxide, graphite, indanthrone blue, cobalt aluminium oxide, carbazole dioxazine, chromium oxide, isoindoline orange, bis-acetoacet- o-tolidiole, benzimidazolon, quinaphtalone yellow, isoindoline yellow, tetrachloro- isoindolinone, quinophthalone yellow.
  • Such materials are characterised in that they render the final paint coating non-transparent and non-translucent.
  • the pigments may further be selected from pigment-like ingredients such as fillers.
  • fillers are calcium carbonate, dolomite, talc, mica, barium sulfate, kaolin, silica, perlite, magnesium oxide, calcite and quartz flour, etc. These materials are characterised in that they do not render the paint non-translucent and therefore do not contribute significantly to hide any material below the coating of the paint of the invention.
  • the paint has a total pigment content (pigment and pigment-like ingredients) in the range of 1-60%, preferably 1-50%, such as 5-40% in particular 1-25% such as 1-15%, of the wet weight of the paint.
  • the total pigment content (pigment and pigment-like ingredients) can be expressed as being in the range of 1-60%, preferably 1-50%, in particular 1-25% such as 1-15%, of the solids volume of the paint.
  • dyes are 1,4-bis(butylamino)anthraquinone and other anthraquinone derivatives; toluidine dyes etc.
  • additives are plasticizers such as chlorinated paraffin; phthalates such as dibutyl phthalate, benzylbutyl phthalate, dioctyl phthalate, diisononyl phthalate and diisodecyl phthalate; phosphate esters such as tricresyl phosphate, nonylphenol phosphate, octyloxipoly(ethyleneoxy)ethyl phosphate, t butoxyethyl phosphate, iso- octylphosphate and 2-ethylhexyl diphenyl phosphate; sulfonamides such as N-ethyl-p- toluensulfonamide, alkyl-p-toluene sulfonamide, adipates such as b ⁇ s(2-ethylhexyl)- adipate), dnsobutyl adipate and dioctyladipate, phosphoric
  • the paints according to the present invention comprises dyes and additives in a cumulative content of 0-10% by wet weight
  • the cumulative content of dyes and additives can be expressed as being 0-15% by solids volume
  • oils such as linseed oil and derivatives thereof, castor oil and derivatives thereof, soy bean oil and derivatives thereof, other polymeric binder components such as saturated polyester resins; polyvinylacetate, polyvinylbutyrate, polyvinylchloride-acetate, copolymers of vinyl acetate and vinyl isobutyl ether; vinylchloride; copolymers of vinyl chloride and vinyl isobutyl ether; alkyd resins or modified alkyd resins; hydrocarbon resins such as petroleum fraction condensates; chlorinated polyolefines such as chlorinated rubber, chlorinated polyethylene, chlorinated polypropylene; styrene copolymers such as styrene/butadiene copolymers, styrene/methacrylate and styrene/acrylate copolymers; acrylic resins such as homopolymers and copolymers of methyl methacrylate, ethyl methacrylate, n
  • polymeric binder components may include polymeric flexibilisers such as those generally and specifically defined in WO 97/44401 which is hereby incorporated by reference.
  • % by wet weight is intended to mean the weight/weight percentage of the wet matter of the paint. It should be understood that solvents are included.
  • % by solids volume is intended to mean the volume/volume percentage of the dry matter of the paint. It should be understood that any solvents are not included in the contents stated as “% by solids volume”. Instead, the content of solvent(s) is expressed as "solids volume ratio" or SVR which indicates the volume of the dry matter in relation to the total volume of the paint including the solvent.
  • the antifouhng paint composition may also comprise fibres (e.g. those generally and specifically described in WO 00/77102 which is hereby incorporated by reference).
  • fibres e.g. those generally and specifically described in WO 00/77102 which is hereby incorporated by reference.
  • mineral fibres such as mineral-glass fibres, wollastonite fibres, montmo ⁇ llonite fibres, tobermo ⁇ te fibres, atapulgite fibres, calcined bauxite fibres, volcanic rock fibres, bauxite fibres, rockwool fibres, and processed mineral fibres from mineral wool
  • organic fibres can be especially advantageous within the present invention
  • Particularly preferred examples of such fibres are aromatic polyamide fibres, aromatic polyester fibres, aromatic polyimide fibres, cellulose fibres, cotton fibres, wood fibres, rubber fibres and fibres of derivatives of rubber, polyolefm fibres, polyacetylene fibres, polyester fibres, acrylic fibres and modified acrylic fibres, acrylonitnle fibres (e g preoxidised acrylonit ⁇ le fibres), elastome ⁇ c fibres, protein fibres, algmate fibres, poly(ethylene terephthalate) fibres, polyvmyl alcohol fibres, aliphatic polyamide fibres, polyvinylchlo ⁇ de fibres, polyurethane fibres, vinyl polymeric fibres, and viscose fibres
  • polyethylene fibres polypropylene fibres, cotton fibres, cellulose fibres, polyacrylonit ⁇ le fibres, preoxidised polyacrylonit ⁇ le
  • fibres including inorganic as well as organic fibres
  • mineral fibres such as mineral-glass fibres, wollastonite fibres, montmo ⁇ llonite fibres, tobermo ⁇ te fibres, atapulgite fibres, calcined bauxite fibres, volcanic rock fibres, bauxite fibres, rockwool fibres, processed mineral fibres from mineral wool, polyethylene fibres, polypropylene fibres, cotton fibres, cellulose fibres, polyacrylonitnle fibres, preoxidised polyacrylonitrile fibres, and polyester fibres
  • the concentration of the fibres is normally in the range of 0 1-50%,e g 0 1-25% by wet weight of the paint, such as 0 5-10% by wet weight of the paint
  • concentrations of fibres may be 2-10%, such as 2-7%, or 3-10%, such as 3-8% by wet weight of the paint
  • the concentration of the fibres is in the range of 0 1-25% by solids volume of the paint, such as 0 5-10% by solids volume of the paint
  • concentrations of fibres may be 2-10%, such as 2- 7%, or 3-10%, such as 3-8% by solids volume of the paint
  • the antifouhng paint composition of the present invention is prepared usually by mixing and dispersing the above components all at once or in a divided fashion by a conventional apparatus for producing paints, such as a ball mill, a pearl mill, a three-roll mill, a high speed disperser.
  • the antifouhng paints according to the invention may be filtrated using bag filters, patron filters, wire gap filters, wedge wire filters, metal edge filters, EGLM turnoclean filters (ex Cuno), DELTA strain filters (ex Cuno), and Jenag Strainer filters (ex Jenag), or by vibration filtration.
  • the antifouhng paint composition of the present invention thus prepared may be coated as it is or after having the viscosity adjusted by a diluting solvent, on a ship or a maritime structure having a rust preventive coating material coated thereon, by e.g. airless spray coating, air spray coating, roller coating or brush coating. .
  • airless spray coating air spray coating
  • roller coating or brush coating.
  • the exact technique chosen depends upon the object to be protected and also upon the particular composition (such as its viscosity etc.) and upon the particular situation.
  • Preferred applications techniques are spraying and by means of a brush or a roller.
  • the paint comprises solvent(s) so that the SVR is in the range of 30-100%, such as 30-70%.
  • the antifouhng paint according to the invention may be applied to the marine structure to be protected in one or several successive layers, typically 1 to 5 layers, preferably 1 to 3 layers.
  • the dry film thickness (DFT) of the coating applied per layer will typically be 10 to 300 ⁇ m, preferably 20 to 250 ⁇ m, such as 40 to 200 ⁇ m.
  • the total dry film thickness of the coating will typically be 10 to 900 ⁇ , preferably 20 to 750 ⁇ m, in particular 40 to 600 ⁇ m, such as 80 to 400 ⁇ m.
  • the marine structure to which the paint according to the invention may be applied to may be any of a wide variety of solid objects that come into contact with water, for example vessels (including but not limited to boats, yachts, motorboats, motor launches, ocean liners, tugboats, tankers, container ships and other cargo ships, submarines (both nuclear and conventional), and naval vessels of all types); pipes; shore and off-shore machinery, constructions and objects of all types such as piers, pilings, bridge substructures, floatation devices, underwater oil well structures etc, nets and other manculture installations, cooling plants, and buoys, and is especially applicable to the hulls of ships and boats and to pipes
  • vessels including but not limited to boats, yachts, motorboats, motor launches, ocean liners, tugboats, tankers, container ships and other cargo ships, submarines (both nuclear and conventional), and naval vessels of all types
  • pipes shore and off-shore machinery, constructions and objects of all types such as piers, pilings, bridge substructures, floatation devices, underwater oil well structures etc
  • the marine structure may first be coated with a primer-system which may comprise several layers and may be any of the conventional primer systems used in connection with application of antifouhng paints to marine structures
  • the primer system may include an anti- corrosive primer optionally followed by a layer of an adhesion-promoting primer
  • the primer-system is a composition having a polishing rate of less than 1 ⁇ m per 10,000 Nautical miles, i e the primer is a non-self-pohshing coating
  • the above-mentioned primer system may, for example, be a combination of an epoxy resin having an epoxy equivalent of from 160 to 600 with its curing agent (such as an am o type, a carboxylic acid type or an acid anhydride type), a combination of a polyol resm with a polyisocyanate type curing agent, or a coating material containing a vinyl ester resin, an unsaturated polyester resm or the like, as a binder, and, if required, further containing a thermoplastic resm (such as chlorinated rubber, an acrylic resm or a vinyl chloride resm), a curing accelerator, a rust preventive pigment, a coloring pigment, an extender pigment, a solvent, a trialkoxysilane compound, a plasticizer, an additive (such as an antisaggmg agent or a precipitation preventive agent), or a tar epoxy resin type coating material, as a typical example
  • a thermoplastic resm such as
  • the coating resulting from the paint according to the present invention is preferably self-polishing
  • the antifouhng paint (actually the coating) should have a polishing rate of at least 1 ⁇ per 10,000 Nautical miles (18,520 km)
  • the polishing rate is in the range of 1-50 ⁇ m, in particular in the range of 1-30 ⁇ m per 10,000 Nautical miles (18,520 km)
  • the present invention relates of a composition
  • a composition comprising
  • the present invention relates to a composition
  • a binder resm in an amount of from 5-75%, preferably from 5 to 60% by wet weight, one or more antifouhng agent(s) in a total amount of from 0 to 80%, preferably from 5-75%, such as 5-60% by wet weight
  • the present invention relates to a composition
  • a composition comprising:
  • additives including dehydrating agents, fibres, pigments, etc. 10-40% by wet weight of a solvent
  • the present invention relates of a composition
  • a composition comprising:
  • An stainless steel test panel (13.5 x 7 cm 2 ) with a curvature corresponding to that of a cylindrical drum with a diameter of 1 m is first coated with 40 ⁇ m of an epoxy primer (Hempadur Primer 15300 ex Hempel's Marine Paints A/S). After 24 hours, the panel is coated with 80 ⁇ m (DFT) of a commercial vinyl primer (Hempanyl Tar 16280 ex Hempel's Marine Paints A/S) applied by air spraying. After minimum 24 hours drying in the laboratory at room temperature the test paint is applied by air spraying in two coats in a DFT of approximately 100 ⁇ m per coat (total test paint DFT: 200 ⁇ m). Recoating interval between two coats of test paint: 24 hours. The initial thickness of the coat of the test paint is measured using an ISOSCOPE MP-3. The panel is dried for at least 1 week in the laboratory at room temperature before testing.
  • the test panel is fixed onto the convex surface of a cylindrical drum of 1 m in diameter and is rotated in sea water with a salinity in the range of 37-38 parts per thousand at an average temperature of 17-18°C at a test site in the harbour of Villanova y La Geltru in Northeastern Spam which is situated at longitude 41 2°N (see also Morale, E & Anas, E , Rev Iber Corros y Prot , vol XIX(2), 1988, pp 91-96)
  • the rotor is rotated at a peripheral speed of 15 knots for a relative distance of 33 100 Nautical miles
  • the thickness is controlled with periodic inspections using the ISOSCOPE MP-3
  • the polishing is the difference between the film thickness measures at a given inspection and the initial film thickness
  • the polishing rate is expressed as the polishing measured in ⁇ m per 10,000 Nm
  • Tests panels are tested in a Cleveland Condensation Tester (QCT from Q-Panel) in condensation and dry-off mode CCT equipment is described in standard method ASTM D 1735-92 Testing water resistance of coatings using water fog apparatus Coated specimens are placed in an enclosed chamber where cycles of water fog (10 hours)/dry ⁇ ng (2 hours) are applied The temperature in the chamber is maintained at 50°C During the water fog cycle water penetrates into the film while during the drying cycle water "escapes" from the paint film The test is operated for two months and the paints are evaluated every week for film defects as described below.
  • Very large cracks generally more than 1 mm wide 5
  • a solution of polymer is applied to a filter paper and the solvent is allowed to evaporate overnight.
  • the dry film is immersed in media and left for hydrolysis.
  • the amount of tri- alkylsilanol liberated by hydrolysis as a function of time can be determined by gas chromatography (GC).
  • Injection port temperature °C 150
  • Calibration standards were made by dissolving 0.02 g of internal standard and 0.02 g of triisopropylsilanol in 2 mL of toluene.
  • An acrylic test panel (15 x 20 cm 2 ), sandblasted on one side to facilitate adhesion of the coating., is first coated with 80 ⁇ m (DFT) of a commercial chlorinated rubber primer (Hempatex HI-BUILD 46330 ex Hempel's Marine Paints A/S) applied by air spraying. After a minimum drying time of 24 hours in the laboratory at room temperature the test paint is applied with a four sided "Bar" type applicator, with four gap sizes with a film width of 80 mm. One coat in a DFT of 90-100 ⁇ m. After at least 72 hours drying the test panels are fixed on a rack and immersed in sea water. Vilanova test variant
  • compositions illustrating the invention were prepared as described in the following-
  • TIPSS-BMA Triisopropylsilylsulfobutyl methacrylate
  • TIPSS-BMA monomer can be synthesised by reacting triisopropylsilane (TIPS) and a monomer having a polymerisable unsaturated double bond and a sulfonic acid group, such as sodium butylmethacrylate sulfonate (SBMAS), in a two-stage reaction.
  • TIPS triisopropylsilane
  • SBMAS sodium butylmethacrylate sulfonate
  • SBMAS butylmethacrylate sulfonic acid
  • TIPSS-BMA triisopropylsilane
  • Non-volatile contents was measured by drying 1 g resin at 150°C for 60 minutes.
  • Acid value was measured by titration of 0.5 g resin in MEK with 0.1 M KOH in methanol.
  • Model Paint Composition A (with the co- polymer A or B or C as described herein, and the references tr ⁇ sopropyls ⁇ lyl(meth) 5 acrylate based copolymer or tnbutyltin methacrylate methyl methacrylate co-polymer (Cutmox 1000/60 He ex Acima AG, Switzerland))
  • Cuprous Thiocyanate Ex Bardyke Chemicals LT, UK
  • Cuprous oxide, low tint LiLo Tint CDC ex American Chemet Export
  • Tr ⁇ sopropyls ⁇ lyl(meth)acrylate based copolymer (non-volatile matter 50% weight)
  • HDK N20 (ex Wacker Chemie, Germany)
  • Aditix M60 (ex Supercolon, Italy)
  • cuprous oxide 24 1% by solids volume of cuprous oxide (Nordox Cuprous oxide Paint Grade, Red, micro
  • Tr ⁇ sopropyls ⁇ lyl(meth) acrylate based copolymer 3 Tr ⁇ sopropyls ⁇ lyl(meth) acrylate based copolymer 3
  • Aditix M60 (ex Supercolo ⁇ , Italy)
  • Disperbyk 164 (ex. Byk Chemie, Germany)
  • Test results are provided in the format "3S1" where the first number, 3, indicates the density of cracking and the last number, 1 , indicates the size of cracking, cf the above description
  • Test results are provided in the format "3S1" where the first number, 3, indicates the density of cracking and the last number, 1 , indicates the size of cracking, cf the above description

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne une composition de peinture antisalissure, comme liant, une résine possédant des groupes de formule (1): -S(O)2-O-(Si(R?4)(R5)-O)¿n-Si(R?1)(R2)R3¿, dans laquelle n est compris entre 0 et 200, de préférence entre 0 et 10, et chacun des éléments R?1, R2, R3, R4 et R5¿, tous indépendants les uns des autres, représente un groupe hydrocarbure sélectionné dans un groupe composé de C¿1-18? groupes alkyle, C1-18 groupes alcoxy, C7-19 groupes aralkyle, C3-9 groupes cycloalkyle et C6-18 groupes aryle, dans sa molécule.
PCT/DK2001/000088 2000-02-15 2001-02-09 Composition de peinture antisalissure WO2001060932A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU31529/01A AU3152901A (en) 2000-02-15 2001-02-09 Antifouling paint composition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DKPA200000235 2000-02-15
DKPA200000235 2000-02-15

Publications (1)

Publication Number Publication Date
WO2001060932A1 true WO2001060932A1 (fr) 2001-08-23

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AU (1) AU3152901A (fr)
WO (1) WO2001060932A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003027194A2 (fr) * 2001-12-20 2003-04-03 Hempel A/S Dispersion non aqueuse reposant sur une composition de peinture antisalissure
CN102140288A (zh) * 2011-05-13 2011-08-03 武汉大学 一种含电解质防覆冰涂料
CN102220063A (zh) * 2011-05-13 2011-10-19 武汉大学 一种低表面能抗覆冰涂料及其制备方法
CN102321415A (zh) * 2011-08-11 2012-01-18 天津大学 一种氟硅丙烯酸树脂纳米复合防覆冰涂料及其制备方法
EP2802622A1 (fr) * 2012-01-13 2014-11-19 The Curators of The University of Missouri Revêtement de plasma à faible température pour la formation d'antibiofilm
EP3981843A4 (fr) * 2019-06-06 2022-07-06 Nitto Kasei Co., Ltd. Composition de revêtement antisalissure

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0232006A2 (fr) * 1986-01-22 1987-08-12 Imperial Chemical Industries Plc Compositions pour traitement de surface, polymères entrant dans ces compositions et procédé de traitement de surface
EP0273457A2 (fr) * 1986-12-30 1988-07-06 Nippon Oil And Fats Company, Limited Peinture antisalissure
US4957989A (en) * 1989-01-27 1990-09-18 Toshiba Silicone Co., Ltd. Vehicle for slow dissolving coating material
US5116611A (en) * 1987-06-28 1992-05-26 Nippon Oil And Fats Company Limited Antifouling paint
WO1996015198A2 (fr) * 1994-11-14 1996-05-23 J.C. Hempel's Skibsfarve-Fabrik A/S Composition de peinture antisallisure
US5795374A (en) * 1996-04-17 1998-08-18 Nof Corporation Coating composition

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0232006A2 (fr) * 1986-01-22 1987-08-12 Imperial Chemical Industries Plc Compositions pour traitement de surface, polymères entrant dans ces compositions et procédé de traitement de surface
EP0273457A2 (fr) * 1986-12-30 1988-07-06 Nippon Oil And Fats Company, Limited Peinture antisalissure
US5116611A (en) * 1987-06-28 1992-05-26 Nippon Oil And Fats Company Limited Antifouling paint
US4957989A (en) * 1989-01-27 1990-09-18 Toshiba Silicone Co., Ltd. Vehicle for slow dissolving coating material
WO1996015198A2 (fr) * 1994-11-14 1996-05-23 J.C. Hempel's Skibsfarve-Fabrik A/S Composition de peinture antisallisure
US5795374A (en) * 1996-04-17 1998-08-18 Nof Corporation Coating composition
US5795374C1 (en) * 1996-04-17 2002-03-05 Nof Corp Coating composition

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003027194A2 (fr) * 2001-12-20 2003-04-03 Hempel A/S Dispersion non aqueuse reposant sur une composition de peinture antisalissure
WO2003027194A3 (fr) * 2001-12-20 2004-03-18 Hempel As Dispersion non aqueuse reposant sur une composition de peinture antisalissure
CN1300263C (zh) * 2001-12-20 2007-02-14 汉伯公司 非水分散体基抗污油漆组合物
CN102140288A (zh) * 2011-05-13 2011-08-03 武汉大学 一种含电解质防覆冰涂料
CN102220063A (zh) * 2011-05-13 2011-10-19 武汉大学 一种低表面能抗覆冰涂料及其制备方法
CN102321415A (zh) * 2011-08-11 2012-01-18 天津大学 一种氟硅丙烯酸树脂纳米复合防覆冰涂料及其制备方法
EP2802622A1 (fr) * 2012-01-13 2014-11-19 The Curators of The University of Missouri Revêtement de plasma à faible température pour la formation d'antibiofilm
EP2802622A4 (fr) * 2012-01-13 2015-08-26 Univ Missouri Revêtement de plasma à faible température pour la formation d'antibiofilm
EP3981843A4 (fr) * 2019-06-06 2022-07-06 Nitto Kasei Co., Ltd. Composition de revêtement antisalissure

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