WO1998039391A1 - Inhibition des salissures - Google Patents

Inhibition des salissures Download PDF

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Publication number
WO1998039391A1
WO1998039391A1 PCT/GB1998/000706 GB9800706W WO9839391A1 WO 1998039391 A1 WO1998039391 A1 WO 1998039391A1 GB 9800706 W GB9800706 W GB 9800706W WO 9839391 A1 WO9839391 A1 WO 9839391A1
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WO
WIPO (PCT)
Prior art keywords
curable
component
groups
curing
silicon
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Application number
PCT/GB1998/000706
Other languages
English (en)
Inventor
Trevor Hamilton
Georgina Elizabeth Green
David Neil Williams
Original Assignee
Courtaulds Coatings (Holdings) Limited
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.)
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Publication date
Application filed by Courtaulds Coatings (Holdings) Limited filed Critical Courtaulds Coatings (Holdings) Limited
Priority to AU65082/98A priority Critical patent/AU6508298A/en
Publication of WO1998039391A1 publication Critical patent/WO1998039391A1/fr

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    • 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
    • C09D5/1675—Polyorganosiloxane-containing compositions
    • 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
    • C09D5/1693—Antifouling paints; Underwater paints as part of a multilayer system

Definitions

  • This invention relates to a process for inhibiting fouling of a substrate in a fouling environment, more especially a marine or other aquatic environment.
  • Man-made structures such as boat hulls, buoys, drilling platforms, oil production rigs and pipes which are immersed in water are prone to fouling by aquatic organisms such as green and brown algae, barnacles, mussels and the like.
  • Marine structures are commonly of metal, but may also comprise other structural materials such as concrete.
  • the hulls may instead comprise, for example, wood or a fibre-reinforced resin. This fouling is a nuisance on boat hulls, because it increases the frictional resistance towards movement through the water, with the consequence of reduced speeds and increased fuel costs.
  • EP 0 032 597 discloses that silicone polymers onto which organic polymeric segments are grafted may be vulcanised to form non-fouling coatings.
  • the vulcanisation procedure may utilise a crosslinking agent such as tetraethyl orthosilicate and a catalyst such as a tin salt.
  • GB 2 188 938 discloses that vinylic polymers containing polymeric silicone side chains may be used to form thermoplastic non-fouling coatings.
  • GB Patent Application 2 192 400 discloses anti- fouling paint compositions which comprise a vinylic copolymer obtained by copolymerisation of: (a) 1-50% by weight of a polymerisable unsaturated polysiloxane compound;
  • the disclosed anti-fouling paint compositions may also comprise a hydroxyalkyl-tipped poly(diorganosiloxane) to the extent of 1-50 parts by weight per 100 parts by weight of the vinylic copolymer.
  • the vinylic copolymer and the poly(diorganosiloxane) are not curable one with the other, and the coatings disclosed in GB-A-2 192 400 are thermoplastic and not vulcanised.
  • GB 1 470 465 discloses the use of silicone oils as slipping agents in a vulcanised silicone rubber formulation.
  • GB 1 581 727 discloses the use of silicone-free organic compounds, for example polyolefins with a molecular weight up to about 5000, as slipping agents in a vulcanised silicone rubber formulation.
  • WO 93/13179 discloses a composition for fouling inhibition which comprises (A) a functional-group containing polymer having no more than a minor proportion of siloxane repeating units and (B) a polysiloxane which is curable with the polymer (A) .
  • the innermost region of the resulting coating generally comprises no more than a minor proportion of siloxane material whereas the coating presents a siloxane-rich surface layer to the external environment.
  • the coating provides fouling inhibition properties whilst at the same time the problems of mechanical weakness of previously proposed silicone rubber coatings are alleviated or avoided.
  • the coating may be worn by fouling attrition to the extent that its fouling inhibition properties are impaired, or there may be physical damage to the coating at any time. There is a need to be able to restore or repair a coating that has been worn or damaged in use.
  • the present invention provides a process for inhibiting fouling of a substrate in a fouling environment, which comprises applying to the substrate, before exposure to the said environment, a composition which comprises:
  • the process of the invention enables the fouling inhibition performance of a coating according to
  • WO 93/13179 to be improved, and also provides a means for restoring or repairing a worn or aged coating of that kind without the expense and difficulty of stripping off the worn or aged material and applying a replacement coating.
  • the curable layer (C) is applied to a freshly- prepared coating formed by curing the composition comprising components (A) and (B). It is considered that the application of the layer (C) to freshly-prepared coating produces a coating which is less susceptible to the detrimental effects of fouling attrition in use.
  • the invention also offers the possibility of repairing damaged areas of coating as necessary and of restoring coatings that have been worn through fouling attrition in use.
  • the curable layer (C) is applied to a coating formed initially by curing the composition comprising components (A) and (B) , but which has been worn and/or damaged in use.
  • Restoration of worn coatings may be carried out at any desired intervals, and will typically be carried out on a regular basis. For example, in the case of a coating applied to yachts, restoration may be carried out on an annual seasonal basis or more or less frequently if desired.
  • the substrate can be any material that is to be used in a fouling, especially aquatic, environment.
  • the substrate may be metal, for instance, steel or aluminium; wood; concrete; a fibre- reinforced resin such as, for instance, a polyester resin; or another plastics material.
  • a known anti- corrosive coating (such as, for instance, an epoxy, vinyl or alkyd coating) may be applied to the substrate before application of the composition comprising components (A) and (B) .
  • a coating formed from a composition comprising components (A) and (B) will in general adhere well to a variety of substrate surfaces without the need to use an adhesion modifier or an intermediate tie-coat.
  • the coating composition may be applied directly to the surface of the substrate, optionally after a preliminary protective treatment (for example, anti-corrosive treatment in the case of a metal substrate) .
  • the invention further provides a substrate bearing a coating which has been applied by the process, i.e., having an outer layer comprising cured component (C).
  • An especially important aspect of the present invention comprises inhibition of fouling of structures in aquatic and, in particular, marine environments, especially the hulls of boats and ships of all sizes.
  • the process may also be used more generally, however, in providing, for example, non-stick, easy-clean or anti- graffiti coatings. Examples of such end uses include reduction of bio-fouling or other unwanted depo- sition in heat exchangers and reduction of deposition of denatured protein material in the production of UHT milk.
  • the outermost surface region of the resulting coating is relatively rich in siloxane material, whereas the innermost region of the coating is relatively rich in the polymer of component (A) , and it is believed that there will generally be a progressive increase in the concentration of siloxane material from the inner to the outer regions of the coating.
  • the applied coating presents a siloxane-rich surface layer to the external environment and the good non-fouling and other protective properties associated with such material are obtained, but at the same time the mechanical weakness of previously proposed silicone rubber coatings is alleviated or avoided.
  • the siloxane-rich surface layer will be substantially free of unreacted functional groups, which might otherwise provide sites for adherence of fouling organisms.
  • each of the various curing reactions involved in the process of the invention will in general be a condensation cure which (in the case of curable silicon- containing functional groups) results in the formation of Si-0 bonding between the components, and generally in the formation of a by-product corresponding to the curable functional groups participating in the reaction; other curing reactions, for example, hydrosilation, are possible in principle, but are very much less preferred.
  • the curing reaction may proceed as follows:
  • R'R 2 CN0H which may hydrolyse to an aldehyde or ketone, R'R 2 C0 and hydroxylamine, NH 2 OH, under the conditions of the condensation.
  • the curing reactions involved in the process of the invention will generally include self-cure of component (B) with itself and, in the case of two or more components (B) , will generally include curing of the components (B) together. If there is more than one component (B), it is in principle only necessary for one of them to cure with (A) , although in practice the chemistries will typically be such that each component (B) will cure with (A) . It may be necessary or desirable to utilise a cross- linking agent for each of the various curing reactions involved in the process of the invention. It will be appreciated that, in principle, the need or otherwise for the use of such an agent for any given reaction will depend on the functionality and reactivity of the component(s) concerned.
  • component (A) may comprise curable functional groups selected from epoxy, a ino, hydroxy and alkoxy groups and hydrogen atoms, and/or curable silicon-containing functional groups.
  • curable functional groups selected from epoxy, a ino, hydroxy and alkoxy groups and hydrogen atoms, and/or curable silicon-containing functional groups.
  • component (A) comprises curable silicon- containing functional groups, and in one form of composition of the invention substantially all of the curable functional groups in component (A) are silicon- containing groups.
  • Component (A) may comprise pendant and/or terminal curable functional groups.
  • Pendant curable functionality is preferred, for example, in the case where the polymer of component (A) is derived from one or more ethyleni- cally unsaturated monomers, and terminal curable func- tionality is preferred, for example, if the polymer of component (A) is polyurethane, epoxy or polyester based.
  • component (A) has di- or tri-functional curable groups, and it is then in general not necessary to provide a separate cross-linking agent for the (A)/(B) curing reaction.
  • curable silicon-containing groups in component (A) may be silanol groups, the presence of such groups is not necessary and may lead to undesirable curing during storage, and it is certainly preferable for the curable silicon-containing groups to be other than trihydroxysilyl groups.
  • curable silicon-containing groups in component (A) are curable by virtue of one or more curable functional groups selected from aliphatic, aromatic and araliphatic ether (for example, alkoxy), ester (for example, acetoxy) and oxime groups.
  • curable silicon-containing groups in component (A) comprise one or more oxi e groups of the formula
  • R 4 and R 5 may be the same or different and each represents a straight-chain or branched, saturated or unsaturated, aliphatic hydrocarbon radical, preferably having up to 7 carbon atoms, more especially up to 4 carbon atoms, especially a methyl or ethyl group; an aromatic group, for example, a phenyl group; or an araliphatic group, for example, a benzyl group; or R 4 and R 5 together represent an alkylene group; or one of R 4 and R 5 represents hydrogen.
  • each of R 4 and R 5 is other than an aromatic group.
  • a group R 4 and/or R 5 may be substituted or unsubstituted.
  • Curable silicon-containing groups in component (A) may contain more than one curable functional group bonded to silicon, and preferably contain three such groups.
  • curable silicon-containing groups in component (A) are preferably of the formula
  • R is a straight-chain or branched alkyl group having from 1 to 4 carbon atoms , preferably a methyl or ethyl group.
  • pendant curable silicon-containing functional groups in component (A) are connected to the polymer by a chemical linkage that is resistant to aqueous hydrolysis in natural waters; sea water, for example, has pH 8.0-8.3.
  • the silicon-containing bonds which are capable of undergoing condensation curing as described above, for example ⁇ ilyl ether and silyl ester, are therefore generally unsuitable for the purpose of attaching silicon-containing groups to the polymer back- bone.
  • the said chemical linkage should contain silicon directly linked to carbon.
  • the chemical linkage may comprise an alkylene group C n H 2n where n is a non-zero integer preferably having the value 1-5, an alkylidene group, or an arylene group, for example phenylene, or may be a direct chemical bond to a carbon atom in the polymer backbone.
  • the polymer of (A) is derived from one or more monomers (Al) which carry curable silicon- containing groups and one or more monomers (A2) which do not carry such groups.
  • the molar proportion of monomer(s) (Al) to that of monomer(s) (A2) may be in the range of from 1% to 30% or 50%, for example from 5% to 16%, advantageously from 5% to 14%, preferably from 5% to 12%, and more especially from 5% to 10% or from 1% to 5%.
  • Polymers (A) carrying curable silicon-containing groups may expediently be manufactured by the polymerisation of one or more monomers containing such groups, advantageously with one or more comonomers which do not contain such groups.
  • silicon- containing monomers may be derivatives of compounds such as acrylic acid, methacrylic acid, styrene, or ethylene.
  • derivatives of acrylic and methacrylic acid are the esters in which the esterifying group includes the said silicon-containing group.
  • Compound I(R represents CH 3 ) is particularly preferred.
  • derivatives of styrene as monomers (Al) are those in which a benzene ring is substituted both with a vinyl or 2-propenyl group and with a silicon- containing group.
  • styrene derivatives there may be mentioned the isomeric tri- ethoxysilylstyrenes and the isomeric 2-(trimethoxysilyl- ethyl )styrenes .
  • derivatives of ethylene as monomers (Al) may be mentioned trimethoxyvinylsilane and triethoxyvinylsilane.
  • the polymer of component (A) may be derived from one or more ethylenically unsaturated monomers, more especially from one or more ethylenically unsaturated monomers selected from unsaturated aliphatic hydrocarbons, for example, ethylene, propylene and butylene; unsaturated halogenated hydrocarbons, for example, vinyl chloride, vinyl fluoride, vinylidene chloride and vinylidene fluoride; vinyl aromatic compounds, for example, vinyl pyridine, vinylnaphthalene, and styrene (including ring-substituted styrenes); unsaturated acids, esters, amides and nitriles; and N-vinyl compounds, for example, N-vinyl pyrrolidone, N-vinyl carbazole and N- vinyl caprolactam. Mention should also be made of polyvinylacetate and polyvinylalcohol .
  • the polymer of component (A) may comprise repeating units derived from urethanes, ureas, urethane-ureas , amides, i ides, amide-imides, epoxy compounds, and esters. Mention should also be made of alkyl resins and polyethers.
  • olefinic monomers such compounds as acrylic and methacrylic acids and their ester, amide and nitrile derivatives, styrene and vinyl chloride.
  • Acrylate and methacrylate esters are preferred monomers, especially those derived from saturated alcohols containing 4-16 carbon atoms, such as the butyl, hexyl, octyl, decyl, dodecyl and hexadecyl esters.
  • one or more monomers with reactive functionality to promote adhesion to the underlying surface, for example epoxy functionality derived, for instance, from glycidyl acrylate or methacrylate, or amino functionality derived, for instance, from an aminoalkyl acrylate or methacrylate such as dimethylaminoethyl methacrylate. It is generally advantageous on grounds of cost, and also to avoid excessive curing, to minimise the proportion of monomers (Al) carrying pendant curable silicon-containing groups in the polymer (A) .
  • the polymer (A) comprises 1-40 mole% 3-(trimethoxy- silyl)propyl methacrylate (TMSPM) and 60-99 mole% dodecyl methacrylate (lauryl methacrylate) .
  • polymer (A) is derived from the following monomers in the following molar proportions:
  • the polymer of component (A) may include a proportion of siloxane repeating units, at least a major proportion of the repeating units, and preferably at least 55% of the units, are other than siloxane units.
  • the proportion of siloxane repeating units is advanta- geously not more than 25%, preferably not more than 10%, and more especially not more than 5%.
  • the polymer of component (A) is substantially free of siloxane repeating units.
  • Polymer (A) may have a number-average molecular weight in the range of from 1000 to 50000, preferably from 5000 to 20000, advantageously from 5000 to 15000 more especially from 3000 to 15000.
  • a chain transfer agent may be used in the production of the polymer of component (A) .
  • chain transfer agents there may be mentioned 1-dodecanethiol and mercaptopropyltrimethoxysilane.
  • the molecular weight of the polymer may also be controlled by varying the content of polymerisation initiator.
  • preferred free-radical initiators include organic peroxides such as tert-butyl peroxy-2-ethyl- hexanoate (available under the trade name Trigonox 215) and the materials available under the trade names Trigonox 27 and Trigonox 41-C 75.
  • the or each polysiloxane of component (B) in a composition according to the invention may be an organohydrogenpolysiloxane or a polydiorganosiloxane.
  • the polysiloxane may, for example, comprise a copolymer of diorganosiloxane units with organohydrogen siloxane units and/or with other diorganosiloxane units, or a homopolymer of organohydrogen siloxane units or of diorganosiloxane units.
  • a curable polysiloxane(s) of the present invention (B) may in principle contain any of the functional groups, which may be pendant and/or terminal, described above in connection with component (A) as susceptible to polysiloxane curing. There are not the same disadvantages, however, arising from the presence of silanol groups in component (B) as in component (A), and component (B) is advantageously curable by virtue of such groups.
  • component (B) may be curable by virtue of curable functional groups selected from aliphatic, aromatic and araliphatic ether, ester and oxime groups, which may be substituted or unsubstituted, or also trialkoxysilyl or hydrosilyl groups.
  • a curable ether group may be, for example, an alkoxy group such as, for instance, methoxy or ethoxy.
  • An example of a curable ester group is acetoxy.
  • a curable polysiloxane (B) may be curable by virtue of oxime groups of the formula R 4
  • a group R 4 and/or R 5 may be substituted or unsubstituted.
  • Oxime-functional polysiloxanes may be prepared by reaction of the corresponding hydroxy-functional siloxane with a ketiminoxysilane, for example, methyl tris(methyl- ethylketiminoxy) silane, or one or more of the following ketiminoxysilanes :
  • Preferred components (B) are linear polymers and advantageously have the structure R 3 0(SiR 1 R 2 0) n R 3 , in which R 1 and R , which may be the same or different on each silicon atom and on different silicon atoms in the polymer, each represents an alkyl group such as, for example, methyl, ethyl, or propyl ; an alkenyl group such as, for example, vinyl or allyl; a cycloalkyl or cyclo- alkenyl group; an aryl group such as, for example, phenyl ; or a halogenated or cyano-substituted hydrocarbon group, with the proviso that one of R 1 and R 2 may represent hydrogen on some or all of the silicon atoms and that R 1 and R 2 may each represent hydrogen on some of the silicon atoms,
  • OR 3 represents a curable functional group in which R 3 represents a monovalent radical such as, for example, hydrogen, alkyl, aryl or R R 5 CN where R 4 and R 5 are as hereinbefore defined, and n represents a degree of polymerisation.
  • R 1 and R 2 are each methyl, although partial or total replacement of R 2 by phenyl may be of advantage.
  • component (B) may in principle be curable by virtue of a ino groups, preferred component(s) (B) do not include any amino functionality.
  • the polysiloxane component (B) may have a number- average molecular weight in the range of from 1500 to 310 000, generally from 1800 to 80 000 or 85 000.
  • the number-average molecular weight of component (B) is at least 5000, advantageously at least 10 000, and more especially at least 15 000.
  • the upper limit of molecular weight will usually be 60 000 or 70 000.
  • the polysiloxane component (B) preferably has a viscosity in the range of from 7.5 to 200 poise at 25 "c.
  • a viscosity in the range of from 7.5 to 200 poise at 25 "c.
  • the proportion of component (A) is in the range of from 50 to 99% by weight, preferably from 84 to 98% by weight, more especially from 90 to 98% by weight
  • the proportion of component (B) is in the range of from 1 to 50% by weight, preferably from 2 to 16% by weight, more especially from 5 to 16% by weight, in particular from 2 to 10% by weight, all percentages being based on the total weight of (A) + (B).
  • the proportion of component (B) is at least 5% by weight, advantageously at least 10% by weight, and more especially from 10 to 25 or 30% by weight, all percentages being based on the total weight of (A) + (B).
  • a composition comprising components (A) and (B) may include a curing catalyst, especially for condensation cure, and in general will include such a catalyst.
  • catalysts which may be used include amines and the carboxylic acid salts of various metals, for example, tin, zinc, iron, lead, barium and zirconium.
  • the salts are preferably salts of long-chain carboxylic acids, for example, dibutyltin dilaurate, dibutyltin dioctoate, iron stearate, tin (II) octoate and lead octoate.
  • Suitable catalysts include organobismuth and organotitanium compounds and organo- phosphates such as bis(2-ethyl hexyl) hydrogen phosphate.
  • Other possible catalysts include chelates such as, for example, dibutyltin acetoacetonate.
  • the catalyst may comprise a halogenated organic acid, which has at least one halogen substituent on a carbon atom which is in opposition relative to the acid group, and/or at least one halogen substituent on a carbon atom which is in ⁇ - position relative to the acid group, or a derivative which is hydrolysable to form such an acid under the conditions of the condensation reaction.
  • references to the acid catalyst include references to hydrolysable derivatives thereof.
  • the acid catalyst may be a mono-, di- or polybasic acid, but is preferably a monobasic acid.
  • the acid catalyst is a protonic acid and may comprise one or more carboxylic and/or sulphonic acid groups, preferably one or more carboxylic acid groups.
  • the or each halogen substituent may be fluorine, chlorine or bromine, but is preferably chlorine.
  • the acid catalyst may comprise dichloroacetic acid, trichloro- acetic acid or tribro oacetic acid.
  • the catalyst may comprise 3-dichloro- 2-dihydroxy propanoic acid, or 3-trichloro-2-dihydroxy- propanoic acid.
  • the acid is advantageously an aliphatic acid, but may comprise one or more aromatic groups , such as phenyl or substituted phenyl , provided that there is preferably no aromatic group attached to the ⁇ -carbon atom or bonded directly to the acid group.
  • An aromatic group may be a heterocyclic group, such as pyridyl or pyrrolyl .
  • An aliphatic acid may be a cyclic or, preferably, an acyclic acid.
  • the catalyst is a halogenated alkanoic acid having up to 5 carbon atoms or a hydroxy- substituted derivative of such an acid.
  • acid derivatives which are hydrolysable to form the acids under the conditions of the condensation reaction there may be mentioned anhydrides , for instance, trichloroacetic acid anhydride, and esters, which may be hydrocarbyl esters , especialy methyl esters , or alkyl silyl esters, advantageously C 1 _ 4 alkylsilyl esters, especially ethylsilyl esters.
  • the catalyst may comprise trimethylsilyl- trichloroacetate .
  • the catalyst contains more than one acid group, there may be halogen substitution on each - and/or ⁇ - carbon atom or on only some of those carbon atoms.
  • the acid catalyst may carry one or more other substituents in addition to the specified halogen substitution.
  • the acid catalyst may be used alone or in conjunction with one or more other such catalysts but in the absence of any metal salt catalyst of the kind previously proposed.
  • acid catalysts of the invention offer the possibility of dispensing with tin-based catalysts such as dibutyltindilaurate.
  • the proportion of catalyst in a composition comprising components (A) and (B) may be in the range of from 0.01 to 5% by weight, advantageously from 0.05 to 2% by weight, and preferably not exceeding 1% by weight, based on the total composition.
  • 0.01-1% by weight on solids of dibutyltin dilaurate may be added to the coating composition soon before application to the surface to be coated. With such a level of catalyst, the applied coating will typically cure tack-free within 1 day and be fully cured within 3-4 days.
  • the catalyst may be packaged separately in a so-called “two-pack" system, or the catalyst may be packaged with one of the components but separately from the other.
  • a cross-linking agent for some or all of the curing reactions involved in the process of the invention.
  • the use of a cross- linking agent tends to lessen the extent to which there is a visible and mechanically removable layer of unreacted siloxane material at the outer surface of the applied coating. It has been observed (using ATR-FTIR spectroscopy) that the concentration of siloxane at the outer surface of a coating formed from a composition including a cross-linking agent is greater than the siloxane concentration at the outer surface (after removal of unreacted siloxane) of a coating formed from a composition having no cross-linking agent.
  • a cross-linking agent comprises a functional silane, more especially a functional silane of the formula
  • each may comprise a straight-chain or branched, saturated or unsaturated, aliphatic hydrocarbon radical, preferably having up to 7 carbon atoms, more especially up to 4 carbon atoms, or an aromatic or araliphatic hydrocarbon radical, such as, for example, phenyl or benzyl, or an aliphatic or aromatic ether group, such as an alkoxy, phenoxy or benzyloxy group, or an ester group.
  • An aliphatic group R 1 to R 4 is preferably an alkyl group, advantageously a C- ⁇ -C ⁇ alkyl group, preferably a methyl or ethyl group, and an alkoxy group R 1 to R 4 is advantageously C -C ⁇ alkoxy, preferably ethoxy or ethoxy.
  • alkoxysilanes of the formula (I) include tetraalkyl orthosilicates such as tetra ethyl, -ethyl, -propyl or -butyl orthosilicate, dimethoxydimethyl silane and diethoxydimethyl silane.
  • a compound of formula (I) in order to serve as a cross- linking agent, must be at least difunctional and preferably at least tri-functional. Any of the groups R 1 to R 4 in formula (I) may be unsubstituted or may be substituted by one or more substituents selected, for example, from halogen (especially chlorine or fluorine), amino groups or alkyl groups, which may themselves be substituted or unsubstituted.
  • substituents especially chlorine or fluorine
  • a functional silane cross-linking agent may be reactive by virtue of one or more oxime groups of the formula
  • R 4 and R 5 may be the same or different and each represents a straight-chain or branched saturated or unsaturated, aliphatic hydrocarbon radical, preferably having up to 7 carbon atoms, more especially up to 4 carbon atoms, especially a methyl or ethyl group; an aromatic group, for example, a phenyl group; or an araliphatic group, for example, a benzyl group, or R 4 and R 5 together represent an alkylene group, or one of R 4 and R 5 represents hydrogen.
  • a group R 4 and/or R 5 may be substituted or unsubstituted.
  • cross-linking or curing agents include oximes such as vinyltris(methylethylketoxime) or methyltris (methylethylketoxime) .
  • a cross-linking or curing agent may comprise a cyclic compound of the following formula:
  • n is an integer of from 3 to 10
  • R represents hydrogen or methyl
  • a silane cross-linking agent may in principle be incorporated in a mono eric form or in the form of a self-condensation product, which may be, for example, a dimer, trimer, heptamer or a low molecular weight polymer.
  • the proportion of cross- linking agent in the composition comprising components (A) and (B) may be in the range of from 0.05 to 10% by weight, generally from 2 to 5% by weight, based on the weight of component (B) in the composition.
  • compositions which comprise a polymer (A) which does not contain silanol groups and a poly(diorganosiloxane) (B) which does contain silanol groups are stable on storage provided that the polymer (A) does not contain groups known to be effective as catalysts in curing silicones, for example amines and the metal salts of carboxylic acids as mentioned above. It has further been found that compositions containing no silanol groups but containing groups effective as catalysts are stable in the absence of moisture.
  • the process for forming the initial coating from the composition comprising components (A) and (B) is most conveniently carried out using a solution of the composition in a non-reacting volatile solvent for the composition.
  • suitable solvents include aromatic hydrocarbons, for example toluene, xylene and trimethylbenzene; alcohols, for example, butanol; ketones, for example 4- methylpentan-2-one (methylisobutylketone) , 5-methylhexan- 2-one ( methylisoamylketone ) and cyclohexanone; esters, for example butyl acetate and 2-ethoxyethyl acetate, and mixtures of the above with one another or with an aliphatic hydrocarbon, for example in the form of white spirit.
  • a solution of the coating composition comprising components (A) and (B) may comprise at least 35% by weight solids, generally at least 50% by weight solids. More concentrated solutions, for example containing at least 70% solids, may be employed if the polymer component (A) is of low molecular weight.
  • the maximum solids content may be as high as 90% by weight or even more, but in general the maximum practicable solids content will be in the range 75-85% by weight, typically 80% by weight.
  • the coating compositions comprising components (A) and (B) of the present invention require the presence of water in order to achieve full cure, but specific addition of water is not normally required, either during or after application of the composition. It has been found that atmospheric moisture or the water commonly found on damp surfaces to be coated is sufficient to induce curing, and it will not normally be necessary or appropriate to heat the applied coating for curing purposes.
  • compositions comprising components (A) and (B) are in general sensitive to the presence of water, it is preferable to take steps to minimise the water content of all ingredients of the composition, and it will be appreciated that no water or aqueous material should be added.
  • commercially available solvents will frequently contain a small amount of water (say, 1-2% by volume) and it is preferable to reduce the water content of such materials before use.
  • such reduction in water content may be achieved by distillation in conjunction with a drying agent such as, for example, sodium, sodium hydride or calcium hydride or anhydrous calcium sulphate, but advantageously a reactive water-scavenger is used, for example, an inorganic salt such as, for example, magnesium sulphate (followed by filtration) or a mono- or di-functional silane, for instance, ethoxytrimethyl silane.
  • a drying agent such as, for example, sodium, sodium hydride or calcium hydride or anhydrous calcium sulphate
  • a reactive water-scavenger is used, for example, an inorganic salt such as, for example, magnesium sulphate (followed by filtration) or a mono- or di-functional silane, for instance, ethoxytrimethyl silane.
  • Compositions comprising components (A) and (B) and the coatings derived therefrom may also include one or more unreactive oils such as, for example, a silicone oil, especially a methyl phenylsilicone oil such as that sold by Rhone-Poulenc under the trademark "Rhodorsil Huile 550" or a petroleum or polyolefin oil or a polyaromatic oil.
  • unreactive oils such as, for example, a silicone oil, especially a methyl phenylsilicone oil such as that sold by Rhone-Poulenc under the trademark "Rhodorsil Huile 550" or a petroleum or polyolefin oil or a polyaromatic oil.
  • the composition includes a quantity of a petrolatum oil.
  • a petrolatum oil In the case of coatings formed from a composition not including petrolatum, there may in some cases be a very thin layer of pure siloxane component at the outer surface, with a siloxane-rich layer underneath.
  • a relatively thick siloxane-rich layer is formed, typically at least an order of magnitude thicker than the siloxane-rich layer formed without the use of petrolatum; such a siloxane-rich layer may comprise a 50/50 mixture of siloxane and petrolatum.
  • the proportion of petrolatum is advantageously in the range of from 5 to 25% by weight (based on the amount of component (A) preferably in the range of from 15 to 20% by weight.
  • the proportion of petrolatum oil used may be higher than 25% by weight, but proportions above 25% by weight in unpigmented systems will in general lead to an undesirable decrease in the integrity of the applied coating.
  • compositions comprising components (A) and (B) can be pigmented, for example at a pigment volume concentration of 0.5 to 25%, or dyed, or can be used as clear transparent coatings.
  • compositions may also contain other excipients and/or fillers such as barium sulphate or other mineral fillers, pyrogenic silica, bentonite or other clays. typically in a proportion of from 0.5 to 5% by weight, preferably from 1 to 2% by weight.
  • excipients and/or fillers such as barium sulphate or other mineral fillers, pyrogenic silica, bentonite or other clays. typically in a proportion of from 0.5 to 5% by weight, preferably from 1 to 2% by weight.
  • the coating compositions comprising components (A) and (B) can be single-pack coatings for moisture cure, or a two-pack system may be used.
  • the polymer component (A) can be packaged separately from the polysiloxane (B) , and any catalyst is preferably packaged separately from the polymer component (A) .
  • Component (A) Component (B)
  • Viscosity (e) Viscosity; (f) Mode of application, including solvent usage and the solids content of an application solution; (g) Optional use of unreactive oil(s); and (h) Optional use of pigments.
  • Silanol functionality is preferred, but alkoxy functionality may also be advantageous.
  • the viscosity of component (C) may be in the range of from 1 to 200 poise at 25 °C, but is preferably from 20 to 50 poise, more especially from 35 to 50 poise.
  • tin catalyst is preferred for the curing of component (C) - in terms of the cure profile for the reaction - but may in some cases be less favoured for the (A)/(B) curing reaction, especially if aminofunctionality is present.
  • an acid catalyst may be less preferred in the curing of component (C) .
  • the use of pigments and other excipients and/or fillers does not in general lead to any difficulties in relation to component (C) , and may be advantageous not only in terms of the appearance of the outer coating but also in facilitating the application of relatively thick layers.
  • component (C) is similar to or substantially identical with component (B) of the initial coating composition, especially in terms of one or more and preferably all of features (a) -(e) above.
  • composition comprising
  • (C) can in principle be packaged in a one-, two- or three-pack system.
  • the thickness of the coating formed by curing of the composition comprising components (A) and (B) may be in the range of from 50 to 100 microns, and the thickness of the layer comprising cured component (C) will typically be in the same range. More than one layer (C) can be applied if desired.
  • Example 1 One-pack composition
  • Example 2 One-pack composition
  • Example 3 One-pack composition
  • Curing agent Tetraethylorthosilicate 2.60
  • Curing agent Tetraethylorthosilicate 2.56
  • Example 9 Three-pack composition Parts by weight
  • Air floated silica 1.35 Trimethylbenzenes 7.77
  • Curing agent Tetraethylorthosilicate 2.57
  • Curing agent Tetraethylorthosilicate 2.56

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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

La présente invention concerne un procédé destiné à inhiber les salissures sur un substrat dans un environnement à salissures. Ce procédé consiste d'abord à appliquer sur le substrat, avant exposition audit environnement d'une composition renfermant: (A) un polymère portant des groupes pendants et/ou fonctionnels durcissables terminaux, au moins une partie principale des unités de répétition du polymère (A) étant différentes des unités de siloxane; (B) un ou plusieurs polysiloxanes possédant des groupes pendants et/ou fonctionnels de durcissement terminaux et sélectionnés parmi des polysiloxanes organohydrogénés durcissables et des polydiorganosiloxanes durcissables, les groupes fonctionnels durcissables du composant (B) pouvant être soumis à une réaction de durcissement avec les groupes fonctionnels durcissables du composant (A); et à durcir ensuite la composition appliquée renfermant les composants (A) et (B) conjointement ou non avec un agent de réticulation, puis à appliquer une couche renfermant (C) un polysiloxane organohydrogéné ou un polydiorganosiloxane durcissables, et à durcir la couche appliquée, conjointement ou non avec un agent de réticulation. Pour augmenter l'efficacité de l'inhibition, la couche durcissable (C) est appliquée sur un revêtement fraîchement préparé formé par le durcissement de la composition renfermant les composants (A) et (B). Par ailleurs, pour la restauration et/ou la réparation, la couche durcissable (C) est appliquée sur un revêtement initialement formé par le durcissement de la composition renfermant les composants (A) et (B), mais qui a été usé et/ou endommagé au cours de son utilisation.
PCT/GB1998/000706 1997-03-07 1998-03-05 Inhibition des salissures WO1998039391A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU65082/98A AU6508298A (en) 1997-03-07 1998-03-05 Fouling inhibition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9704794.8 1997-03-07
GBGB9704794.8A GB9704794D0 (en) 1997-03-07 1997-03-07 Fouling inhibition

Publications (1)

Publication Number Publication Date
WO1998039391A1 true WO1998039391A1 (fr) 1998-09-11

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AU (1) AU6508298A (fr)
GB (1) GB9704794D0 (fr)
WO (1) WO1998039391A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1584664A3 (fr) * 2004-04-07 2006-02-22 Shin-Etsu Chemical Co., Ltd. Composition de revêtement antifouling et articles revêtus
US7033673B2 (en) * 2003-07-25 2006-04-25 Analytical Services & Materials, Inc. Erosion-resistant silicone coatings for protection of fluid-handling parts
EP1990366A1 (fr) * 2006-02-17 2008-11-12 Chugoku Marine Paints, Ltd. Composition de polyorganosiloxane durcissable et film de revêtement composite antisalissure
CN102766861A (zh) * 2004-11-10 2012-11-07 凯密特尔有限责任公司 在已涂布的金属表面上制备修补涂层的方法
US10385221B2 (en) 2014-04-03 2019-08-20 Ppg Coatings Europe B.V. Erodible antifouling coating composition
US11413652B2 (en) 2020-04-10 2022-08-16 Formula No. 37, Llc Coated oilfield operational components and methods for protecting and extending the service life of oilfield operational components

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0032597A1 (fr) * 1979-12-11 1981-07-29 Shell Internationale Researchmaatschappij B.V. Structure marine revêtue
EP0089066A1 (fr) * 1982-03-17 1983-09-21 Wacker-Chemie GmbH Procédé permettant de modifier l'adhérence d'élastomères d'organopolysiloxanes
EP0532273A1 (fr) * 1991-09-13 1993-03-17 Courtaulds Coatings (Holdings) Limited Protection de substrats contre la salissure aquatique
WO1993013179A1 (fr) * 1991-12-20 1993-07-08 Courtaulds Coatings (Holdings) Limited Compositions de revetement
GB2300370A (en) * 1995-05-01 1996-11-06 Gen Electric Anti-fouling coating with anti-corrosive layer

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0032597A1 (fr) * 1979-12-11 1981-07-29 Shell Internationale Researchmaatschappij B.V. Structure marine revêtue
EP0089066A1 (fr) * 1982-03-17 1983-09-21 Wacker-Chemie GmbH Procédé permettant de modifier l'adhérence d'élastomères d'organopolysiloxanes
EP0532273A1 (fr) * 1991-09-13 1993-03-17 Courtaulds Coatings (Holdings) Limited Protection de substrats contre la salissure aquatique
WO1993013179A1 (fr) * 1991-12-20 1993-07-08 Courtaulds Coatings (Holdings) Limited Compositions de revetement
GB2300370A (en) * 1995-05-01 1996-11-06 Gen Electric Anti-fouling coating with anti-corrosive layer

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7033673B2 (en) * 2003-07-25 2006-04-25 Analytical Services & Materials, Inc. Erosion-resistant silicone coatings for protection of fluid-handling parts
EP1584664A3 (fr) * 2004-04-07 2006-02-22 Shin-Etsu Chemical Co., Ltd. Composition de revêtement antifouling et articles revêtus
US7351477B2 (en) 2004-04-07 2008-04-01 Shin-Etsu Chemical Co., Ltd. Antifouling coating compositions and coated articles
CN102766861A (zh) * 2004-11-10 2012-11-07 凯密特尔有限责任公司 在已涂布的金属表面上制备修补涂层的方法
CN102766861B (zh) * 2004-11-10 2015-12-16 凯密特尔有限责任公司 在已涂布的金属表面上制备修补涂层的方法
EP1990366A1 (fr) * 2006-02-17 2008-11-12 Chugoku Marine Paints, Ltd. Composition de polyorganosiloxane durcissable et film de revêtement composite antisalissure
EP1990366A4 (fr) * 2006-02-17 2012-07-25 Chugoku Marine Paints Composition de polyorganosiloxane durcissable et film de revêtement composite antisalissure
US10385221B2 (en) 2014-04-03 2019-08-20 Ppg Coatings Europe B.V. Erodible antifouling coating composition
US11413652B2 (en) 2020-04-10 2022-08-16 Formula No. 37, Llc Coated oilfield operational components and methods for protecting and extending the service life of oilfield operational components
US11446700B1 (en) 2020-04-10 2022-09-20 S+S Industries Technology Llc Methods for preparing coating compositions for protecting oilfield operational components
US11484909B1 (en) 2020-04-10 2022-11-01 S+S Industries Technology Llc Coated oilfield operational components and methods for protecting and extending the service life of oilfield operational components
US11559826B2 (en) 2020-04-10 2023-01-24 S+S Industries Technology Llc Methods for providing flexible and/or elastic coatings on oilfield operational components
US11583892B1 (en) 2020-04-10 2023-02-21 S+S Industries Technology Llc Coated oilfield operational components and methods for protecting and extending the service life of oilfield operational components
US11596976B2 (en) 2020-04-10 2023-03-07 S+S Industries Technology Llc Methods for preparing coating compositions for protecting oilfield operational components
US11618055B2 (en) 2020-04-10 2023-04-04 S+S Industries Technology Llc Methods for providing flexible and/or elastic coatings on oilfield operational components
US11826780B2 (en) 2020-04-10 2023-11-28 S+S Industries Technology Llc Methods for providing flexible and/or elastic coatings on oilfield operational components
US11845107B2 (en) 2020-04-10 2023-12-19 S+S Industries Technology Llc Methods for protecting oilfield operational components from damage from fluid flow
US12059705B2 (en) 2020-04-10 2024-08-13 S+S Industries Technology Llc Coating and methods for extending service life of oilfield operational components
US12059706B2 (en) 2020-04-10 2024-08-13 S+S Industries Technology Llc Methods for preparing coating compositions for protecting oilfield operational components

Also Published As

Publication number Publication date
AU6508298A (en) 1998-09-22
GB9704794D0 (en) 1997-04-23

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