• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    antifouling composition comprising a curable polymer and a polymer or oligomer containing fluorinated oxyalkylene, method of inhibiting fouling of a substrate in an aquatic environment by applying the antifouling composition, and substrate. antifouling composition comprising a curable polymer and a fluorinated oxyalkylene-containing polymer or oligomer, wherein the fluorinated oxyalkylene-containing polymer or oligomer comprises: (a) one or more fluoride moieties of the formula: wherein: - if there are more than a fluoridated moiety, the fluoridated moiety may be identical or different; - can be independently 0 or 1; - m can independently be an integer from 0 to 6; and - r1, r2, r3 and r4 may independently be h; f; cl; br; a linear, branched or cyclic alkyl group containing from 1 to 16 carbon atoms optionally substituted by f; or a linear, branched or cyclic alkyloxyalkane group containing from 1 to 16 carbon atoms optionally substituted by f; and: (b) on average, 4.0 to 100.0 oxyalkylene moieties per polymer or oligomer, of the formula wherein: - if there is more than one oxyalkylene moiety, the oxyalkylene moiety may be identical or different; - n can independently be an integer from 0 to 4; and - r5, r6, r7 and r8 may independently be h or a linear, branched or cyclic C1-C16 alkyl group.
    公开号:BR112015019146B1
    申请号:R112015019146-0
    申请日:2014-02-21
    公开日:2022-01-04
    发明作者:Kevin John Reynolds；Brent Vickers Tyson
    申请人:Akzo Nobel Coatings International B.V.；
    IPC主号:
    专利说明:

    [001] The present invention relates to an antifouling composition comprising a curable polymer and a polymer or oligomer containing fluorinated oxyalkylene, a method of inhibiting scale in an aquatic environment and a substrate coated with the antifouling composition.
    [002] Man-made structures such as boat and ship hulls, buoys, drilling platforms, dry dock equipment, oil and gas production platforms, floating oil and gas processing, oil storage and offloading vessels, networks and aquaculture equipment, power generation devices, inlets, cables and pipes from power stations that are immersed in water and tanks, pipes and conduits used to store and transport water are prone to fouling by aquatic organisms such as diatoms, biological films of sludge, green and brown algae, barnacles, mussels and the like. Such structures are generally of metal, but may also comprise other structural materials such as wood, glass-reinforced plastic or concrete. Such fouling in the marine environment is an inconvenience on ship hulls because it increases frictional resistance during movement through the water, consequently reducing speed and increasing fuel consumption. It is an inconvenience in static structures such as the pillars of drilling rigs and oil and gas production, storage, processing and offloading platforms, primarily because the resistance of thick layers of fouling to waves and currents can cause unpredictable and potentially dangerous stresses in the structure, and second, because scale makes it difficult to inspect for defects in the structure, such as pressure cracks and corrosion. It is an inconvenience in pipes, such as cooling water inlets and outlets, as the effective cross-sectional area is reduced by fouling, with a consequent reduction in flow velocities.
    [003] The most commercially effective fouling inhibition methods have involved the use of antifouling coatings that contain substances toxic to aquatic life, eg tributyltin chloride or cuprous oxide. These coatings, however, are being increasingly neglected due to the harmful effects that these toxins can have if released into the aquatic environment in excessive amounts. Consequently, there is a need for antifouling coatings that do not release markedly toxic materials in excessive amounts.
    [004] It has been known for many years, for example, as described in GB 1,307,001 and US 3,702,778, that silicone rubber coatings resist fouling by aquatic organisms. These coatings are believed to have a surface to which organisms cannot easily adhere and can therefore be termed scale release coatings rather than antifouling. Silicone compounds and silicone rubbers generally have very low toxicity. The disadvantage of this anti-fouling system, when applied to the hulls of ships, is that while the build-up of marine organisms is reduced, very high vessel speeds are required to remove all species of fouling. Thus, in some cases, it has been shown that, for effective release of a hull that has been treated with this polymer, it is necessary to sail at a speed of at least 14 knots. For this reason, silicone rubbers have had limited commercial success and there is a need to improve the antifouling and scale release properties of these environmentally benign coatings.
    [005] FR 2,537,985 describes an antifouling coating composition comprising a methyl organosiloxane resin, silicone elastomer, polytetrafluoroethylene, acrylic binder and a solvent or diluent. As polytetrafluoroethylene does not contain oxyalkylene functionality, this document does not describe a coating composition comprising a polymer or oligomer containing fluorinated oxyalkylene.
    [006] EP 0,903,389 describes an antifouling composition comprising a photocatalytic oxide, a silicone or silica resin and a water repellent fluororesin. Tetrafluoroethylene is mentioned as a preferred hydrophobic fluororesin, and in the examples polytetrafluoroethylene particles were used. This document does not describe a coating composition comprising a polymer or oligomer containing fluorinated oxyalkylene.
    [007] WO 02/074870 describes an antifouling composition comprising a crosslinkable or curable polymer and an alkyl- or alkoxy-containing polymer or oligomer. There is no disclosure at present of a coating composition comprising polymers or oligomers containing fluorinated oxyalkylene which comprise, on average, 4.0 to 100.0 portions of oxyalkylene per polymer or oligomer.
    [008] The present invention provides an antifouling composition comprising a curable polymer and a fluorinated oxyalkylene-containing polymer or oligomer, wherein the fluorinated oxyalkylene-containing polymer or oligomer comprises: (a) one or more fluoride moieties of the formula:
    wherein: - if there is more than one fluoridated moiety, the fluoridated moiety may be identical or different; - p can independently be 0 or 1; - m can independently be an integer from 0 to 6; and - R1, R2, R3 and R4 may independently be H; F; Cl; BR; a linear, branched or cyclic alkyl group containing from 1 to 16 carbon atoms optionally substituted by F; or a linear, branched or cyclic alkyloxyalkane group containing from 1 to 16 carbon atoms optionally substituted by F; and (b) on average, 4 to 100 portions of oxyalkylene of the formula:
    wherein: - if there is more than one oxyalkylene moiety, the oxyalkylene moiety may be identical or different; - n can independently be an integer from 0 to 4; and - R5, R6, R7 and R8 may independently be H or a linear, branched or cyclic C1-C16 alkyl group.
    [009] It has been found that the antifouling composition according to the present invention has better fouling resistance and fouling release properties than other known and described non-biocidal antifouling compositions. CURABLE POLYMER:
    [010] The antifouling composition according to the present invention comprises a curable polymer. In one embodiment, the curable polymer is free of polyperfluoropolyether moieties.
    [011] Curable means a polymer that is capable of hardening or stiffening to form a coating as a result of a chemical reaction between functional groups located on the polymer and/or located on a crosslinker (screening), through solvent evaporation or by other physical means. The curable polymer may be a thermoplastic or heat-shrinkable polymer.
    [012] In one embodiment, the caravel polymer forms an "elastomeric coating" when cured.
    [013] By "elastomeric coating", we mean rubber-like coatings that demonstrate small and rapid plastic flow and recover almost completely from an extension force. When tested at room temperature (25°C) using a Zwick strain tester and ASTM D63810 compliant laser strain gauge, elastomer liners can be stretched to 25% (stretch speed 30 mm/minute) and, after being stretched to 25%, held for 5 minutes and then released, they are able to retract to 10% of their original length within 5 minutes of release. Free films for testing in this method shall have sample dimensions of 90 x 15 x 0.5 mm, prepared using the procedure provided in chapter 8.2.2 of ASTM D2370-98.
    [014] In one embodiment, the curable polymer is a polymer that contains organosiloxane. The organosiloxane-containing polymer may comprise a repeating unit with the general structure:
    wherein R9 and R10 are independently selected from hydrogen, alkyl, aryl, aralkyl, alkenyl and vinyl groups. It is preferred that R9 and R10 are independently selected from an alkyl selected from C1-C16 alkyl, phenyl, C1-C16 alkylphenyl or C1-C16 alkylene. More preferably, R9 and R10 are independently selected from methyl and phenyl. Another preferred organosiloxane-containing polymer is a polymer wherein R9 and R10 are methyl.
    [015] The organosiloxane-containing polymer may have one or more, preferably two or more reactive functional groups such as silanol, hydroxyl, alkoxy, acetoxy, carboxyl, hydroxysilyl, alkoxysilyl, amine, epoxy, vinyl, acrylic, methacrylic, isocyanate functional groups , thiol, carboxylic acid, carboxylic acid ester, urethane, ester or oxime.
    [016] In one embodiment, the curable polymer may be condensation curable (dihydroxy functional) polydimethylsiloxane that is crosslinked with tetraethyl orthosilicate and a condensation cure catalyst such as dibutyltin dilaurate or dioctyltin dilaurate. Polydimethylsiloxane may have a viscosity of 10 to 1,000,000 mPa.s at 25°C, measured according to ASTM D4287 using a cone and plate viscometer.
    [017] The curable polymer may contain siloxane groups that are substantially free of backbone carbon, such as polydimethylsiloxane (where substantially free of carbon indicates that less than 1% by weight of carbon is present). Other suitable polymers are those described in WO 99/33927, particularly the polymers described on page 12, lines 23-31, namely an organohydrogen polysiloxane or a polydiorganosiloxane. The polysiloxane may comprise, for example, a copolymer of diorganosiloxane units with organohydrogen siloxane units and/or with other diorganosiloxane units or a homopolymer of organohydrogen siloxane units or diorganosiloxane units.
    [018] Polysiloxanes that can be cross-linked through hydrosilylation reaction can also be used. Such polymers are known as "hydride silicones" and are described, for example, in EP 874032-A2 on page 3, namely a polydiorganosiloxane with the formula R' - (SiOR'2)m - SIR'3, where each R' is independently a hydrocarbon or fluorinated hydrocarbon radical, at least two R' radicals per molecule are unsaturated or hydrogen, at least two R' radicals per molecule are hydrogen and have an average value in the range of about 101500. They can also be used cyclic polydiorganosiloxanes analogous to the formula above. The hydride silicone is preferably a hydrogen polydimethylsiloxane.
    [019] The numerical average molecular weight range for silicon hydride is in the range of about 1,000-28,000, corresponding to a value of m in the range of about 13-380.
    [020] In another embodiment, the curable polymer may comprise two or more organosiloxanes with different chemical structures and viscosities.
    [021] Alternatively, the curable polymer may be the polymer as described in WO 2008/132196, wherein the polymer is a polyorganosiloxane polyoxyalkylene block copolymer of the form PS - (A - PO - A - PS)n, wherein PS represents a polyorganosiloxane block, PO represents a polyoxyalkylene block, A represents a divalent moiety and n has a value of at least 1, for example 10250. The polymer described in WO 2008/132196 has two or three reactive groups X on a block of polyorganosiloxane per molecule that can self-condense and cross-link in the presence or absence of a catalyst that can optionally be cross-linked with another organosilicon cross-linking agent that contains two or more Y groups that are reactive to said X groups. Other suitable polymers are those discussed in WO 2013/000478 and WO 2013/000479.
    [022] In another embodiment, the curable polymer may be one or more siloxane-acrylic hybrid polymers. The siloxane-acrylic hybrid polymers are free of perfluoropolyether moieties. Preferably, they contain less than 10% by weight of fluorine, more preferably less than 1% by weight. Even more preferably, they are polymers that are curable or contain no detectable concentration of fluorine.
    [023] Polymer or oligomer containing fluorinated oxyalkylene:
    [024] The antifouling composition according to the present invention comprises a fluorinated oxyalkylene-containing polymer or oligomer comprising: (a) one or more fluoridated portions of the formula:
    m where: - if there is more than one fluoridated moiety, the fluoridated moiety may be identical or different; - p can independently be 0 or 1; - m can independently be an integer from 0 to 6; and - R1, R2, R3 and R4 may independently be H; F; Cl; BR; a linear, branched or cyclic alkyl group containing from 1 to 16 carbon atoms optionally substituted by F; or a linear, branched or cyclic alkyloxyalkane group containing from 1 to 16 carbon atoms optionally substituted by F; and (b) on average, 4.0 to 100.0 oxyalkylene portions of the formula:
    wherein: - if there is more than one oxyalkylene moiety, the oxyalkylene moiety may be identical or different; - n can independently be an integer from 0 to 4; and - R5, R6, R7 and R8 may independently be H or a linear, branched or cyclic C1-C16 alkyl group.
    [025] For the avoidance of doubt, by definition, "fluoridated portion" must contain at least one fluorine atom, that is, at least one of R1, R2, R3 and R4, in the fluoridated portion, must comprise a fluorine atom ( F).
    [026] For the avoidance of doubt, the terms "fluoridated moiety", "fluoridated moieties", "oxyalkylene moiety" and "oxyalkylene moieties" shall be understood to have the structures defined above and as further defined herein.
    [027] The quantitative determination of the number of fluoridated moieties and oxyalkylene moieties per polymer/oligomer can be determined by means of conventional NMR analysis (19F NMR, 1H NMR and 13C NMR), for example as described in Macromolecules 1995, Vol. 28, No. 21, pages 7271-7275.
    [028] Preferably, there are on average 4.0 to 20.0 portions of oxyalkylene in the polymer or oligomer that contains fluorinated oxyalkylene.
    [029] Preferably, the oxyalkylene moieties are oxyethylene moieties.
    [030] R1, R2, R3 and R4 may independently be H; F; Cl; BR; a linear, branched or cyclic alkyl group containing from 1 to 16 carbon atoms optionally substituted by F; or a linear, branched or cyclic alkyloxyalkane group containing from 1 to 16 carbon atoms optionally substituted by F.
    [031] Examples of linear alkyl groups that contain from 1 to 16 carbon atoms substituted by F include CF3, -CF2CF3, -CF2CF2CF3 and -CF2CF2CF2CF3.
    [032] Examples of linear alkyloxyalkane groups containing from 1 to 16 carbon atoms optionally substituted by F include -CH2OCH2CF3 or -CH2OCH2CF2CF3. For example, R1, R2, R3 and R4 may independently be any one or more of: F, -CF3, -CH2OCH2CF3 or -CH2OCH2CF2CF3, preferably F and/or -CF3.
    [033] Preferably, R5, R6, R7 and R8 are independently H or -CH3, -CH2CH3, and more preferably wherein R5, R6, R7 and R8 are H.
    [034] The fluoridated portions and/or oxyalkylene portions at the ends of the polymer or oligomer containing fluorinated oxyalkylene may be terminated with a hydrogen or a linear, branched or cyclic C1-C12 alkyl group, such as methyl, phenyl or acyl groups, such as ethanol groups. Fluoride moieties and oxyalkylene moieties located at the ends of the fluorinated oxyalkylene-containing polymer or oligomer are preferably terminated with a hydrogen group or an alkyl group, for example a linear, branched or cyclic C1-C12 alkyl group, preferably a C1- alkyl group. C6 and more preferably H or -CH3 (methyl group), phenyl or acyl groups such as ethanol groups. Other optional acyl groups include methanoyl, ethanoyl, propanoyl, benzoyl or propenoyl. Additional groups that may enclose the fluoridated moieties and/or oxyalkylene moieties include carboxyl, amine, amide, phosphate, epoxy, vinyl, acrylic, methacrylic, isocyanate, thiol, carboxylic acid, carboxylic acid ester, urethane, ester or oxime functional groups or fluoride moieties such as -CF3.
    [035] A hydrogen-terminated oxyalkylene moiety or an alkyl group may hereinafter be termed a hydrogen-terminated oxyalkylene moiety or an alkyl-terminated oxyalkylene moiety. A hydrogen-terminated fluoridated moiety or an alkyl group may hereinafter be termed a hydrogen-terminated fluoridated moiety or an alkyl-terminated fluoridated moiety.
    [036] As an example, the polymer or oligomer containing fluorinated oxyalkylene may comprise: (ai) one or more fluoridated portions of the formula:
    and/or (aii) one or more fluoridated moieties of the formula:
    and (b) on average, 4.0 to 100.0 portions of oxyalkylene per polymer or oligomer of the formula:

    [037] As another example, the fluorinated oxyalkylene-containing polymer or oligomer may comprise: (ai) one or more fluoridated moieties of the formula:
    and/or (aii) one or more fluoridated moieties of the formula:
    and (b) on average, 4.0 to 100.0 portions of oxyalkylene per polymer or oligomer of the formula:

    [038] As another example, the fluorinated oxyalkylene-containing polymer or oligomer may comprise: (ai) one or more fluoridated portions of the formula:
    and/or (aii) one or more fluoridated moieties of the formula:
    and (b) on average, 4.0 to 100.0 portions of oxyalkylene per polymer or oligomer of the formula:

    [039] The polymer or oligomer that contains fluorinated oxyalkylene may have a numerical average molecular weight (Mn) in the range of 400 to 40,000. More preferably, the average molecular weight (Mn) is in the range of 750 to 10,000.
    [040] The numerical average molecular weight is determined by means of Fluorine-19 NMR analysis according to S. Turri et al, Macromolecules, 1995, 28, 7271-7275 and S. Turri et al, Macromol. Chem. Phys. 198 3215-3228 (1997).
    [041] The polymer or oligomer that contains fluorinated oxyalkylene can be a fluid or a solid. Preferably, the fluorinated oxyalkylene-containing polymer is a fluid having a viscosity of from 10 to 1,000,000 mPa.s at 25°C and more preferably from 50 to 100,000 mPa.s at 25°C, measured in accordance with ASTM D4287, using a cone and plate viscometer.
    [042] The oxyalkylene moieties and fluoride moieties can be positioned as part of the polymer/oligomer backbone or as pendant groups on the polymer/oligomer backbone.
    [043] In a preferred embodiment, the polymer or oligomer containing fluorinated oxyalkylene can be defined as an essentially linear copolymer with chains composed of blocks of one or more fluoridated moieties and blocks of one or more oxyalkylene moieties, in which the blocks are bonded with each other in an essentially linear fashion, e.g. alternating or random. Preferably, the blocks of oxyalkylene moieties contain, independently of one another, on average 2.0 to 50.0 parts of oxyalkylene per polymer or oligomer, more preferably on average 2.0 to 10.0 parts of oxyalkylene per polymer or oligomer .
    [044] For example, the polymer or oligomer containing fluorinated oxyalkylene is preferably in the form OA-(F-OA)n, where OA is a block of one or more oxyalkylene moieties and F is a block of one or more more fluoridated portions. n is an integer and preferably is 1. The number average molecular weight (Mn) of the polymer/oligomer is preferably in the range of 400 to 40,000 (determined using Fluor-19 NMR spectroscopy as mentioned above). The average number of oxyalkylene moieties in the fluorinated oxyalkylene-containing polymer or oligomer is from 4.0 to 100.0. Preferably, n is 1 and the average number of oxyalkylene moieties in each block of oxyalkylene moieties independently ranges from 2.0 to 50.0, more preferably from 2.0 to 10.0. Suitably, the OA moieties are terminated with hydrogen or an alkyl group, for example a C1-C12 alkyl group, preferably a C1-C6 alkyl group.
    [045] As another example, the polymer or oligomer containing fluorinated oxyalkylene is in the form F-(OA-F)n, where OA is a block of one or more oxyalkylene moieties and F is a block of one or more more fluoridated portions. n is an integer such as 1. The number average molecular weight (Mn) of the polymer/oligomer is preferably in the range of 400 to 40,000 (determined using Fluorine-19 NMR spectroscopy as mentioned above). The average number of oxyalkylene moieties in the fluorinated oxyalkylene-containing polymer or oligomer is from 4.0 to 100.0. Preferably, n is 1 and the average number of oxyalkylene moieties in each block of oxyalkylene moieties independently ranges from 2.0 to 50.0, more preferably from 2.0 to 10.0. Suitably the F moieties are terminated with hydrogen or an alkyl group, for example a C1-C12 alkyl group, preferably a C1-C6 alkyl group.
    [046] In an alternative embodiment, the fluorinated oxyalkylene-containing polymer or oligomer is a polymer having a backbone of one or more fluoridated moieties which has, dangling therefrom, blocks of one or more oxyalkylene moieties.
    [047] In a further embodiment, the fluorinated oxyalkylene-containing polymer or oligomer is a polymer that has a backbone of, on average, 4.0 to 100.0 oxyalkylene moieties that has, dangling from it, one or more blocks of one or more oxyalkylene moieties.
    [048] Alternatively, the fluorinated oxyalkylene-containing polymer or oligomer may be a combination of any of the aforementioned embodiments, i.e., the fluorinated oxyalkylene-containing polymer or oligomer may be an essentially linear copolymer with chains composed of blocks of one or more moieties fluoride and/or blocks of one or more oxyalkylene moieties, wherein the blocks are linked together in an essentially linear fashion, which have, hanging therefrom, blocks of one or more oxyalkylene moieties and/or one or more fluoridated moieties .
    [049] In all embodiments, the average number of oxyalkylene moieties per polymer or oligomer containing fluorinated oxyalkylene is from 4.0 to 100.0. Preferably, the average number of oxyalkylene moieties in each block of oxyalkylene moieties ranges from 2.0 to 50.0, more preferably from 2.0 to 10.0.
    [050] In all embodiments, preferably, the number average molecular weight (Mn) of the polymer/oligomer is in the range of 400 to 40,000.
    [051] The fluoridated moieties and/or oxyalkylene moieties located at the ends of the polymer or oligomer containing fluorinated oxyalkylene are preferably terminated with hydrogen or an alkyl group (for example, a methyl or ethyl group).
    [052] The oxyalkylene portions in the polymer or oligomer containing fluorinated oxyalkylene are preferably oxyethylene portions of the structure:

    [053] There can be, on average, 4.0 to 100.0 portions of oxyethylene in the polymer or oligomer that contains fluorinated oxyalkylene. Preferably, the average number of oxyethylene moieties in each block of oxyethylene moieties ranges from 2.0 to 50.0, more preferably from 2.0 to 10.0.
    [054] In a preferred embodiment, the fluorinated oxyalkylene-containing polymer or oligomer is an essentially linear copolymer with chains composed of blocks of one or more fluoridated moieties and blocks of one or more oxyethylene moieties, wherein the blocks are linked together. itself essentially linearly, e.g. alternating or random. Preferably, the blocks of oxyethylene moieties contain, independently of one another, on average from 2.0 to 50.0 moieties of oxyethylene, more preferably from 2.0 to 10.0 moieties of oxyethylene.
    [055] For example, the polymer or oligomer containing fluorinated oxyethylene is an oxyethylene-terminated copolymer of the form OE-(F-OE)n, where OE is a block of one or more oxyethylene moieties and F is a block of one or more fluoridated moieties. n is an integer and preferably is 1. The number average molecular weight (Mn) of the polymer/oligomer is preferably in the range of 400 to 40,000. The average number of oxyethylene moieties per polymer or oligomer containing fluorinated oxyethylene ranges from 4.0 to 100.0, preferably from 4.0 to 20.0. Preferably, n is 1 and the average number of oxyethylene moieties in each block of oxyethylene moieties ranges from 2.0 to 50, more preferably from 2.0 to 10.0.
    [056] Suitably, the OE moieties are terminated with hydrogen or an alkyl group (eg methyl or ethyl group).
    [057] In one embodiment, the antifouling composition according to the present invention may comprise one or more or two or more polymers or oligomers that contain fluorinated oxyalkylene.
    [058] In another embodiment, the antifouling composition according to the present invention may comprise one or more or two or more polymers or oligomers that contain fluid fluorinated alkyl or alkoxy as described in WO 02/074870.
    [059] Examples of polymers or oligomers that contain fluorinated oxyalkylene that can be used in the antifouling composition according to the present invention are: Fluorolink® E10-6, Fluorolink® 5144X and Fluorolink® 5147X (Solvay Specialty Polymers) and PolyFox® PF-651 and Polyfox® PF-652 (Omnova Solutions Inc). Other examples of suitable fluorinated oxyalkylene-containing polymers or oligomers are described in WO 2004/035656 and EP 1553123.
    [060] It is currently understood that the polymer or oligomer containing fluorinated oxyalkylene is not chemically reactive to curable polymers and does not participate in any crosslinking reaction. LOADS:
    [061] The antifouling composition according to the present invention may also comprise fillers. Examples of fillers that can be used in the coating composition according to the present invention are barium sulfate, calcium sulfate, calcium carbonate, silicas or silicates (such as talc, feldspar and clay) including fumed silica, bentonite and other clays. and solid silicone resins, which are generally branched condensed polysiloxanes, such as a silicone resin comprising Q units of the formula SiO4/2 and M units of the formula Rm3SiO1/2, wherein the Rm substituents are selected from alkyl groups that contain 1 to 6 carbon atoms and the ratio of M units to Q units is in the range of 0.4:1 to 1:1. Some fillers such as fumed silica can have a thixotropic effect on the coating composition. The proportion of fillers may be in the range of 0 to 25% by weight, based on the total weight of the coating composition, preferably in the range of 0 to 10% by weight and most preferably in the range of 0 to 5% by weight. Weight. PIGMENTS:
    [062] The antifouling composition according to the present invention may also comprise pigments.
    [063] Examples of pigments include iron oxide black, iron oxide red, iron oxide yellow, titanium dioxide, zinc oxide, soot, graphite, molybdate red, molybdate yellow, zinc sulfide, antimony oxide, sodium aluminum sulfosilicates, quinacridones, phthalocyanine blue, phthalocyanine green, indanthrone blue, cobalt aluminum oxide, carbazolodioxazine, chromium oxide, isoindoline orange, bisacetoacetotolidiol, benzimidazolone, quinaphthalone yellow, isoindoline yellow, tetrachloroisoindolinone and quinophthalone yellow, metallic flake materials (e.g. aluminum flakes) or other so-called barrier pigments or anti-corrosive pigments such as zinc dust or zinc alloys or other so-called lubricating pigments such as graphite, molybdenum disulfide, tungsten or boron nitride.
    [064] Preferred pigments are iron oxide black, iron oxide red, iron oxide yellow, sodium aluminum sulfosilicate and titanium dioxide.
    [065] The proportion of pigment may be in the range of 0 to 25% by weight based on the total weight of the coating composition, preferably in the range of 0 to 15% by weight. CATALYSTS:
    [066] The antifouling composition according to the present invention may also comprise a catalyst. Examples of catalysts that can be used include transition metal compounds, metal salts and organometallic complexes of various metals such as tin, iron, lead, barium, cobalt, zinc, antimony, cadmium, manganese, chromium, nickel, aluminum, gallium. , germanium and zirconium. The salts are preferably salts of long chain carboxylic acids and/or chelates or organometallic salts. Examples of suitable catalysts include, for example, dibutyltin dilaurate, dibutyltin dioctoate, dibutyltin diacetate, dibutyltin 2-ethylhexanoate, dibutyltin dineodecanoate, dibutyltin dimethoxide, dibutyltin dibenzoate, dibutyltin acetoacetonate, dibutyltin acetylacetonate, alkylacetoacetonate dibutyltin, dioctyltin dilaurate, dioctyltin dioctoate, dioctyltin diacetate, dioctyltin 2-ethylhexanoate, dioctyltin dineodecanoate, dioctyltin dimethoxide, dioctyltin dibenzoate, dioctyltin acetoacetonate, dioctyltin acetylacetonate, dioctyltin alkylacetatoacetonate,dimethylstanhonate,dimethylstanhonate , dimethyltin bisneodecanoate, dimethyltin dineodecanoate, tin naphthenate, tin butyrate, tin oleate, tin caprylate, tin octanoate, tin stearate, tin octoate, iron stearate, fer 2-ethylhexanoate ro, lead octoate, lead 2-ethyl hexanoate, cobalt 2-ethyl hexanoate, cobalt naphthenate, manganese 2-ethyl hexanoate, zinc 2-ethyl hexanoate, zinc naphthenate, zinc stearate, metal triflates , triethyltin tartrate, stannous octoate, carbomethoxyphenyltin trisuberate and isobutyltin triceroate.
    [067] Additional examples of suitable catalysts include organobismuth compounds such as bismuth 2-ethylhexanoate, bismuth octanoate and bismuth neodecanoate.
    [068] Additional examples of suitable catalysts include organotitanium, organozirconium and organohafnium compounds, titanates and zirconate esters such as: titanium naphthenate, zirconium naphthenate, tetrabutyl titanate, tetrakis(2-ethylhexyl) titanate, triethanolamine, tetra(isopropenyloxy) titanate, titanium tetrabutanolate, titanium tetrapropanolate, titanium tetraisopropanolate, tetrabutyl zirconate, tetrakis(2-ethylhexyl) zirconate, triethanolamine zirconate, tetra(isopropenyloxy) zirconate, zirconium tetrabutanolate , zirconium tetrapropanolate, zirconium tetraisopropanolate and chelated titanates such as diisopropyl bis(acetylacetonyl)titanate, diisopropyl bis(ethylacetoacetonyl)titanate, diisopropoxytitanium bis(ethylacetoacetate) and the like.
    [069] Additional examples of suitable catalysts include amines such as laurylamine, tertiary amines such as triethylamine, tetramethylethylenediamine, pentamethyldiethylenetriamine and 1,4-ethylenepiperazine or quaternary ammonium compounds such as tetramethylammonium hydroxide.
    [070] Additional examples of suitable catalysts include guanidine-based catalysts such as 1-butyl-2,3-dicyclohexyl-1-methyl guanidine.
    [071] Additional examples of suitable catalysts include organophosphates such as bis(2-ethylhexyl)hydrogen phosphate, (trimethylsilyl)octylphosphonic acid), octylphosphonic acid, bis(trimethylsilyl)octylphosphate and (2-ethylhexyl)hydrogen phosphonic acid. .
    [072] Alternatively, the catalyst may be a Lewis acid catalyst, for example BF3, B(C6F5)3, FeCl3, AlCl3, ZnCl2, ZnBr2 or compounds of boron, aluminum, gallium, indium or thallium with a monovalent aromatic moiety having preferably at least one electron-withdrawing element or group such as -CF3 , -NO2 , -CN or substituted by at least two halogen atoms.
    [073] Additionally, the catalyst may comprise a halogenated organic acid that has at least one halogen substituent on a carbon atom that is in the α-position with respect to the acid group and/or at least one halogen substituent on a carbon atom which is in the β position with respect to the acid group or a derivative that can be hydrolyzed to form that acid under the conditions of the condensation reaction. Alternatively, the catalyst may be as described in any one of: EP 1254192 , WO 2001/49774 , US 2004/006190 , WO 2007/122325A1 , WO 2008/132196 , WO 2008/055985A1 , WO 2009/106717A2 , WO 2009/106718A2 , WO 2009/106718A , WO 2009 / 106719A1, WO 2009 / 106720A1, WO 2009 / 106721A1, WO 2009 / 106722A1, WO 2009 / 106723A1, WO 2009 / 106724A1, WO 2009 / 103894A1, WO 2009 / 118307A1, WO 2009 / 133085A1 , WO 2009/156608A2 , WO 2009/156609A2 , WO 2012/130861A1 and WO 2013/013111 .
    [074] Preferably, the catalyst is present in a concentration of from 0.01 to 5% by weight based on the total weight of the coating composition. RETICULANT:
    [075] The antifouling composition according to the present invention may also comprise a crosslinker. If the curable polymer contains only two reactive functional groups, eg silanol groups, it may be necessary to use an additional reagent as a crosslinker.
    [076] The crosslinker optionally present may be an alkoxysilane such as methyltrimethoxysilane, tetraethoxysilane, vinyltris(methylethylximo)silane, methyltris(methylethyloximo)silane, vinyltrimethoxysilane, methyltrimethoxysilane, [(cyclohexylamino)methyl]triethoxysilane, N,N-dibutylaminomethyltriethoxysilane or vinyltri - isopropenoxysilane, as well as its hydrolysis-condensation products. Alternatively, the cross-linking agent may be as described in WO 99/33927.
    [077] A preferred cross-linking agent is an orthosilicate; the cross-linking agent may be, for example, tetraethylorthosilicate.
    [078] Preferably, the crosslinking agent is present in a concentration of 0 to 10% by weight based on the total weight of the coating composition.
    [079] Mixtures of different crosslinkers can also be used. SOLVENT:
    [080] The antifouling composition according to the present invention may also comprise a solvent.
    [081] Suitable solvents include aliphatic, cycloaliphatic and aromatic hydrocarbons, alcohols, ketones, esters and mixtures thereof. Examples of suitable solvents are mineral solvent, cyclohexane, toluene, xylene and naphtha solvent, esters such as methoxypropyl acetate, n-butyl acetate and 2-ethoxyethyl acetate; octamethyltrisiloxane and mixtures thereof.
    [082] In order to minimize the use of solvents in the environmental field, it is advantageous to use a solution as concentrated as possible that is compatible with the application technique employed. Solvents, when present, typically constitute from 5 to 50% by weight based on the total weight of the coating composition. The solids content can be determined according to ASTM method D2697. BIOCIDES:
    [083] An advantage of the antifouling coating composition according to the present invention is that the coatings have excellent antifouling properties without the use of biocides. In one embodiment of the present invention, the coating composition is free or substantially free of biocides.
    [084] Alternatively, to further improve antifouling performance, a biocide may be included in the coating composition. In an alternative embodiment, therefore, the antifouling composition according to the present invention may comprise one or more biocide(s).
    [085] The biocide may be one or more of an inorganic, organometallic, organic metal or organic biocide for aquatic organisms such as marine or freshwater organisms. Examples of inorganic biocides include copper salts such as copper oxide, copper thiocyanate, copper bronze alloys, copper carbonate, copper chloride, copper nickel alloys and silver salts such as silver chloride or nitrate; Organometallic and organic metal biocides include zinc pyrithione (the zinc salt of 2-pyridinethiol 1-oxide), copper pyrithione, bis(N-cyclohexyldiazenium dioxy) copper, zinc ethylenebis(dithiocarbamate) (i.e., zineb ), zinc dimethyl dithiocarbamate (ziram) and manganese ethylene bis(dithiocarbamate) complexed with zinc salt (i.e. mancozeb); and organic biocides include formaldehyde, dodecylguanidine monohydrochloride, thiabendazole, N-trihalomethyl thiophthalimides, trihalomethyl thiosulfamides, N-aryl maleimides such as N-(2,4,6-trichlorophenyl)maleimide, 3-(3,-dichlorophenyl )-1,1-dimethylurea (diuron), 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine, 2-methylthio-4-butylamino-6-cyclopopylamino-s-triazine, 3- benzo[b]thienyl-5,6-dihydro-1,4,2-oxathiazine, 4,5-dichloro-2-(n-octyl)-3(2H)-isothiazolone, 2,4,5,6 - tetrachloroisophthalonitrile, tolylfluanid, dichlofluanid, diiodomethyl-p-tosylsulfone, capsciacin, N-cyclopropyl-N'-(1,1-dimethylethyl)-6-(methylthio)-1,3,5-triazine-2,4- diamine, 3-iodo-2-propynylbutyl carbamate, medetomidine, 1,4-dithia-anthraquinone-2,3-dicarbonitrile (dithianon), boranes such as pyridine triphenylborane, a 2-trihalomethyl-3-halogeno- 4-cyanopyrol substituted at the 5-position and optionally the 1-position, such as 2-(p-chlorophenyl)-3-cyano-4-bromo-5-trifluoromethyl pyrrole (tralopyryl) and a furanone, such as 3-butyl-5-(dibromomethylidene)-2(5H)-furanone and mixtures thereof, macrocyclic lactones such as avermectins, for example, avermectin B1, ivermectin, doramectin, abamectin, amectin and selamectin and salts of quaternary ammonium such as didecyldimethylammonium chloride and alkyldimethylbenzylammonium chloride.
    [086] In further embodiments, the biocide is fully or partially encapsulated, adsorbed or attached to a support.
    [087] If the fouling resistant composition comprises biocide, this means that the biocide is present within the body of the cured coating layer (meaning that it has been mixed into the coating composition prior to curing). ADDITIONS:
    [088] Optionally, the antifouling composition according to the present invention may also comprise other additive substances which are known to have a non-biocidal antifouling effect such as non-reactive organopolysiloxanes; for example polydimethylsiloxane, methylphenyl polysiloxane or hydrophilic modified polysiloxane as described in EP 0885938 and WO 2011/076856; carboxyl functional organosiloxanes as described in WO 2008/132195 ; petroleum oils or lanolin and lanolin derivatives and other sterol(s) and/or sterol derivative(s) as described in PCT Patent Application No. PCT/EP2012/065920 and combinations thereof. APPLICATION:
    [089] The coating composition can be applied using normal techniques such as brushing, roller coating or spraying (airless and air-assisted). To obtain adequate adhesion to the substrate, application of the antifouling coating composition to a prepared substrate is preferred. The primer can be any primer/sealant coating system. Good results, particularly with respect to adhesion, have been found when using a primer comprising a siloxy-functional acrylic polymer, a solvent, a thixotropic agent, a filler and, optionally, a moisture remover. Such a primer is described in WO 99/33927. It is also possible to apply the coating composition according to the present invention to a substrate which contains an aged antifouling coating layer. Before the coating composition according to the present invention is applied to that aged layer, that aged layer is cleaned by high pressure water washing to remove any scale. The primer described in WO 99/33927 can be used as a bond coat between the aged coating layer and the coating composition according to the present invention.
    [090] Optionally, the primer may comprise adhesion promoters as described in WO 2010/18164.
    [091] Optionally, the primer may comprise a biocide as described in WO 2012/175459.
    [092] After the coating cures, it can be immersed immediately and provides immediate anti-fouling protection and fouling release. As indicated above, the coating composition according to the present invention has very good antifouling and scale releasing properties. This makes these coating compositions very suitable for use as anti-fouling or non-fouling coatings for marine applications. The coating can be used for both dynamic and static structures, such as ship hulls, buoys, drilling rigs, dry dock equipment, oil and/or gas production platforms, processing ships, floating oil storage and offloading and gas, aquaculture equipment, nets and cages, power generating devices such as coastal wind turbines and tidal and wave power devices, cooling water inlets for power plants and power stations, and pipes that are immersed in water and tanks, pipes and conduits used to store and transport water. The coating can be applied over any substrate that is used for these structures, such as metal, concrete, wood or fiber reinforced plastic. OTHERS:
    [093] In another embodiment, the present invention relates to a substrate or structure coated with the antifouling composition as described herein.
    [094] A further embodiment of the present invention is a method of inhibiting fouling of a substrate in an aquatic environment by applying the antifouling composition to the substrate, allowing the antifouling composition to be cured/hardened to form a coating on the substrate. substrate and then positioning the coated substrate in the aquatic environment. For the avoidance of doubt, aquatic environment in the context of the present invention is an environment in which fouling occurs by marine and freshwater organisms such as diatoms, biological slime films, green and brown algae, barnacles, mussels and the like.
    [095] A further embodiment of the present invention is the use of the antifouling composition as described and claimed herein to inhibit fouling on a substrate in an aquatic environment.
    [096] The present invention will be elucidated with respect to the following examples. EXAMPLES EXAMPLES 1-7
    [097] Seven different coating compositions were prepared by mixing the components shown in Table 1. TABLE 1
    *Examples 1-4 are comparative examples.
    [098] The composition of Example 1 does not contain a polymer or oligomer that contains fluorinated oxyalkylene.
    [099] The compositions of Example 2 and Example 3 comprise a fluorinated polymer or oligomer, but the fluorinated polymer or oligomer does not contain oxyalkylene moieties. These comparative examples are included as representative examples of a fluorinated polymer or oligomer(s) of WO 02/074870.
    [0100] The composition of Example 4 comprises a fluorinated polymer or oligomer and the fluorinated polymer or oligomer contains an average of 3 portions of oxyethylene per polymer/oligomer. (1) Fluorolink® D10-H (Solvay Specialty Polymers) (contains no oxyalkylene moieties; viscosity at 25°C = 108 mPa.s). (2) PolyFox® AT-1035 (Omnova Solutions Inc) (contains no oxyalkylene moieties; viscosity at 25°C = 13.674 mPa.s). (3) Fluorolink® E10-H (Solvay Specialty Polymers) (contains on average 3 oxyalkylene moieties per polymer; oxyethylene moieties are located at the ends of the polymers; viscosity at 25°C = 144 mPa.s). (4) Fluorolink® E10-6 (Solvay Specialty Polymers) (contains an average of 9 oxyalkylene moieties per polymer; oxyethylene moieties are located at the ends of the polymers; viscosity at 25°C = 443 mPa.s). (5) Fluorolink® 5147X (Solvay Specialty Polymers) (contains an average of 13 oxyethylene moieties per polymer; oxyethylene moieties are located at the ends of the polymers; viscosity at 25°C = 629 mPa.s). (6) Polyfox® PF-652 (Omnova Solutions Inc) (contains an average of 16 oxyalkylene moieties per polymer; oxyethylene moieties are located at the ends of the polymers; viscosity at 25°C = 6214 mPa.s). (7) Dow Corning® 3-0213 polymer (Dow Corning) (viscosity at 25°C = 3678 mPa.s). (8) Aerosil® R972 (Evonik). (9) Molsiv® 5A-AP (OMYA). (10) Tioxide® TR92 (Huntsman). (11) Bayferrox® 318M (Lanxess). (12) Wacker® TES 40 (Wacker-Chemie). (13) Xylene (Total). (14) Tib Kat® 216 (Tib Chemicals). (15) Camdate® PLE (Camide).
    [0101] Scale Resistance Test (1) - Chanqi, Singapore:
    [0102] Examples of coating compositions were applied by brush to wood substrates prepared with a suitable coat. The coated substrates were immersed in an aquatic environment where marine fouling is known to occur (Changi, Singapore). Coated substrates were determined after 44 weeks of immersion and the degree of fouling coverage was recorded as percentage fouling coverage. The test results are shown in Table 2. TABLE 2

    [0103] After 44 weeks, Example 5 and Example 6 achieved lower fouling coverage than Example 1, Example 2 and Example 4. Reduction of fouling over Examples 5 and 6 demonstrates improved antifouling performance compared to compositions described in WO 02/074870.
    [0104] Scale Resistance Test (2) - Chanqi, Singapore:
    [0105] In a separate test, examples of coating compositions were applied by brush to wood substrates prepared with a suitable coat. The coated substrates were immersed in an aquatic environment where marine fouling is known to occur (Changi, Singapore). Coated substrates were determined after 35 weeks of immersion and the degree of fouling coverage recorded as percent fouling coverage. The test results are shown in Table 3. TABLE 3


    [0106] After 35 weeks, Example 7 showed lower fouling coverage than Example 3 and Example 4. Less fouling in Example 7 demonstrates increased antifouling performance compared to the compositions described in WO 02/074870.
    [0107] Scale release test (1) - water recirculation chamber:
    [0108] Examples of coating compositions were applied by brush on glass substrates prepared with a suitable coat. The coated substrates were immersed in a water recirculation chamber, in which water and environmental conditions are controlled so that biological films of marine scale can be cultivated. After a period of 80 days, the fouled substrates were placed in a water flow tank. The water flow velocity in the tank was increased from 0 to 1.5 m/s and then to 2.6 m/s. The degree of fouling coverage of the coated substrates was recorded and the percentage of fouling removed was calculated. The test results are shown in Table 4. TABLE 4

    [0109] As the flow speed increases, scale is removed. More scale is removed from Example 5 and Example 6 than is removed from Example 1, Example 2 and Example 4. Greater removal from Example 5 and Example 6 demonstrates improved scale release properties compared to the coatings described in WO 02/074870.
    [0110] Scale release test (2) - water recirculation chamber:
    [0111] In a separate test, examples of coating compositions were applied by brush onto prepared glass substrates with a suitable coat. The coated substrates were immersed in a recirculating water chamber in which water and environmental conditions are controlled so that biological films of marine scale can be cultivated. After a period of 7 days, the fouled substrates were placed in a water flow tank. The water flow velocity in the tank increased from 0 to 1.5 m/s and then to 2.6 m/s. The degree of fouling coverage of the coated substrates was recorded and the percentage of fouling removed was calculated. The test results are shown in Table 5. TABLE 5

    [0112] As the flow velocity increases, scale is removed. More scale is removed from Example 7 than is removed from Example 3 and Example 4. Greater removal from Example 7 demonstrates improved scale release properties compared to the coatings described in WO 02/074870.
    权利要求:
    Claims (17)
    [0001]
    1. ANTI-FOULING COMPOSITION COMPRISING A CURABLE POLYMER AND A FLUORIDED OXYALKYLENE CONTAINING POLYMER OR OLIGOMER, characterized by a fluorinated oxyalkylene containing polymer or oligomer comprising: (a) one or more fluoridated moieties of the formula:
    [0002]
    2. ANTI-FOULING COMPOSITION, according to claim 1, characterized in that the oxyalkylene moieties are oxyethylene moieties.
    [0003]
    3. ANTI-FOULING COMPOSITION, according to any one of claims 1 or 2, characterized in that the polymer or oligomer containing fluorinated oxyalkylene is in the form of OA-(F-OA)n, in which OA is a block of a or more oxyalkylene moieties, F is a block of one or more fluoridated moieties and n is an integer.
    [0004]
    4. ANTI-FOULING COMPOSITION, according to claim 3, characterized in that n is 1 and the average number of oxyalkylene moieties in each block of oxyalkylene moieties varies independently in the range of 2.0 to 50.0.
    [0005]
    5. ANTI-FOULING COMPOSITION, according to any one of claims 1 to 4, characterized in that the number average molecular weight (Mn) of the polymer/oligomer is in the range of 400 to 40,000.
    [0006]
    6. ANTI-FOULING COMPOSITION, according to any one of claims 1 to 5, characterized in that fluoridated moieties and/or oxyalkylene moieties at the ends of the polymer or oligomer containing fluorinated oxyalkylene are terminated with a hydrogen or a C1-C12 alkyl group. linear, branched or cyclic such as a methyl, phenyl group or acyl groups such as ethanol groups.
    [0007]
    7. ANTI-FOULING COMPOSITION, according to any one of claims 1 to 6, characterized in that R1, R2, R3 and R4 are independently any one or more of: F, -CF3, -CH2OCH2CF3 or -CH2OCH2CF2CF3, preferably F and/ or -CF3.
    [0008]
    ANTI-FOULING COMPOSITION according to any one of claims 1 to 7, characterized in that R5, R6, R7 and R8 are independently -H, -CH3 or -CH2CH3, preferably wherein R5, R6, R7 and R8 are -H.
    [0009]
    9. ANTI-FOULING COMPOSITION, according to any one of claims 1 to 9, characterized in that the polymer or oligomer containing fluorinated oxyalkylene is a fluid, preferably having a viscosity of 10 to 1,000,000 mPa.s at 25°C.
    [0010]
    10. ANTI-FOULING COMPOSITION, according to any one of claims 1 to 9, characterized in that the curable polymer is one or a mixture of polymer(s) that contain(s) organosiloxane that comprise(s) a repeating unit of the formula:
    [0011]
    11. ANTI-FOULING COMPOSITION according to any one of claims 1 to 10, characterized in that the curable polymer is free from perfluoropolyether moieties.
    [0012]
    ANTI-FOULING COMPOSITION according to claim 10, characterized in that R9 and R10 are independently selected from methyl and phenyl, preferably when both R9 and R10 are methyl.
    [0013]
    13. ANTI-FOULING COMPOSITION, according to any one of claims 1 to 12, characterized in that it further comprises a biocide.
    [0014]
    14. ANTI-FOULING COMPOSITION, according to any one of claims 1 to 13, characterized in that it is for application to a substrate.
    [0015]
    15. ANTI-FOULING COMPOSITION, according to claim 14, characterized in that the substrate is selected from ship hulls, buoys, drilling platforms, dry dock equipment, oil and/or gas production platforms, processing ships, storage and floating offloading of oil and gas, aquaculture equipment, nets and cages, coastal wind turbines, and tidal and wave energy devices.
    [0016]
    16. ANTI-FOULING COMPOSITION, according to any one of claims 14 or 15, characterized in that the substrate is made of metal, concrete, wood or fiber-reinforced plastic.
    [0017]
    17. METHOD OF INHIBITION OF FOLLOWING OF A SUBSTRATE IN AQUATIC ENVIRONMENT BY APPLYING THE ANTI-FOULING COMPOSITION, as defined in any of claims 1 to 13, to the substrate, characterized by allowing the anti-fouling composition to be cured to form a coating on the substrate and then positioning the coated substrate in the aquatic environment.
    类似技术:
    公开号 | 公开日 | 专利标题
    BR112015019146B1|2022-01-04|ANTI-FOULING COMPOSITION COMPRISING A CURABLE POLYMER AND A POLYMER OR OLIGOMER CONTAINING FLUORIDED OXYALKYLENE, AND METHOD OF INHIBITING FOLLOWING OF A SUBSTRATE IN AQUATIC ENVIRONMENT BY APPLYING THE ANTI-FOULING COMPOSITION
    ES2356867T3|2011-04-13|COATING COMPOSITIONS AGAINST INCRUSTATIONS CONTAINING A CARBOXI-FUNCTIONAL ORGANOSILICONE.
    JP5860536B2|2016-02-16|Fouling resistant composition comprising sterol and / or a derivative thereof
    RU2279458C2|2006-07-10|Composition for non-overgrowing covers involving polymer or oligomer comprising alkyl- or alkoxy-groups
    US20100003211A1|2010-01-07|Antifouling coating composition and underwater structure using the same
    JP6385437B2|2018-09-05|Method for covering an aging coating layer on a substrate and a coating composition suitable for use in the method
    EP2492323A1|2012-08-29|Biofouling resistant composition
    同族专利:
    公开号 | 公开日
    JP2016509110A|2016-03-24|
    US20150361280A1|2015-12-17|
    EP2961805A1|2016-01-06|
    BR112015019146A2|2017-07-18|
    ES2616437T3|2017-06-13|
    KR20150123835A|2015-11-04|
    TW201500488A|2015-01-01|
    CN104995271A|2015-10-21|
    AU2014222855B2|2017-04-13|
    PL2961805T3|2017-06-30|
    AU2014222855A1|2015-07-30|
    SG11201506525WA|2015-09-29|
    ZA201505252B|2016-07-27|
    KR102201787B1|2021-01-12|
    MX2015010754A|2015-11-30|
    WO2014131695A1|2014-09-04|
    EP2961805B1|2016-12-21|
    CL2015002374A1|2016-03-11|
    DK2961805T3|2017-03-27|
    JP6074067B2|2017-02-01|
    PT2961805T|2017-03-08|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    GB1307001A|1970-01-12|1973-02-14|Kroyer K K K|Marine structure having a surface coating for the prevention ofaccumulation of marine organisms|
    US3702778A|1970-03-23|1972-11-14|Battelle Memorial Institute|Ship's hull coated with antifouling silicone rubber|
    FR2537985B1|1982-12-17|1985-04-26|Bourit Claude|
    JPH09286853A|1996-04-23|1997-11-04|Kao Corp|Production of fluoropolyether|
    AU2977797A|1996-05-31|1998-01-05|Toto Ltd.|Antifouling member and antifouling coating composition|
    EP0831134A1|1996-09-19|1998-03-25|Sigma Coatings B.V.|Light- and bright-coloured antifouling paints|
    US5906893A|1997-04-25|1999-05-25|General Electric Company|Sprayable, addition curable silicone foul release coatings and articles coated therewith|
    EP0885938B1|1997-06-16|2002-07-31|General Electric Company|Condensation curable silicone foul release coatings and articles coated therewith|
    GB9727261D0|1997-12-23|1998-02-25|Courtaulds Coatings Holdings|Fouling inhibition|
    JP2000290489A|1999-04-07|2000-10-17|Asahi Glass Co Ltd|Curable composition|
    WO2001049774A2|2000-01-06|2001-07-12|Dow Corning Corporation|Organosiloxane compositions|
    CA2397715C|2000-01-06|2008-11-25|Dow Corning S.A.|Organosiloxane compositions|
    JP3675315B2|2000-08-24|2005-07-27|Ｔｄｋ株式会社|Head gimbal assembly having an actuator for minute positioning of a head element and disk apparatus having the head gimbal assembly|
    NZ528084A|2001-03-21|2005-04-29|Akzo Nobel Nv|Anti-fouling compositions with a fluorinated alkyl- or alkoxy-containing polymer or oligomer|
    JP3835796B2|2002-07-03|2006-10-18|信越化学工業株式会社|Room temperature curable organopolysiloxane composition|
    JP4501111B2|2002-10-18|2010-07-14|旭硝子株式会社|Perfluoropolyether derivative|
    FR2900153B1|2006-04-21|2008-07-18|Rhodia Recherches & Tech|PROCESS FOR CONDENSING SILYLATED PATTERNS USING CARBENE TYPE CATALYST|
    FR2908420A1|2006-11-09|2008-05-16|Rhodia Recherches & Tech|SELF-CONTAINING SILICONE COMPOSITION TENABLE TO ELASTOMER|
    UA92292C2|2007-05-01|2010-10-11|Акцо Нобель Коатингс Интернешнл Б.В.|Process to physically deter fouling from a substrate in an aquatic fouling environment by means of antifouling coating composition based on curable polyorganosiloxane polyoxyalkylene copolymers|
    AT489436T|2007-05-01|2010-12-15|Akzo Nobel Coatings Int Bv|AGENTS PREVENTING COATING COMPOSITIONS WITH A CARBOXYL FUNCTIONAL ORGANOSILICIUM COMPOUND|
    FR2925515A1|2007-12-20|2009-06-26|Bluestar Silicones France Soc|ORGANOPOLYSILOXANIC COMPOSITION VULCANIZABLE AT ROOM TEMPERATURE IN ELASTOMER AND NEW POLYCONDENSATION CATALYSTS OF ORGANOPOLYSILOXANES.|
    FR2925511A1|2007-12-20|2009-06-26|Bluestar Silicones France Soc|ORGANOPOLYSILOXANIC COMPOSITION VULCANIZABLE AT ROOM TEMPERATURE IN ELASTOMER AND NEW POLYCONDENSATION CATALYSTS OF ORGANOPOLYSILOXANES.|
    CN105440288A|2007-12-20|2016-03-30|蓝星有机硅法国公司|Room-temperature vulcanisable organopolysiloxane compound to give an elastomer and novel organopolysiloxane polycondensation catalysts|
    FR2925512A1|2007-12-20|2009-06-26|Bluestar Silicones France Soc|ORGANOPOLYSILOXANIC COMPOSITION VULCANIZABLE AT ROOM TEMPERATURE IN ELASTOMER AND NEW POLYCONDENSATION CATALYSTS OF ORGANOPOLYSILOXANES.|
    FR2925514A1|2007-12-20|2009-06-26|Bluestar Silicones France Soc|ORGANOPOLYSILOXANIC COMPOSITION VULCANIZABLE AT ROOM TEMPERATURE IN ELASTOMER AND NEW POLYCONDENSATION CATALYSTS OF ORGANOPOLYSILOXANES.|
    FR2925516A1|2007-12-20|2009-06-26|Bluestar Silicones France Soc|ORGANOPOLYSILOXANIC COMPOSITION VULCANIZABLE AT ROOM TEMPERATURE IN ELASTOMER AND NEW POLYCONDENSATION CATALYSTS OF ORGANOPOLYSILOXANES.|
    FR2925513A1|2007-12-20|2009-06-26|Bluestar Silicones France Soc|ORGANOPOLYSILOXANIC COMPOSITION VULCANIZABLE AT ROOM TEMPERATURE IN ELASTOMER AND NEW POLYCONDENSATION CATALYSTS OF ORGANOPOLYSILOXANES.|
    FR2925510A1|2007-12-20|2009-06-26|Bluestar Silicones France Soc|Organopolysiloxane composition, useful e.g. for preparing elastomer, resins or synthetic foams, comprises silicone base hardened by polycondensation of silicone elastomer, and at least one catalytic system, which comprises metal salt|
    FR2925496A1|2007-12-20|2009-06-26|Bluestar Silicones France Soc|New guanidine compound useful as a catalyst for the polycondensation reaction of organopolysiloxane|
    FR2929286A1|2008-03-28|2009-10-02|Bluestar Silicones France Soc|GUANIDINE-STRUCTURED COMPOUNDS AND THEIR USE AS ORGANOPOLYSILOXANE POLYCONDENSATION CATALYSTS|
    JP5232912B2|2008-04-30|2013-07-10|ブルースター・シリコーンズ・フランス|Articles that have antifouling properties and are used for underwater applications, especially marine applications|
    FR2930778A1|2008-04-30|2009-11-06|Bluestar Silicones France Soc|ARTICLE HAVING ANTIFOULING PROPERTIES AND INTENDED FOR USE IN AQUATIC APPLICATIONS, IN PARTICULAR MARINE|
    US9840640B2|2008-05-29|2017-12-12|Bluestar Silicones France|Article having antifouling properties for aquatic and particularly sea use|
    KR101246007B1|2008-05-29|2013-03-21|블루스타 실리콘즈 프랑스 에스에이에스|Article having antifouling properties for aquatic and particularly sea use|
    US20110250350A1|2008-08-11|2011-10-13|Hempel A/S|Novel tie-coat compositions|
    JP2010254832A|2009-04-27|2010-11-11|Shin-Etsu Chemical Co Ltd|Antifouling coating composition and antifouling method|
    PT2516559E|2009-12-22|2015-02-06|Hempel As|Novel fouling control coating compositions|
    US8921503B2|2011-03-31|2014-12-30|Akzo Nobel Coatings International B.V.|Foul preventing coating composition|
    MY163188A|2011-06-21|2017-08-15|Akzo Nobel Coatings Int Bv|Biocidal foul release coating systems|
    PL2726561T3|2011-06-30|2017-03-31|Hempel A/S|Fouling control coating compositions|
    WO2013013111A1|2011-07-21|2013-01-24|Dow Corning Corporation|Yttrium containing complex and condensation reaction catalysts, methods for preparing the catalysts, and compositions containing the catalysts|WO2017111984A1|2015-12-22|2017-06-29|Hrl Laboratories, Llc|Low-friction fluorinated coatings|
    EP3478786A4|2016-06-30|2020-03-18|HRL Laboratories, LLC|Low-adhesion coatings with solid-state lubricants|
    US10696917B2|2014-03-14|2020-06-30|Hrl Laboratories, Llc|Low-friction fluorinated coatings|
    US10836974B2|2014-03-14|2020-11-17|Hrl Laboratories, Llc|Low-adhesion coatings with solid-state lubricants|
    CN108137954B|2015-07-13|2021-03-19|佐敦公司|Antifouling composition|
    CN106146820B|2016-07-13|2018-02-13|天津科技大学|The method that perfluor iodine prepares single-ended Z-type PFPE siloxanes|
    US10442935B2|2016-08-06|2019-10-15|Hrl Laboratories, Llc|Coatings combining oil-absorbing and oil-repelling components for increased smudge resistance|
    KR101820432B1|2016-10-20|2018-01-19|주식회사 에프알에스아이|Eco-friendly antifouling composition, manufacturing method thereof, and eco-friendly antifouling film using the same|
    KR102289888B1|2017-01-17|2021-08-13|아크조노벨코팅스인터내셔널비.브이.|Antifouling coating compositions, substrates coated with such coating compositions, and uses of such coating compositions|
    WO2018134291A1|2017-01-19|2018-07-26|Jotun A/S|Antifouling composition|
    EP3489311A1|2017-11-24|2019-05-29|Jotun A/S|Antifouling composition|
    EP3489310A1|2017-11-24|2019-05-29|Jotun A/S|Antifouling composition|
    KR102230998B1|2017-12-14|2021-03-23|아크조노벨코팅스인터내셔널비.브이.|Substrates coated with a multilayer coating system, and a method for controlling aquatic bioadhesion on artificial objects using such a multilayer coating system|
    EP3724278A1|2017-12-14|2020-10-21|Hempel A/S|Controlled release antifouling coating composition via biocide interaction|
    JP2019143020A|2018-02-19|2019-08-29|住友化学株式会社|Coating film|
    DE102018106465A1|2018-03-20|2019-09-26|Osram Opto Semiconductors Gmbh|Optoelectronic component|
    KR20210021368A|2018-07-13|2021-02-25|아크조노벨코팅스인터내셔널비.브이.|Tie-Coat Composition|
    US11214707B2|2018-09-21|2022-01-04|The Boeing Company|Compositions and methods for fabricating coatings|
    EP3828240A1|2019-11-29|2021-06-02|Jotun A/S|Fouling release coating|
    法律状态:
    2019-10-22| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-08-10| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2021-11-03| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2022-01-04| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 21/02/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP13156771|2013-02-26|
    EP13156771.1|2013-02-26|
    US201361772084P| true| 2013-03-04|2013-03-04|
    US61/772,084|2013-03-04|
    PCT/EP2014/053379|WO2014131695A1|2013-02-26|2014-02-21|Anti-fouling compositions with a fluorinated oxyalkylene-containing polymer or oligomer|
    [返回顶部]