CN103608411A - Biocidal foul release coating systems - Google Patents
Biocidal foul release coating systems Download PDFInfo
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- CN103608411A CN103608411A CN201280029226.3A CN201280029226A CN103608411A CN 103608411 A CN103608411 A CN 103608411A CN 201280029226 A CN201280029226 A CN 201280029226A CN 103608411 A CN103608411 A CN 103608411A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B63—SHIPS OR OTHER WATERBORNE VESSELS; RELATED EQUIPMENT
- B63B—SHIPS OR OTHER WATERBORNE VESSELS; EQUIPMENT FOR SHIPPING
- B63B59/00—Hull protection specially adapted for vessels; Cleaning devices specially adapted for vessels
- B63B59/04—Preventing hull fouling
-
- 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
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
-
- 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
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1625—Non-macromolecular compounds organic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
-
- 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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- 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
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31663—As siloxane, silicone or silane
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Mechanical Engineering (AREA)
- Ocean & Marine Engineering (AREA)
- Plant Pathology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Provided is a structure coated with a biocidal foul release coating system. The structure is obtained by a. providing a substrate, b. coating the substrate with a first coating layer, c. applying at least one subsequent coating layer on top of the first coating layer, the first coating layer containing a biocide, the subsequent coating layer(s) containing less biocide than the first coating layer and which is(are) free or substantially free of biocide, and wherein the first and the subsequent coating layer(s) form a biocidal foul release coating system showing a controlled leaching of the biocide.
Description
Invention field
The present invention relates to the purposes of dirt release coatings (foul release coating) in the leaching of controlling biocides coating system of coating from comprising this dirt release coatings and biocidal.In addition, the present invention relates to purposes in this coating system, its incrustation on suppressing substrate and through the substrate of this linkable paint system.
Background technology
Artificial ocean structure is if ship and boat body, buoy, production platform, graving dry dock equipment, produce oil rig and pipeline under water are easily because of incrustation such as hydrobiont such as green alga and brown alga, barnacle (barnacle), mussels.These structures are made of metal conventionally, but also can comprise other structured materials as concrete.This incrustation causes the puzzlement on hull, and this is because its increase moves through the friction resistance during water, and result is Speed Reduction and increases fuel cost.It causes static structure body as the puzzlement on the support of production platform and produce oil rig, first this be because thick incrustation layer can cause unpredictable and stress potentially dangerous to the resistance of wave and current in structure, is secondly because incrustation causes the defect that is difficult to check structure as stress crack and corrosion.It causes pipeline as the puzzlement in entrance of cooling water and outlet, and this is because effective cross section is long-pending because incrustation reduces, and flow velocity is reduced.
By the antifouling varnish that contains biocides, suppress incrustation traditionally, this biocides can leach gradually from paint.The commercial incrustation method that the most successfully suppresses relates to use antifouling paint, and it contains the material poisonous to aquatic life, for example triorganotin compound.Yet, if the damage effect that may have while being released under specific circumstances in aquatic environment due to some these toxin, thereby these coating are more and more out of favour.
Known (be for example disclosed in GB1,307,001 and US3,702,778 in) some coating for many years, for example elastomerics (as polysiloxane rubber) tolerates hydrobiological incrustation.These coating are non-biocidal, are generally hydrophobicity, and it is believed that it has the surface that stops sedimentation and/or organism to adhere to easily with physics mode, so it can be called dirt release coatings but not antifouling paint.Dirt releasing properties can adhere to measurement (for example ASTM D5618-94) by barnacle and characterize.Method records following barnacle adhesion value thus: polysiloxane surface (0.05MPa), polypropylene surface (0.85MPa), polycarbonate surface (0.96MPa), epoxy surface (1.52MPa) and carbamate surface (1.53MPa) (J.C.Lewthwaite, A.F.Molland and K.W.Thomas, " An Investigation into the variation of ship skin fictional resistance with fouling ", Trans.R.I.N.A., the 127th volume, 269-284 page, London (1984)).As coating being regarded as to the indication of dirt release type: dirt release coatings has the average barnacle adhesion value that is less than 0.4MPa conventionally.
Polysiloxane rubber and polysiloxane compound have low-down toxicity conventionally.When being applied to boat body, although the accumulation that a shortcoming of this dirt delivery systme is incrustation biology reduces, need relatively high container speed to remove all incrustation materials.Therefore, in some cases, shown and need navigate by water from the hull of processing through this coating, to remove incrustation satisfactorily with the speed of at least 10 joints.For this reason, polysiloxane rubber only obtains limited business effect so far.
Also known polysiloxane dirt release coatings is conventionally poor for the adhesion of protective system for a long time, unless used suitable linking coating or link coating (link coat) to guarantee enough adhesions.These are connected coating conventionally containing polysiloxane.The example that contains the linking coating of polysiloxane is described in EP521983 and EP1832630.
Sometimes the combination of suitable linking coating and the second dope layer is called to " dual " dirt delivery systme.Up to now, be described in these dual systems of the prior art, be used as be connected coating composition conventionally containing the biocides adding, and WO2008/013825 clearly instructs and does not use biocides as a part for its system.
The open ocean of GB1409048 polyurethane(s) top layer coating composition, it can absorb the seawater of the 30-300% of himself weight, and is applied on biocidal antifouling paint.The polyurethane(s) top layer coating of GB1409048 not dirt release coatings for the present invention (referring to " Redefining antifouling coatings ", Journal of Protective Coatings and Linings, in September, 1999,26-35 page, openly comparing polyurethane(s) with polysiloxane has high barnacle adhesion strength for it).Unexposed or propose follow-up dirt release coatings layer in GB1409048.
EP0313233 describes a kind of antifouling Marine Paints, and it comprises and contains the second layer that the first layer of the antifouling anticorrosive ocean paint of marine organisms toxic substance and the porous organo polysilica that adheres to this first layer is closed to film; This porous organo polysilica closes film and is preferably tetrafluoroethylene (EPTFE).It is not coating for the present invention that porous organo polysilica closes film, and this is because it not uses and be dried or be solidified to form again subsequently dry continuous film as liquid mixture.In addition, tetrafluoroethylene is the material that is not suitable for use in dirt release surface (referring to above-mentioned " Redefining antifouling coatings ", it points out high barnacle adhesion strength).Both unexposedly in EP0313233 also propose not use follow-up dirt release coatings layer.
US4,129,610 describe a kind of water-soluble coating composition for boat bottom, and it comprises ethylenic copolymer and soluble epoxide compound.This water-soluble coating composition is applied on the primer base layer with toxic materials.US4,129,610 water-soluble coating composition is not regarded as dirt release coatings (referring to above-mentioned document " Redefining antifouling coatings ", the barnacle adhesion strength of its report epoxy coating is high) for the present invention.Both unexposedly also propose not use follow-up dirt release coatings layer.
The chlorination that FR2636958 describes for silicone elastomer adheres to priming paint.According to the disclosure, three organotin oxides or halogenide biocides or cupric oxide can be added into this priming paint.Tributyl tin oxide compound or fluorochemical and cupric oxide are suitable biocides additive that this system is only mentioned, and do not contain any biocides priming paint embodiment or further illustrate.The leaching of the complete not mentioned biocides of the document, and do not there is the instruction of the dirt delivery systme of the priming paint that contains any biocides.
WO95/32862 openly can be used on substrate to resist the dual dirt delivery systme of marine organisms incrustation.This dual system is comprised of bonding coat and releasing layer, wherein 3-isothiazolones biocides is embedded in this bonding coat or releasing layer.The document is only instructed and should be used 3-isothiazolones as biocides, and speed and time square root that biocides leaches from bonding coat be inversely proportional to, and may, except the solubleness of biocides in water, there is no other controlling factors leaching rates.Therefore, in these systems, the leaching of biocides is only subject to bad control, and it is not suitable as the biocidal dirt release coatings system with controlled biocides leaching rate in framework of the present invention.Find the substrate through applying such as the disclosed system of WO95/32862 (wherein biocides is inversely proportional to from the leaching rate of bonding coat and the square root of time), after in this substrate is immersed to seawater soon, substrate substantially keep without incrustation and with through the substrate not applying containing the dirt release coatings system of biocides, compare, it demonstrates excellent properties.Yet this excellent properties is without maintaining, the substrate through applying covers through biological incrustation gradually, and in 4-6 month, and the system of WO95/32862 demonstrates the severe deposits similar to substrate through not applying containing the dirt release coatings system of biocides.
Summary of the invention
Shockingly, discovery can be prepared the structure applying through biocidal dirt release coatings system of the controlled leaching that demonstrates biocides.
According to the present invention, this structure can obtain by following steps:
A., substrate is provided,
B. with the first dope layer, apply this substrate,
C. on the top of this first dope layer, use at least one follow-up dope layer,
Wherein this first dope layer and this follow-up dope layer form biocidal dirt release coatings system, this first dope layer contains biocides, this follow-up dope layer contains the biocides fewer than this first dope layer, and this follow-up dope layer does not contain or substantially contain biocides.
As defined biocidal dirt release coatings system in the application demonstrates the controlled leaching of biocides.
The controlled leaching that what is called demonstrates biocides means after 5 days, from dirt release coatings system of the present invention, to discharge the speed (R of biocides using this coating
5) with use the rate of release (R of 30 days artifact kill agent of this coating
30) ratio R
5/ R
30be less than or equal to (≤) 1.5, preferably≤1.33, more preferably≤1.11.
In the short period of time of biocidal dirt release coatings system of the present invention after in this substrate is immersed to seawater and long period, demonstrate outstanding anti-incrustation.
In framework of the present invention, biocidal dirt release coatings system is to have with physics mode to stop sedimentation and/or aquatic/marine organisms to be not easy to the surperficial coating system adhering to, and biocides is discharged by coating system from this surface.
For improving the adhesion of the first dope layer to substrate, between this substrate and this first dope layer, can exist and be connected coating or adhesion promoter layer.For improving the erosion resistance of this substrate, before using this first dope layer, on this substrate, also can use anti-corrosive paints.More generally, before the first dope layer that comprises biocides is applied to this substrate, on substrate, can there are one or more dope layers.
For preparing dope layer, the coating composition as liquid mixture is applied to this surface (for example, to this substrate or another dope layer); Subsequently, dry or curing this coating composition to form dry continuous paint film/layer on this surface.
The inventor finds can control by follow-up dope layer by the applied on top at the first dope layer from the speed of biocidal dirt release coatings system leaching biocides, wherein this first dope layer contains biocides, and this follow-up dope layer contains than the few biocides of this first dope layer and do not contain or substantially contain biocides.Its advantage is adjustable biocides leaching rate, reduces and the dependency of time and the more linear relation of actual sustain and time.Therefore, can reach required and more constant biocides leaching rate.This is favourable, because it causes extending the usefulness life-span, more effectively utilizes biocides and reduces environmental impact.In addition, can control biocides and leach, make especially to strengthen the ability that this incrustation release coatings system prevents incrustation under low speed or static conditions.
For the present invention, biocides should be leached to (being sometimes referred to as biocides discharges) and biocides leaching rate (biocides rate of release) and discharge clear differentiation with dirt.Leaching rate is that biocides is released into the speed in ambient water via coating system and is typically expressed as the biocides quality of per unit area time per unit.Dirt discharges to relate to and prevents incrustation and/or its easness removing from immersing the surface of substrate by non-biocidal mode.For example, dirt releasing properties can adhere to measure by barnacle and characterize, and it can use ASTM D5618-94, and standard method of test or the methods involving of measuring barnacle adhesion shearing resistance carry out.The two is for controlling the complementary mechanisms of incrustation but being mutually independent.
More particularly, the inventor finds to control leaching rate by changing the composition of this follow-up dope layer.The first dope layer is as the reservoir of the biocides of supplying with containing the preparation that needs to be discharged biocides.The leaching rate of this biocides can be controlled by changing some characteristic of this first dope layer and this follow-up dope layer.These characteristics include but not limited to: pigment volume concentration (PVC), cross-linking density, pigment size and shape, the molecular weight of polymkeric substance, the existence of incompatible fluid whether with cross-linking chemistry and the film thickness of amount, this follow-up dope layer.
Allow to regulate biocides leaching rate according to end-use with the reservoir of the biocides of the controlling mechanism combination of this follow-up dope layer.
In framework of the present invention, the coating system that demonstrates the controlled leaching of biocides is the rate of release (R that is immersed in the water 30 days artifact kill agent
30) for being at least immersed in the water the rate of release (R after 5 days
5) 67% system.In other words, the coating system that demonstrates the controlled leaching of biocides is R wherein
5/ R
30≤ 1.5 system.
In one embodiment of the invention, R
5/ R
30≤ 1.5.In another embodiment of the invention, R
5/ R
30≤ 1.33.In yet another embodiment of the present invention, R
5/ R
30≤ 1.11.
In WO95/32862, dual dirt delivery systme is described as having the biocides that is inversely proportional to time square root from the leaching rate of bonding coat, and may be except the solubleness of biocides in water, without other controlling factors leaching rates.For this system, the rate of release of biocides is described as F (t)～36/t
0.5, wherein F is with μ g/cm
2/ day (μ g cm
-2my god
-1) leaching rate of meter and t be in time in sky.For this system, R
5/ R
30=F (5)/F (30)=30
0.5/ 5
0.5=2.45.WO95/32862 do not instruct wherein substrate first the dope layer through containing biocides apply, apply thereon more subsequently substantially not containing the biocidal dirt release coatings system of the succeeding layer of biocides by cause biocides from dirt release coatings surface more gradually with lasting release profiles.
According to the present invention, the follow-up dope layer that is applied in this first dope layer top contains the biocides fewer than this first dope layer.In addition, this follow-up dope layer does not contain or substantially contains biocides.Substantially containing biocides, do not mean this follow-up dope layer and contain the biocides that is less than 1.0wt% (gross weight based on this coating composition).Preferably, this follow-up dope layer contains and is less than 0.5wt%, is more preferably less than the biocides of 0.1wt%.For avoiding query, weight percent (wt%) is the weight percent of the gross weight based on this coating composition.
In one embodiment, this follow-up dope layer further comprises incompatible fluid.
Incompatible fluid in this follow-up dope layer contributes to realize improved dirt release performance.Do not wish to be limited to theory, it is believed that this fluid may affect the conveying of biocides.
In another embodiment, biocides is through partly or entirely sealing or absorption or load or combination.
Sealing or absorption or load or in conjunction with being provided for controlling the secondary mechanisms (secondary mechanism) that biocides leaches from this coating system of biocides, to realize release even more gradually and longer lasting effect.
The present invention relates to (i) biocidal dirt release coatings system, and the structure (ii) applying through this biocidal dirt release coatings system, this biocidal dirt release coatings system comprises:
A. substrate,
B. the first dope layer,
C. the follow-up dope layer of at least one on the top of this first dope layer,
This first dope layer contains biocides, and this follow-up dope layer contains the biocides fewer than this first dope layer, and this follow-up dope layer does not contain or substantially contain biocides.This biocidal dirt release coatings body demonstrates the controlled leaching of biocides.
One embodiment of the invention are the structure applying through biocidal dirt release coatings system defined above.
Detailed Description Of The Invention
The first dope layer that contains biocides
The composition of the first dope layer there is no particular restriction, but the composition of this first dope layer preferably comprises polymkeric substance.This polymkeric substance is preferably formed elastomerics.More preferably, it is organopolysiloxane.Even more preferably, it is polydimethylsiloxane.In addition, this organopolysiloxane also can comprise the organopolysiloxane of two or more different viscosity.
Preferably, this organopolysiloxane has one or more, more preferably two or more reactive functional groups, for example hydroxyl, alkoxyl group, acetoxyl group, carboxyl, hydrogen silyl (hydrosilyl), amine, epoxy group(ing), vinyl Huo Wo functional group.
The amount that the gross weight that this polymkeric substance preferably be take based on this coating composition is 5-50wt% exists.It more preferably exists with the amount of 8-20wt%.
This polymkeric substance is preferably crosslinkable.The type that depends on crosslinkable polymer, this coating composition may need linking agent.The necessity that linking agent exists will depend on type and the quantity that is present in the functional group in this polymkeric substance.If this polymkeric substance comprises alkoxyl group-silyl, exist a small amount of water and optionally condensation catalyst be conventionally enough to realize completely curing after using of coating.For these compositions, atmospheric water is conventionally enough to induction and solidifies, and conventionally need to not use this coating composition of post-heating.
This linking agent optionally existing can be any or multiple linking agent comprising in functionalized silane and/or acetoxyl group, alkoxyl group, amido, alkene oxygen base and oximido.The example of these linking agents is in WO99/33927, and the 19th page the 9th is walked in the 21st page of the 17th row and propose.Also can use the mixture of different linking agents.
The amount that the gross weight that this linking agent preferably be take based on this coating composition is 0.1-20wt% exists.
This first dope layer comprises biocides.So-called " comprising "/" containing " means biocides and is present in this dope layer body (mean it was mixed in this coating composition before cure/dry).
Biocides of the present invention can be one or more in inorganic, organo-metallic with Yu Haiyang or limnobios, metal-organic or organic biocide.The example of lithotroph kill agent comprises that mantoquita is if cupric oxide, cupric thiocyanide, bronze, copper carbonate, cupric chloride, cupronickel and silver salt are as silver chloride or Silver Nitrate, organo-metallic and metal-organic biocide comprise Zinc Pyrithione (zinc salt of 2-pyridinethiol-1-oxide), copper pyrithione, two (N-cyclohexyl diazene
dioxy (diazeniumdioxy)) copper, ethylenebis (dithiocarbamic acid) zinc (being zineb (zineb)), ziram (ziram (ziram)) and ethylenebis (dithiocarbamic acid) manganese (being zinc manganese ethylenebisdithiocarbamate (mancozeb)) coordinating with zinc salt, and organic biocide comprises formaldehyde, Cyprex mono-hydrochloric salts, Apl-Luster (thiabendazole), N-trihalomethyl group sulfo-phthalic imidine, trihalomethyl group sulfo-sulphamide, N-aryl maleimide is as N-(2, 4, 6-trichlorophenyl) maleimide, 3-(3, 4-dichlorophenyl)-1, 1-Dimethylurea (Diuron Tech (diuron)), 2, 3, 5, 6-tetrachloro-4-(methyl sulphonyl) pyridine, 2-methylthio group-4-fourth amino-6-cyclopropylamino-s-triazine, 3-benzo [b] thienyl-5, 6-dihydro-Isosorbide-5-Nitrae, 2-
thiazine 4-oxide compound, the chloro-2-of 4,5-bis-(n-octyl)-3 (2H)-isothiazolones, 2,4,5,6-termil, tolylfluanid (tolylfluanid), Pecudin (dichlofluanid), diiodomethyl is to toluene sulfone, capsaicine (capsciacin), N-cyclopropyl-N'-(1,1-dimethyl ethyl)-6-(methyl sulfenyl)-1,3,5-triazines-2,4-diamines, IPBC, dexmedetomidine (medetomidine), 1, 4-dithia anthraquinone-2, 3-dimethoxy nitrile (Delan (dithianon)), borine is as pyridine triphenylborane, at 5 with optionally at 1 2-trihalogenmethyl-3-halogen-4-cyanopyrrole derivative 5-trifluoromethyl pyrpole as bromo-in 2-(rubigan)-3-cyano group-4-(tralopyril) being substituted, with furanone as 3-butyl-5-(dibromo methylene radical)-2 (5H)-furanones and its mixture, large cyclic ester is avermectin (avermectin) for example, as avermectin B1, ivermectin (ivermectin), doramectin (doramectin), abamectin (abamectin), abamectin (amamectin) and selamectin (selamectin), and quaternary ammonium salt is as Timbercote 2000 and alkyl dimethyl benzyl ammonium chloride.In one embodiment, this biocides can be 3-isothiazolones, however the inventor found this biocides preferably should be seal, absorption or combining form.In another embodiment, biocides is not 3-isothiazolones.
This biocides is preferably organic or metal-organically.Do not wish to be subject to theoretical institute to retrain, the leaching that it is believed that biocides relates to biocides and from this first dope layer physical diffusion, passes through this follow-up dope layer by passive course of conveying.Therefore, from the flux of the biocides of this coating system by part diffusing through this follow-up dope layer and controlling with the consistency of this follow-up dope layer by biocides.If this diffusion or consistency are high inherently, as as desired in organotin etc. to organo-metallic biocides, the leaching rate of gained is also will be inherently high and be difficult to control, and the life-span that makes this coating is by minimizing and may cause undesirable environmental influence.If this diffusion or consistency are low inherently, as desired in inorganic mantoquita etc. to lithotroph kill agent, leaching rate is also will be inherently low and may cause incrustation.Conventionally with organic or metal-organic biocide, allow the coating system of the application of the invention to control suitably leaching rate, and avoid unacceptable environmental disruption.
For the present invention, lithotroph kill agent is the biocides that chemical structure comprises atoms metal and non-carbon atoms; Organo-metallic biocides is the biocides that chemical structure comprises atoms metal, carbon atom and metal-carbon key; Metal-organic biocide is that chemical structure comprises atoms metal, carbon atom and the biocides of containing metal-carbon bond not; With organic biocide be that chemical structure comprises carbon atom and the biocides of containing metal atom not.
Preferably, for obtaining outstanding antifouling property, this biocides is at 5 and one or more in 1 2-trihalogenmethyl-3-halogen-4-cyanopyrrole derivative being substituted optionally, for example tralopyril, Isosorbide-5-Nitrae-dithia anthraquinone-2,3-dimethoxy nitrile (Delan), copper pyrithione, Zinc Pyrithione, tolylfluanid, Pecudin and N-cyclopropyl-N'-(1,1-dimethyl ethyl)-6-(methylthio group)-1,3,5-triazine-2,4-diamines.
Preferably, this biocides is with 0.05-50wt%, more preferably 3-30wt%, and most preferably the amount of 10-20wt% (gross weight of the composition based on this first dope layer) is stored in this first dope layer composition.Under any circumstance, when dope layer is applied to this substrate, the amount that is stored in the biocides in this first dope layer must be greater than the amount of the biocides at least one follow-up dope layer.
In addition, this biocides optionally all or part of through sealing, absorption or load or combination.The processing of some biocides be difficult or dangerous and its can be advantageously with through sealing or the form of absorption or load or combination is used.In addition, the sealing of this biocides, absorption or load or in conjunction with can be provided for controlling biocides from the secondary mechanisms of the leaching rate of this coating system to realize release and long-term lasting effect even more gradually.
For the purpose of the present invention, seal, absorption or load or there is no particular restriction in conjunction with the method for biocides.Can prepare the present invention used through seal the example of the method for biocides comprise single and double wall amino-formaldehyde or through hydrolysis polyvinyl acetate-phenol resin capsule or microcapsule, described in EP1791424.The suitable example through sealing biocides for through sealing 4, the chloro-2-of 5-bis-(n-octyl)-3 (2H)-isothiazolones, it is as sold with Sea-Nine CR2Marine Antifoulant Agent by Dow Microbial Control.
Can prepare through absorb or through load or through the example of the method in conjunction with biocides comprise the main consuming body-object title complex (being for example described in the clathrate in EP0709358), phenol resin as be described in EP0880892 those, sorbent material based on carbon is for example, as being described in those or the inorganic microporous carrier (being described in amorphous silicon di-oxide, non-crystalline state aluminum oxide, pseudo-boehmite or zeolite in EP1115282) in EP1142477.
In the crosslinkable situation of polymkeric substance of this biocidal the first dope layer composition, said composition optionally comprises catalyzer.The example of suitable catalyst is that various metals are as the carboxylate salt of tin, zinc, iron, lead, barium and zirconium.These salt are preferably long-chain carboxylic acid's salt, for example dibutyl tin laurate, two sad dibutyl tins, iron stearate, stannous octoate (II) and lead octoate 36.Other examples of suitable catalyst comprise that organo-bismuth and organic titanic compound and organophosphate are as two (2-ethyl-hexyl) hydrophosphate.Other possible catalyzer comprise sequestrant, for example acetopyruvic acid dibutyl tin.In addition, this catalyzer can comprise halogenation organic acid, it has at least one halogenic substituent and/or at least one halogenic substituent on the carbon atom of [β] position with respect to this acidic group on the carbon atom of [α] position with respect to this acidic group, or hydrolyzable to form this sour derivative under condensation reaction condition.
Or this catalyzer can be as described in any of WO2007122325A1, WO2008055985A1, WO2009106717A2, WO2009106718A2, WO2009106719A1, WO2009106720A1, WO2009106721A1, WO2009106722A1, WO2009106723A1, WO2009106724A1, WO2009103894A1, WO2009118307A1, WO2009133084A1, WO2009133085A1, WO2009156608A2 and WO2009156609A2.
The amount that the gross weight that the catalyzer of this biocidal the first dope layer composition preferably be take based on this coating composition is 0.01-4wt% exists.
Preferably, biocidal the first dope layer composition according to the present invention also comprises one or more fillers, pigment, other catalyzer and/or solvent.The example of suitable filler is barium sulfate, calcium sulfate, calcium carbonate, silicon-dioxide or silicate (for example talcum, feldspar and china clay), aluminum paste/flake aluminum, wilkinite or other clays.Some fillers have thixotropic effect to this coating composition as pyrogenic silica.The ratio of filler can the scope that be 0-25wt% in the gross weight based on this coating composition in.This clay preferably exists with the amount of 0-1wt%, and this thixotropic agent preferably exists (gross weight based on this coating composition) with the amount of 0-5wt%.
The example of suitable pigments is that iron oxide black, red iron oxide, iron oxide yellow, titanium dioxide, zinc oxide, carbon black, graphite, molybdate are red, bismuth vanadate yellow, molybdate Huang, zinc sulphide, weisspiessglanz, cobalt oxide/zinc titanium are green, zinc titanate/tin orange, lanthanum sulfide is orange and red, tetra-sodium manganese violet, sulfo group sodium aluminium silicate, quinacridone, phthalocyanine blue, phthalocyanine green, iron oxide black, indanthrone blue, cobalt oxide aluminium, carbazole two
piperazine, chromic oxide (III), isoindoline orange, di-acetyl acetyltoluene diazole (tolidiole), benzimidazolone, quinophthalone are yellow, isoindoline is yellow, tetrachloro iso-dihydro-indole and quinophthalone yellow.The ratio of pigment can the scope that be 0-10wt% in the gross weight based on this coating composition in.Suitable solvent comprises aromatic hydrocarbon, alcohol, ketone, ester and above-mentioned substance and each other or the mixture of aliphatic hydrocrbon.Preferred solvent comprises methyl isoamyl ketone and/or dimethylbenzene.The amount that the gross weight that this solvent preferably be take based on said composition is 10-40wt% exists.
Said composition optionally can comprise adhesion and promote material, and its amount conventionally gross weight based on said composition is 0.01-0.5wt%.The example of suitable adhesion promoter comprises that silane is as aminosilane, epoxy radicals silicone hydride, methacryloxypropyl silane and hydrosulphonyl silane.
This adhesion promoter is preferably the aminosilane with Types Below:
(RO)
xR
3-xSiR
1N(R
2)
2
Wherein each R is independently selected from C
1-8alkyl (such as methyl, ethyl, hexyl, octyl group etc.), C
1-4alkyl, O, C
2-4alkyl; Aryl (for example phenyl) and aryl C
1-4alkyl (for example benzyl); R
1be selected from (CH
2)
1-4, methyl-be substituted trimethylene and (CH
2)
2-3, O, (CH
2)
2-3; R
2be selected from hydrogen, alkyl, cycloalkyl, aralkyl or aromatic yl group or (CH
2)
2-4-NH
2.
Or this adhesion promoter is " both feet (the dipodal) " silane with Types Below as mentioned in WO2010018164
(R
3o)
3siR
1nHR
2si (OR
4)
3or (R
3o)
3siR
1nHR
5nHR
2si (OR
4)
3
R wherein
1, R
2and R
5be C independently
1-C
5alkylidene group and R
3and R
4independently selected from methyl or ethyl.
Or this adhesion promoter is the epoxy radicals silicone hydride with Types Below:
Si(R)
a(OR)
(3-a)
Wherein A is the monovalence alkyl replacing through epoxide with 2 to 12 carbon atoms; And each R is independently selected from C
1-8alkyl (such as methyl, ethyl, hexyl, octyl group etc.), C
1-4alkyl-, O-, C
2-4alkyl; Aryl (for example phenyl) and aryl C
1-4alkyl (for example benzyl); And a is 0 or 1.
Group A in this epoxy radicals silicone hydride is preferably the alkyl replacing through glycidoxy, for example 3-glycidoxy propyl group.This epoxy radicals silicone hydride can be for example 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl-triethoxysilicane, 3-glycidoxy propyl group diethoxy methoxy silane, 2-glycidoxypropyltrime,hoxysilane, 2-(3,4-epoxy group(ing)-4-methylcyclohexyl) ethyl trimethoxy silane, 5,6-epoxy group(ing) hexyl triethoxyl silane; Or its oligopolymer.
This adhesion promoter is N-2-amino-ethyl-3-TSL 8330 more preferably.Extra optional additives comprises dispersion agent, for example unsaturated polyester amic acid ester salt.
Follow-up dope layer, dirt releasing layer
There is no particular restriction for the composition of this follow-up dope layer, but said composition preferably comprises polymkeric substance.This polymkeric substance is preferably formed elastomerics.It is organopolysiloxane more preferably.Even more preferably, it is polydimethylsiloxane.In addition, this organopolysiloxane also can comprise the organopolysiloxane of two or more different viscosity.
This organopolysiloxane has one or more, and preferably two or more reactive functional groups are as hydroxyl, alkoxyl group, acetoxyl group, carboxyl, hydrogen silyl, amine, epoxy group(ing), vinyl Huo Wo functional group.
Or, this polymkeric substance can be described in WO2008132196, wherein this polymkeric substance is the polyorganosiloxane polyoxyalkylene segmented copolymer of PS-(A-PO-A-PS) n form, wherein PS represents organopolysiloxane block, PO represents polyoxyalkylene block, and A represents that divalence structure division and n have 1 or be greater than 1 value.
This polymkeric substance per molecule has 2 or 3 reactive group X on organopolysiloxane block, it can exist or not exist under catalyzer (as previously defined in the document) from condensation and crosslinked, and it optionally contains two or more organosilicon cross-linking agents that these radicals X are to reactive group Y with another and is cross-linked.
The amount that the gross weight that this organo-siloxanes polymer preferably be take based on this coating composition is 30-90wt% exists.
This polymkeric substance is preferably crosslinkable.The type that depends on crosslinkable polymer, this coating composition may need linking agent.Only at this curable polymer, cannot just need to there is linking agent by condensation cured in the situation that.This will depend on type and the quantity that is present in the functional group in this polymkeric substance.If this polymkeric substance comprises alkoxyl group-silylation, exist a small amount of water and condensation catalyst to be optionally conventionally enough to realize the completely curing of coating after using.For these compositions, atmospheric water is conventionally enough to induction and solidifies, and conventionally after using, will not need to heat this coating composition.
This linking agent optionally existing can be any or multiple linking agent comprising in functionalized silane and/or acetoxyl group, alkoxyl group, amido, alkene oxygen base and oximido.The example of these linking agents is in WO99/33927, and the 19th page the 9th is walked in the 21st page of the 17th row and propose.Also can use the mixture of different linking agents.
The amount that the gross weight that this linking agent preferably be take based on this coating composition is 1-25wt% exists.
In the crosslinkable situation of polymkeric substance of this follow-up dope layer composition, said composition optionally comprises catalyzer.The example of suitable catalyst is that various metals is as the carboxylate salt of tin, zinc, iron, lead, barium and zirconium.These salt are preferably long-chain carboxylic acid's salt, for example dibutyl tin laurate, two sad dibutyl tins, iron stearate, stannous octoate (II) and lead octoate 36.Other examples of suitable catalyst comprise that organo-bismuth and organic titanic compound and organophosphate are as two (2-ethylhexyl) hydrophosphate.Other possible catalyzer comprise sequestrant, for example acetopyruvic acid dibutyl tin.In addition, this catalyzer can comprise and has at least one halogenic substituent on the carbon atom of [the α]-position with respect to acid groups and/or the halogenation organic acid of at least one halogenic substituent on the carbon atom of [the β]-position with respect to acid groups, or can be in condensation reaction Water Under solution to form this sour derivative.
Or this catalyzer can be as in WO2007122325A1, WO2008055985A1, WO2009106717A2, WO2009106718A2, WO2009106719A1, WO2009106720A1, WO2009106721A1, WO2009106722A1, WO2009106723A1, WO2009106724A1, WO2009103894A1, WO2009118307A1, WO2009133084A1, WO2009133085A1, WO2009156608A2 and WO2009156609A2 as described in any.
The amount that the gross weight that this catalyzer preferably be take based on this coating composition is 0.05-4wt% exists.
Preferably, follow-up dope layer composition according to the present invention also comprises one or more fillers, pigment, catalyzer and/or solvent.The example of suitable filler is barium sulfate, calcium sulfate, calcium carbonate, silicon-dioxide or silicate (for example talcum, feldspar and china clay), aluminum paste/flake aluminum, wilkinite or other clays.Some fillers can have thixotropic effect to this coating composition as pyrogenic silica.The ratio of this filler can the scope that be 0-25wt% in the gross weight based on this coating composition in.This clay preferably exists with the amount of 0-1wt%, and this thixotropic agent preferably exists (gross weight based on this coating composition) with the amount of 0-5wt%.
The example of suitable pigments is iron oxide black, red iron oxide, iron oxide yellow, titanium dioxide, zinc oxide, carbon black, graphite, molybdate is red, molybdate is yellow, zinc sulphide, weisspiessglanz, sulfo group sodium aluminium silicate, quinacridone, phthalocyanine blue, phthalocyanine green, iron oxide black, indanthrone blue, cobalt oxide aluminium, carbazole two
piperazine, chromic oxide, isoindoline orange, di-acetyl acetyltoluene diazole, benzimidazolone, quinophthalone are yellow, isoindoline is yellow, tetrachloro iso-dihydro-indole and quinophthalone yellow.The ratio of pigment can the scope that be 0-25wt% in the gross weight based on this coating composition in.Suitable solvent comprises aromatic hydrocarbon, alcohol, ketone, ester and above-mentioned substance and each other or the mixture of aliphatic hydrocrbon.Preferred solvent comprises methyl isoamyl ketone and/or dimethylbenzene.The amount that the gross weight that this solvent preferably be take based on said composition is 0-40wt% exists.
When dry or when curing, when this follow-up dope layer composition forms the dirt release coat that is generally hydrophobic or amphipathic, the dirt release performance of coating system of the present invention is improved conventionally.The integral body of this follow-up dope layer and surface hydrophobicity can be characterized by several different methods, for example, by Absorption by Sea Water, measure or Surface Contact angular measurement.The Absorption by Sea Water of this follow-up dope layer is preferably less than 30 quality %, is more preferably less than 25 quality %.At 23 ℃, the equilibrium water contact angle of this follow-up dope layer is preferably greater than 30 degree.
In a preferred embodiment, this follow-up dope layer composition contains inconsistent fluid or grease.For the present invention, incompatible fluid means polysiloxane, organic or inorganic molecule or polymkeric substance, be generally liquid, but be optionally also organic soluble grease or wax, itself and this follow-up dope layer (elastomer network) is immiscible (all or part of).Once this first dope layer and follow-up dope layer solidify, this fluid forms and is enriched in the surface of this follow-up dope layer and strengthens its dirt release performance.The example of incompatible fluid provides in WO2007/10274.In WO2007/10274, this incompatible fluid is fluorinated polymer or the oligopolymer in polysiloxane coating materials; Due to surface can difference, fluorinated polymer/oligopolymer is enriched in surperficial process through solidifying polysiloxane coating materials layer through thermodynamic-driven.The dirt release performance of this coating is provided with the elastic performance combination being provided by the curing polysiloxane of warp the low surface energy being provided by fluorinated polymer or oligopolymer.
The example of suitable fluid is:
A) PFPE of linear and trifluoromethyl branching fluorine end-blocking (Fomblin Y for example
, Krytox K
fluid or Demnum S
oil);
B) PFPE of linear two-organic (OH) end-blockings (Fomblin Z DOL for example
, FluorolinkE
);
C) polymonochlorotrifluoroethylene of low MW is (as Daifloil CTFE
fluid).
In all cases, the polymkeric substance that contains fluorinated alkyl or alkoxyl group or oligopolymer do not participate in any crosslinking reaction substantially.Also can use other polymkeric substance that contains fluorinated alkyl or alkoxyl group or oligopolymer (polymkeric substance or the oligopolymer that for example contain carboxyl, ester group official energy fluorinated alkyl or alkoxyl group) single and two organo-functional group end-blockings.
Or this fluid can be silicone oil, for example, there is following formula:
Q
3Si-O-(SiQ
2-O-)
nSiQ
3
Wherein each group Q represents that alkyl and the n with 1 to 10 carbon atom make silicone oil have the integer of the viscosity of 20 to 5000m Pa s.Conventionally at least 10% group Q is that the group Q of methyl and at least 2% is phenyl.Most preferably, at least 10%-SiQ
2-O-unit is methylphenyl siloxane unit.Most preferably, poly-(methylphenyl siloxane) that this silicone oil is methyl blocking.This oil preferably has the viscosity of 20-1000m Pa s.The example of suitable silicone oil is sold by Bluestar Silicones with trade mark Rhodorsil Huile510V100 and Rhodorsil Huile550.This silicone oil improves the resistance of this coating system to aquatic incrustation.
This fluid also can be organopolysiloxane as follows:
Wherein:
R1 can be identical or different and be selected from alkyl, aryl and alkenyl, optionally through oxy radical amino, formula OR5, replaces, and wherein R5 is hydrogen or C
1-6alkyl, and according to the functional group of formula (I):
-R6-N(R7)-C(O)-R8-C(O)-XR3
Wherein:
R6 is selected to be had alkyl, hydroxyalkyl, the carboxyalkyl of 1 to 12 carbon atom and has the polyoxyalkylene of 10 carbon atoms at the most;
R7 is selected from hydrogen, have alkyl, hydroxyalkyl, the carboxyalkyl of 1 to 6 carbon atom and have the polyoxyalkylene of 1 to 10 carbon atom; R7 can be with R8 bonding to form ring;
R8 is the alkyl with 1 to 20 carbon atom;
R9 is hydrogen or the alkyl optionally replacing through containing oxygen or nitrogen-containing group with 1 to 10 carbon atom; X is selected from O, S and NH;
Condition is that at least one the R1 group in organopolysiloxane polymer is according to the functional group of above formula (I) or its salt derivative;
R2 can be identical or different and be selected from alkyl, aryl and alkenyl;
R3 and R4 can be identical or different and be selected from alkyl, aryl, end-blocking or not end-blocking polyoxyalkylene, alkaryl, sub-aralkyl and alkenyl;
A is 0 to 50,000 integer;
B is 0 to 100 integer; And
A+b is at least 25.
In one embodiment,
R2, R3 and R4 are independently selected from methyl and phenyl, more preferably methyl.
R6 is for having 1 to 12, more preferably the alkyl of 2 to 5 carbon atoms.
R7 is hydrogen or the alkyl with 1 to 4 carbon atom.
R8 is the alkyl with 2 to 10 carbon atoms.
R9 is hydrogen or the alkyl with 1 to 5 carbon atom.
X is Sauerstoffatom.
A+b is 100 to 300.
In one embodiment, the gross weight that this fluid be take based on this coating composition exists as 0.01-10wt%.This fluid most preferably exists with the scope of 2-7wt%.
Control the method for biocides rate of release
According to the present invention, provide a kind of control from dirt release coatings system, to discharge the method for biocides speed, wherein use this coating and after 5 days, from dirt release coatings system, discharge the speed (R of biocides
5) with use the rate of release (R of 30 days artifact kill agent of this coating
30) ratio R
5/ R
30≤ 1.5, the method comprises:
A., substrate is provided,
B. with the first dope layer, apply this substrate,
C. on the top of this first dope layer, use at least one follow-up dope layer,
This first dope layer contains biocides, and this follow-up dope layer contains than the few biocides of this first dope layer and its and do not contain or substantially contain biocides.
In one embodiment, method of the present invention can be controlled the speed that discharges biocides from dirt release coatings system, makes ratio R
5/ R
30be less than or equal to (≤) 1.33, be preferably less than or equal to (≤) 1.11.
This first dope layer and/or this follow-up dope layer comprise elastomeric polymer suitably.This elastomeric polymer is described in above-mentioned whole paragraphs.
This first dope layer and/or this follow-up dope layer comprise organopolysiloxane suitably.This follow-up dope layer is described in above-mentioned whole paragraphs.
This substrate is used as the linking coating on this anti-corrosive paints with corrosion resistant coatings and this first dope layer suitably.
Biocides in this first dope layer is organic or metal-organic biocide suitably.This biocides is described in above-mentioned whole paragraphs.
This biocides is one or more in any above-mentioned biocides suitably, and it is most suitable at 5 and the 2-trihalogenmethyl-3-halogen-4-cyanopyrrole derivative or Isosorbide-5-Nitrae-dithia anthraquinone-2 that are optionally substituted on 1,3-dimethoxy nitrile.
This follow-up dope layer comprises incompatible fluid suitably, for example polysiloxane, organic or inorganic molecule or polymkeric substance, itself and this follow-up dope layer unmixing.
Application
According to coating system of the present invention, can pass through routine techniques, for example brushing, roller coat, dip-coating or spraying (without air and for conventional) are applied to substrate.
After this follow-up dope layer solidifies, its can be immediately through soaking and anti-incrustation and incrustation release guard being immediately provided.The coating system of gained has extraordinary anti-incrustation and incrustation release performance.This makes coating system according to the present invention be highly suitable for preventing incrustation in ocean and fresh water application.This coating system can be used for dynamically and static structure body, such as cooling water intake, fishnet, fish pot and other all or part of water-immersed culture fisheries and the oceanographic equipment/structure etc. in ship and boat body, buoy, production platform, produce oil rig, floating production storage and removal container (FPSO), pipeline, power station.This coating system can be applied on these structures any substrate used, for example metal (as steel, aluminium), concrete, timber, plastics or fiber-reinforced resin.
Coating system according to the present invention makes to use this coating and 5 days, from dirt release coatings system, discharges the speed (R of biocides except having the controlled speed that discharges biocides from dirt release coatings system
5) with use the rate of release (R of 30 days artifact kill agent of this coating
30) ratio R
5/ R
30be less than or equal to outside (≤) 1.5 (preferably≤1.33), also find to compare with the system that does not comprise biocides or dirt release coatings layer, it can effectively resist and comprise (i) cement incrustation, (ii) sea grass incrustation, (iii) software incrustation and (iv) the incrustation type of the relative broad range of hardware incrustation, especially in slowly mobile water on container.
This coating system can be applied directly to undressed substrate.Or, coating system of the present invention can be applied to previously to application surface is processed or the substrate of other dope layers.The example of these surface treatments and other dope layers comprises anti-corrosive paints, the anti-incrustation coating of biocidal, seal coating, linking coating, adhesion promoting layer etc.
For being applied to ship and the boat body of newly making, conventionally this system is applied directly on the substrate with one or more corrosion-resistant coatings.In maintenance with when repairing or applying again, conventionally optionally this mechanism is applied to and on existing coating mechanism, (there is optional link coating) or be applied directly on this substrate after removing existing coating mechanism and using again one or more anti-corrosive paints layers.
There is no particular restriction and it comprises any steel, plastics, concrete, timber, fiber-reinforced resin and aluminium for the substrate of incrustation to be suppressed.
In a typical case, for being applied on ship and boat body, use the first dope layer to be created in the build within the scope of 100-200 μ m, and use this follow-up dope layer to be created in the build within the scope of 100-200 μ m.When the larger build of needs, can produce required film thickness by sequential application, it has the build of 100-200 μ m separately.On other substrates, will use this first dope layer to be created in the build within the scope of 50-500 μ m, and use this follow-up dope layer to be created in the build within the scope of 50-500 μ m.
With reference now to following instance explanation the present invention.It is intended to illustrate the present invention, but should be interpreted as limiting by any way the scope of the invention.
Embodiment
Embodiment 1 to 8
Preparation is according to eight kinds of different coating systems of the present invention (embodiment 1 to 8).
The biocides leaching rate of each coating system of measuring.In a word, the replica plate through each linkable paint system (duplicate panel) is soaked in the storage tanks of synthetic sea water.Regularly flat board be transferred in the leaching rate measuring vessel of fresh synthetic sea water and stir the set time gently.When finish this period, flat board is back to and in storage tanks and by chemical analysis, measures the amount that is leached to the biocides in this container.Due to the measured quantity of known leaching biocides, through exposed surface area and the soak time in this leaching rate measuring vessel of Coated Flat Plate, can measure biocides leaching rate, and with μ g cm
-2d
-1represent.
Synthetic sea water
That uses business uses ocean sea salt (Instant Ocean Sea Salt) by every liter of deionized water mixing 33g salt is prepared to synthetic sea water.
Dull and stereotyped preparation
Cover the polycarbonate flat board of 15x10cm to obtain known surface area (common about 100cm
2).By drawing bar, with 125 μ m builds, use the anticorrosive paint of bi-component epoxy (Intershield300, International Paint), then via drawing bar, with 100 μ m builds, use the dope layer containing biocides.After dry, via drawing bar, with the build of 15 μ m, incite somebody to action final " cover " coating and be applied to this film (except using the embodiment 5 of 100 μ m builds).Remove this and cover band, and use brush to seal the edge through Coated Flat Plate with the anticorrosive paint of bi-component epoxy (Intershield300, International Paint).Before using follow-up dope layer and before immersing this storage tanks, make each coating under condition, solidify around.
Storage tanks
Flat board is immersed in 40 liters of synthetic sea waters in strict clean glass guide channel completely, and make water cycle through consistently activated charcoal filter to avoid gathering of biocides or its degraded product.The temperature of this storage tanks maintains at about 22-23 ℃.Except use when the scheduled measurement number of days leaching rate measuring vessel carry out leaching rate measuring process in, all flat boards keep being soaked in this storage tanks in experimental session.
Leaching rate measuring vessel
When scheduled measurement number of days, flat board is transferred to strict clean the adding a cover in polypropylene container (15 * 8 * 8cm, l * w * h) separately that contains 100ml synthetic sea water at the temperature of about 22-23 ℃.Use rail mounted mixing tank (orbital mixer) stirred vessel 2 hours gently, and make subsequently flat board be back to storage tanks.
Leaching rate mensuration-routine
In leaching rate measuring vessel, the concentration of biocides can be used and be familiar with standard method of analysis mensuration known to the skilled, for example high efficiency liquid chromatography (HPLC).Can with following equation, measure leaching rate R by the concentration of biocides in leaching rate measuring vessel subsequently.
Wherein C is the equivalent concentration of biocides in leaching rate measuring vessel, V is the volume (liter) of synthetic sea water in leaching rate measuring vessel, t be dull and stereotyped immersion period in leaching rate measuring vessel (hour), and A is the exposed surface area (cm of coating system on this flat board
2).
Leaching rate mensuration-tralopyril of embodiment 1 to 8
When stirring finishes period, the synthetic sea water of the approximately 12ml from each leaching rate measuring vessel is transferred in vial.This bottle is maintained at 45 ℃ whole night, take and guarantee that the tralopyril Quantitative yield leaching is the bromo-5-of 3-(4-chloro-phenyl-)-4-cyano group-1H-pyrroles-3-formic acid (BCCPCA).
By use, Pursuit UPS2.4 is installed
μacetonitrile, water and ortho-phosphoric mixture that the Agilent1100HPLC system of m C18 tubing string (50x3mm) and use volume parts ratio are 50:49.95:0.05 pass through via direct injection the concentration that high efficiency liquid chromatography (HPLC) is measured treated sample BCCPCA as moving phase.
Every day is by suitably diluting the 1000 μ g liters of BCCPCA in tetrahydrofuran (THF) with synthetic sea water
-1stock solution, and 10-500 μ g liter is contained in fresh preparation
-1minimum 6 calibration criterions of scope.Before these standards and afterwards and after each sample sets, analyze synthetic sea water blank sample.After every 5 samples, carry out examination criteria, with the reproducibility of determination method.At each time point, validating analysis method can be reproduced.
By the BCCPCA concentration recording being multiplied by the relative molar mass of tralopyril and BCCPCA, calculate when stirring finishes period the equivalent concentration of tralopyril in this leaching rate measuring vessel, and according to following equation, calculate subsequently the leaching rate R of tralopyril:
Table 3 is presented at measures number of days 5 (R
5) and 30 (R
30) time collected leaching rate result and R
5/ R
30.In each situation, result is the average result to the replica plate of each coating system.
Can find out, each coating system is illustrated in defined controlled leaching in framework of the present invention, and these coating are not all shown the proportional biocides leaching rate of the square root behavior to the time corresponding to biocides leaching rate.In addition, by changing the special parameter of this follow-up dope layer, can control the behavior of biocides leaching rate, can make it reduce in time, raise or substantially keep constant.
In addition, can realize different average biocides leaching rates, and by changing the special parameter of follow-up dope layer, can control biocides leaching rate, make to select at any given time the higher or lower biocides leaching rate of acquisition.
Table 1: first dope layer formulation-embodiment 1 to 8
| Material | % by weight |
| Polydimethylsiloxane | 13.8 |
| The tensio-active agent of the salt based on long-chain unsaturated polyester amino amides and high molecular acid esters | 0.6 |
| tralopyril | 13.6 |
| Titanium dioxide | 6.7 |
| Pyrogenic silica | 0.6 |
| Methyl isoamyl ketone | 18.6 |
| Oxime-curing thick painting coating of polysiloxane | 37.2 |
| Dimethylbenzene | 7.8 |
| Chlorinatedpolyolefins | 0.8 |
| N-2-amino-ethyl-3-TSL 8330 | 0.2 |
| Two dioctyltin laurate | 0.1 |
Table 2: the detailed formulation of the second dope layer (the volume % of the composition of the cumulative volume based on said composition)
* corresponding to the embodiment 12 of WO2008/132236
Table 3: leaching rate results-example 1 to 8
1): soak the biocides rate of release after 5 days
2): soak the biocides rate of release after 30 days
Embodiment 9 to 12
As shown in table 4, prepare according to other coating systems of the present invention (embodiment 9 to 12) not compare containing the dirt release coatings system (all embodiment) of biocides with business.
The first dope layer formulation of table 4: embodiment 9 to 12:
| Embodiment | Biocides |
| 9 | tralopyril |
| 10 | Delan |
| 11 | Copper pyrithione (CPT) |
| 12 | Zinc Pyrithione (ZPT) |
Prepare test slab and measure each coating system control biocides from the ability of the first dope layer leaching and inhibition incrustation.By cylinder, the coating system of embodiment 9 to 12 is applied to 60x60cm ocean glued board flat board so that the first dope layer and the follow-up dope layer of the build that is about respectively 100 μ m and 150 μ m to be provided.Pre-priming paint by a coating of the anticorrosive paint of bi-component epoxy (Intershield300, International Paint) as plate, each coating has the DFT of approximately 125 μ m.The linkable paint system of half of each flat board (left-hand side) corresponding to one of embodiment 9 to 12 coating systems, and second half (right hand side) of this flat board is discharged and is connected coating (Intersleek737, International Paint) coating in contrast with business dirt.Subsequently both sides are used the dirt release overlay coating (Intersleek757, International paint) of standard.Before using follow-up dope layer and starting test, make each coating completely curing under condition around.
Test slab is immersed simultaneously in the naturally tropical seawater of the 0.5-1.0m degree of depth of Singapore's Zhangyi (the incrustation growth at known this place is serious).Regularly these flat boards are shifted out from water, take pictures and before soaking flat board again, assess the incrustation growth on coating system.
Even after soaking 8 months, the coating system that contains tralopyril (embodiment 9) and Delan (embodiment 10) still keeps substantially without incrustation.After 8 months, the coating system that contains copper pyrithione (embodiment 11) and Zinc Pyrithione (embodiment 12) shows than embodiment 9 and the growth of 10 more serious incrustation, but is coated with material property specific volume dirt and grows more not serious with contrast.
In all cases, after soaking 8 months, the coating system of embodiment 9 to 12 is bubbles and crack not.
These results obviously show that the ability that coating system according to the present invention suppresses incrustation in prolonging period improves significantly with respect to normal business dirt release coatings system.
Claims (11)
1. the structure applying through biocidal dirt release coatings system, this structure obtains by following steps:
A., substrate is provided,
B. with the first dope layer, apply this substrate,
C. on the top of this first dope layer, use at least one follow-up dope layer,
This first dope layer comprises biocides, this follow-up dope layer comprise than the few biocides of this first dope layer and its not containing or substantially containing biocides, and wherein this first dope layer and this follow-up dope layer form the biocidal dirt release coatings system of the controlled leaching that demonstrates this biocides.
2. according to the structure of claim 1, wherein use this coating and after 5 days, from this dirt release coatings system, discharge the speed (R of biocides
5) and use the speed (R that this coating discharges biocides for 30 days afterwards
30) ratio R
5/ R
30≤ 1.5.
3. according to the structure of claim 2, this ratio R wherein
5/ R
30≤ 1.33.
4. according to the structure of any one in aforementioned claim, wherein this first dope layer and/or this follow-up dope layer comprise elastomeric polymer.
5. according to the structure of any one in aforementioned claim, wherein this first dope layer and/or this follow-up dope layer comprise organopolysiloxane.
6. according to the structure of any one in aforementioned claim, wherein this substrate is used as the linking coating on this anti-corrosive paints through corrosion resistant coatings and this first dope layer.
7. according to the structure of any one in aforementioned claim, wherein the biocides in this first dope layer is organic or metal-organic biocide.
8. according to the structure of any one in aforementioned claim, wherein this biocides is at 5 and the 2-trihalogenmethyl-3-halogen-4-cyanopyrrole derivative or Isosorbide-5-Nitrae-dithia anthraquinone-2 that are optionally substituted on 1, one or more in 3-dimethoxy nitrile.
9. according to the structure of any one in aforementioned claim, wherein this follow-up dope layer comprises incompatible fluid.
10. according to the structure of any one in aforementioned claim, wherein this substrate is the structure of ocean or culture fishery, for example cooling water intake, fishnet or the fish pot in hull, boat body, buoy, production platform, produce oil rig, floating production storage and removal container (FPSO), pipeline, power station.
11. 1 kinds of controls discharge the method for the speed of biocides from dirt release coatings system, wherein use this coating and after 5 days, from this dirt release coatings system, discharge the speed (R of biocides
5) and use the speed (R that this coating discharges biocides for 30 days afterwards
30) ratio R
5/ R
30≤ 1.5, the method comprises:
A., substrate is provided,
B. with the first dope layer, apply this substrate,
C. on the top of this first dope layer, use at least one follow-up dope layer,
This first dope layer comprises biocides, and this follow-up dope layer comprises than the few biocides of this first dope layer and its and do not contain or substantially contain biocides.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201161499430P | 2011-06-21 | 2011-06-21 | |
| EP11170712 | 2011-06-21 | ||
| EP11170712.1 | 2011-06-21 | ||
| US61/499,430 | 2011-06-21 | ||
| PCT/EP2012/061625 WO2012175459A1 (en) | 2011-06-21 | 2012-06-19 | Biocidal foul release coating systems |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103608411A true CN103608411A (en) | 2014-02-26 |
Family
ID=44904675
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280029226.3A Pending CN103608411A (en) | 2011-06-21 | 2012-06-19 | Biocidal foul release coating systems |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US20140141263A1 (en) |
| EP (1) | EP2723821A1 (en) |
| JP (1) | JP5993451B2 (en) |
| KR (1) | KR101980220B1 (en) |
| CN (1) | CN103608411A (en) |
| AU (1) | AU2012271948B2 (en) |
| BR (1) | BR112013032015A2 (en) |
| MX (1) | MX2013015164A (en) |
| MY (1) | MY163188A (en) |
| SA (1) | SA112330621B1 (en) |
| TW (1) | TWI575038B (en) |
| WO (1) | WO2012175459A1 (en) |
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Also Published As
| Publication number | Publication date |
|---|---|
| EP2723821A1 (en) | 2014-04-30 |
| BR112013032015A2 (en) | 2016-12-20 |
| TW201305289A (en) | 2013-02-01 |
| US20140141263A1 (en) | 2014-05-22 |
| KR101980220B1 (en) | 2019-05-20 |
| SA112330621B1 (en) | 2016-01-14 |
| AU2012271948B2 (en) | 2015-10-15 |
| MY163188A (en) | 2017-08-15 |
| WO2012175459A1 (en) | 2012-12-27 |
| JP5993451B2 (en) | 2016-09-14 |
| JP2014519978A (en) | 2014-08-21 |
| TWI575038B (en) | 2017-03-21 |
| KR20140038520A (en) | 2014-03-28 |
| MX2013015164A (en) | 2014-03-31 |
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