Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • 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
  • 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
  • C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
• • 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
  • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
• • 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
  • C09D5/002—Priming 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
  • C09D5/1693—Antifouling paints; Underwater paints as part of a multilayer system
• • 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

Definitions

• the present invention relates to tie-coat compositions for fouling-release paint systems.
• the invention provides a method of coating a substrate with a coating composition comprising at least two types of functional polysiloxane compounds selected from epoxy-functional polysiloxanes, amino-functional polysiloxanes, and particular adhesion promoting agents of the polysiloxane type.
• the present invention also provides a substrate coated with such a composition and a composition particularly useful for said method.
• Fouling release paint systems are abundantly used for such structures, e.g. ships, buoys, watercraft structures, etc. in order to suppress settlement of such marine organisms.
• Fouling-release coating systems for steel structures typically include three principal layers, namely an epoxy- based anticorrosive layer applied to the steel substrate, a fouling-release layer which typically comprises a polysiloxane-based matrix, and an intermediate layer, often referred to as a "tie- coat", for establishing strong bonding between the otherwise incompatible epoxy-based anticorrosive layer and the polysiloxane-based fouling release layer.
• organosiloxane compositions comprising 100 parts by weight of an ⁇ , ⁇ -dihydroxydiorganopolysiloxane polymer, 0.5-20 parts by weight of a cross-linking agent, 0.1-10 parts by weight of a bonding agent comprising an aminoorganosilicon compound having at least one amino functional group and an organosilicon compound having at least one epoxy functional group, 2-250 parts by weight of inorganic filler material, and 0.0004-3 parts by weight of a metal catalyst.
• the compositions are useful for the coating of marine surfaces, e.g. a ship's hull or a net.
• EP 1 013 727 Al, US 6,391,464 and US 6,110,536 disclose an epoxy- silicone adhesive paint as a tie-coat for a fouling-release coating.
• the paint comprises 80- 85% by weight of an epoxy resin paint, and 15-20% by weight of a silicone adhesive promoter.
• the silicone adhesive promoter comprises a volatile hydrocarbon solvent, a partially condensed organosilicate, a solubilized metallic catalyst, and an aminoalkyltrialkoxy- silane.
• GB 2 300 370 Al discloses an article having a fouling-release layer on top of an adhesion promoting layer.
• the adhesion promoting layer comprises an anticorrosive material (typically an epoxy-functionalized base material (e.g. an epoxy resin) combined with a curing catalyst) and a bonding agent.
• the bonding agent may be (i) a moisture curable grafted copolymer comprising a polydialkylsiloxane and at least one ethylenically unsaturated monomer, (ii) an aminofunctionalized polysiloxane fluid, or (iii) an ⁇ , ⁇ -diaminofunctionalized polysiloxane fluid.
• WO 99/33927 discloses a process for inhibiting fouling.
• the process includes the formation of a coating comprising a film-forming polymer carrying unreacted curable silicon-containing functional groups providing latent reactivity, and subsequently applying a layer comprising a curable polymeric fouling-inhibiting material and bonding the applied layer to the said coating by a condensation curing reaction involving the unreacted functional groups thereon.
• JP 03-258876-A discloses a tie-coat composition
• a tie-coat composition comprising the reaction product of an epoxy resin and a dirnethylpolysiloxane, and a hardener.
• the hardener should have an active hydrogen and is selected from polyamines, polyamides, aminosilane coupling agents, phenol resins, alkyd resins, melamine resins and polyurethane resins.
• the ratio between the epoxy equivalent number of the reaction product and the active hydrogen equivalent number of the hardener should be in the range of 100:50 to 100:200.
• EP 0 521 983 discloses a primer composition
• a primer composition comprising (A) (i) a primary amine-functional silane, or (ii) the reaction product of a primary amine-functional silane and an epoxy- functional silane, or (iii) the reaction product of a primary amine-functional silane and an ⁇ , ⁇ -dihydroxypolydimethylsiloxane oil, (B) a chlorinated polyolefin, and (C) a room- temperature-cu rable polydiorganosiloxane.
• the present invention relates to a method of coating a substrate, cf. claim 1.
• a further aspect of the present invention relates to a coating composition, cf. claim 37.
• a further aspect of the present invention relates to an article comprising a substrate, an epoxy-based coating on at least a part of the surface of said substrate, a tie-coat on said epoxy-based coating, and a fouling release coating on said tie-coat, cf. claim 49.
• the present invention provides an improved method and an advantageous tie-coat composition particularly useful in connection with fouling-release coating systems.
• the present invention provides a method involving a tie-coat composition wherein at least two types of functional polysiloxanes are included.
• the binder phase of the tie-coat composition may include a substantial portion of polysiloxane type compounds, or the binder phase of the composition may include polysiloxane type compounds in combination with amino- and/or epoxy- compounds of non-silicon origin, in particular typical constituents of epoxy paint compositions.
• the binder phase may in a simplified fashion consider the binder phase as having - as the principal non-solvent constituents - a polysiloxane fraction (polysiloxanes and silanes) and possibly also a fraction of one or more constituents of an epoxy paint composition.
• the fraction of one or more constituents of an epoxy paint composition may - when measured by %-by wet weight - be fairly large, but in all instances, the binder phase of the tie-coat composition must include at least two types of functional polysiloxanes. This will be explained in details in the following.
• the simultaneous presence of amino-functional compounds and epoxy-functional compounds ensures that curing of the composition can take place, namely reaction between amino groups and epoxy groups.
• the adhesion promoting agent will in most cases further facilitate adhesion between the substrate (or a substrate coated with a primer, in particular an epoxy primer) and tie-coat as well as between the tie-coat and a subsequently applied fouling release coating.
• the present invention provides a method of coating a substrate, the method comprising:
• a coating composition comprises (i) 0- 60%, such as 0-50%, preferably 5-45%, such as 5-40% or 5-35%, by wet weight of pigments and fillers; and (ii) the balance of a binder phase (i.e. the coating composition devoid of any pigments and fillers) comprising:
• binder phase comprises at least two types, (a), (b), (c), of polysiloxane compounds selected from the group consisting of:
• adhesion promoting agents selected from the group consisting of hydroxy-functional polysiloxanes, hydroxyalkyl-functional polysiloxanes and C ⁇ -4 -alkoxy-functional polysiloxanes;
• binder phase of the coating composition means the sum of the constituents of the coating composition not being pigments and/or fillers.
• the binder phase of the composition constitutes 40-100%, such as 50-100%, e.g. 55-95%, such as 60-95% or 65- 95%, by wet weight of the composition.
• the coating composition typically comprises 0-60%, such as 0-50%, preferably 5-45%, such as 5-40% or 5-35%, by wet weight of pigments and fillers.
• % by wet weight of the composition means the percentage of the respective constituent based on the composition including any solvents.
• the binder phase of the coating composition comprises one or more amino-functional compounds, one or more epoxy-functional compounds and, optionally, one or more adhesion promoting agents.
• the epoxy-functional compound(s) typically include(s) epoxy- functional silicon compounds (most often epoxy-functional polysiloxanes and/or epoxy- functional silanes), and the amino-functional compound(s) typically include(s) amino- functional silicon compounds (most often amino-functional polysiloxanes and/or amino- functional silanes).
• the adhesion promoting agent may be selected from the group consisting of hydroxy-functional polysiloxanes, hydroxyalkyl-functional polysiloxanes and C ⁇ - 4 -alkoxy-functional polysiloxanes.
• polysiloxane compounds selected from from the group consisting of: (a) amino-functional polysiloxanes; (b) epoxy-functional polysiloxanes; and (c) adhesion promoting agents selected from the group consisting of hydroxy-functional polysiloxanes, hydroxyalkyl- functional polysiloxanes and C ⁇ -4 -alkoxy-functional polysiloxanes.
• polysiloxane is intended to mean a polydiorganosiloxane, i.e. a polymeric constituent comprising a plurality of diorganosiloxane units.
• the coating composition is a polysiloxane-based coating composition.
• polysiloxane-based coating composition is intended to mean a coating composition wherein the binder phase, to the extent of at least 40% by wet weight, is made up of polysiloxane-based constituents.
• polysiloxane-based constituents include any epoxy-functional silicon compounds, amino-functional silicon compounds, and adhesion promoting agent, insofar the latter is of the polysiloxane type.
• the epoxy-functional compound(s) essentially consists of one or more epoxy-functional silicon compounds
• the amino-functional compound(s) essentially consists of one or more amino-functional silicon compounds.
• the binder phase of the coating composition comprises one or more constituents of an epoxy paint composition in addition to the mandatory polysiloxane compounds (see further below).
• the selection of the ratio between the hydrogen equivalents of the amino-functional compound and the epoxy equivalents of the epoxy-functional compound can play a certain role for the performance of the coating composition.
• the ratio is in the range of 20 : 100 to 200: 100.
• the number of "hydrogen equivalents" in relation to the amino-functional compound is defined as grams of the amino-functional compound divided by the hydrogen equivalent weight of the amino-functional compound, where the hydrogen equivalent weight of the amino-functional compou nd is determined as: grams of the amino-functional compound equivalent to 1 mol of active hydrogens.
• the number of "epoxy eq uivalents" in relation to the epoxy-functional compound is defined as grams of the epoxy-fu nctional compound divided by the epoxy equivalent weight of the epoxy-functional compou nd, where the epoxy equivalent weight of the epoxy-functional compound is determined as: grams of the epoxy-functional compound equivalent to 1 mol of epoxy groups.
• the binder phase of the coating composition comprises 1-90% by wet weight of epoxy-functional compound(s), in particular 1-90% by wet weight of epoxy-functional silicon compound(s).
• % by wet weight in connection with the binder phase means the percentage of the respective constituent based on the binder phase including any solvents.
• epoxy-functional compound(s) is intended to encompass epoxy-functional silicon compound(s) (see below) as well as epoxy-functional compounds of non-silicon origin as those conventionally utilized in epoxy paint compositions (see further below).
• amino-functional compound(s) is intended to encompass amino-functional silicon compound(s) (see below) as well as amino-functional compounds of non-silicon origin as those conventionally utilized in epoxy paint compositions (see further below).
• epoxy-functional compound(s) essentially consists of one or more epoxy-functional silicon compounds
• amino-functional compound(s) essentially consists of one or more amino-functional silicon compounds
• epoxy-functional silicon compound is to be understood in the conventional sense, and means a silicon compound, e.g. a silane or polysiloxane compound, having pendant and/or terminal epoxy groups.
• epoxy-functional silicon compounds are epoxy-functional polysiloxanes and epoxysilanes.
• the epoxy-functional silicon compound(s) is/are epoxy-functional polysiloxane(s).
• epoxy-functional polysiloxane is to be understood in the conventional sense, and means a linear or branched polymeric constituent having one or more polysiloxane blocks and having pendant and/or terminal epoxy-functionalities.
• the epoxy functionalities may, e.g., be introduced to the polysiloxane by means of an epoxysilane or by means of an epoxy resin, see e.g. EP 1 086 974 A.
• the epoxy- functional polysiloxane is prepared by the reaction between an epoxy resin and a reactive polysiloxane, optionally by the concurrent action of further constituents such as constituents having hydroxyl and/or alkoxy groups, etc.
• the epoxy-functional polysiloxane may be prepared by subjecting an epoxysilane and an alkoxysilane mixture to partial hydrolysis and condensation. It should be understood that the epoxy-functional polysiloxane may be prepared in situ if desirable. It should also be understood that the epoxy-functional polysiloxane may advantageously comprise alkoxy- and/or hydroxyl- functionalities.
• At least one epoxy-functional polysiloxane wherein the polysiloxane backbone or side chains to the polysiloxane backbone include -OH groups or alkoxy groups. Without being bound to any particular theory, it is believed that such hydroxy groups or alkoxy groups may participate in the curing of the tie-coat composition upon exposure to humid environments.
• Illustrative examples of commercially available epoxy-functional polysiloxanes are SILKOFTAL ED (epoxy, methoxy polydimethylpolysiloxane) ex Tego; SLM 43226 ex Wacker; ES-1002T and ES-1001T (silicone modified epoxy resin) ex Shin Etsu; etc.
• the epoxy-functional polysiloxane(s) typically constitute(s) 25-90%, such as 30-90%, e.g. 40-90% by wet weight of the binder phase.
• the epoxy-functional silicon compound(s) is/are epoxysilane(s).
• an amino-functional polysiloxane must be present. Epoxysilanes are frequently defined as silanes of the formula:
• A is an epoxide-substituted monovalent hydrocarbon radical having 2 to 12 carbon atoms; and each R independently is selected from C 1-8 -alkyl (e.g. methyl, ethyl, hexyl, octyl, etc.), Ci- 4 -alkyI-0-C 2-4 -alkyl; aryl (e.g. phenyl) and aryl-C ⁇ -4 -alkyl (e.g. benzyl); and a is 0 or 1.
• the group A in the epoxysilane is preferably a glycidoxy-substituted alkyl group, for example 3-glycidoxypropyl.
• the epoxysilane can for example be 3-glycidoxypropyltrimethoxysilane, 3- glycidoxypropyltriethoxysilane, 3-glycidoxypropyldiethoxymethoxysilane, 2-glycidoxypropyl- trimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 2-(3,4 ⁇ epoxy-4-methyl- cyclohexyl)-ethyltrimethoxysilane, 5,6-epoxy-hexyltriethoxysilane.
• epoxysilanes are 5,6-epoxy-hexyl triethoxysilane (ABCR GmbH & Co. KG, Germany); 3-glycidoxypropyl methyldiethoxysilane (ABCR GmbH & Co. KG, Germany), ⁇ -glycidoxypropyyltrimethoxysilane (Dynasylan, Glymo, Sivento Chemie GmbH, Germany).
• the binder phase comprises 1-60% by wet weight of the epoxysilane(s).
• the epoxy-functional silicon compound is the combination of epoxy-functional polysiloxane(s) and epoxysilane(s), i.e. the binder phase comprises one or more epoxy-functional polysiloxanes as well as one or more epoxysilanes.
• This combination can be accomplished by adding an epoxy-functional polysiloxane (as described above) and an epoxysilane (as defined above), or by using a reaction product between an epoxysilane and a polysiloxane in which a portion of the epoxysilane remains unreacted.
• the binder phase typically comprises 2-90%, such as 5-85%, by wet weight of the epoxy-functional polysiloxane(s)/epoxysilane(s) (i.e. the combination of the epoxy-functional polysiloxane and the epoxysilane).
• the binder phase also comprises 1-90% by wet weight of amino-functional compound(s), in particular 1-90%, by wet weight of amino-functional silicon compound(s).
• amino-functional silicon compound is to be understood in the conventional sense, and means a silicon compound, e.g. a silane or polysiloxane compound, having pendant and/or terminal amino groups.
• amino-functional silicon compounds are amino-functional polysiloxanes and aminosilanes.
• the amino-functional silicon compound(s) is/are amino- functional polysiloxane(s).
• amino-functional polysiloxane means a linear or branched polymeric constituent having one or more polysiloxane blocks and having pendant and/or terminal amino-functionalities.
• an aminosilane can be reacted with an ⁇ , ⁇ -dirrydroxypolydimethylsiloxane at a temperature in the range of 20- 80°C, preferably using 0.4-1.2 alkoxy groups of the aminosilane per silanol group of the polysiloxane. If an excess of aminosilane is used, or if the reaction is not allowed to proceed to completion, a small amount of aminosilane may remain in the product.
• at least one amino-functional polysiloxane is the reaction product of a polysiloxane and an aminosilane.
• amino-functional polysiloxanes examples include ⁇ , ⁇ -diamino-functional polysiloxanes (e.g. polysiloxane fluids).
• Illustrative examples of commercially available amino-functional polysiloxanes are SILRES HP 2000 (amino-functionalised methyl-phenyl silicone) ex Wacker; SF1708 (Amino functionalised polysiloxane fluid) ex General Electric Co.; etc.
• polysiloxane backbone or side chains to the polysiloxane backbone include -OH groups or alkoxy groups.
• hydroxy groups or alkoxy groups may participate in the curing of the tie-coat composition upon exposure to humid environments.
• the binder phase typically comprises 1-60%, such as 15-60%, e.g. 15- 50% or 20-40%, by wet weight of the amino-functional polysiloxane(s).
• the ratio between the hydrogen equivalents of the amino-functional polysiloxane(s) and the epoxy equivalents of the epoxy-functional silicon compound(s) is in the range of 40: 100 to 200: 100.
• the amino-functional silicon compound(s) is/are aminosilane(s).
• an epoxy-functional polysiloxane must be present. Aminosilanes are frequently defined as silanes of the formula:
• each R independently is selected from C ⁇ -8 -alkyl (e.g. methyl, ethyl, hexyl, octyl, etc.), C ⁇ -alkyl-O-C ⁇ -alkyl; aryl (e.g. phenyl) and aryl-C 1- -alkyl (e.g. benzyl); R 1 is selected from -(CH 2 ) 2-4 -, methyl-substituted trimethylene, and -(CH 2 ) 2 - 3 -0-(CH 2 )2- 3 ; R 2 is selected from hydrogen and -(CH 2 ) 2 - -NH 2 .
• C ⁇ -8 -alkyl e.g. methyl, ethyl, hexyl, octyl, etc.
• R 1 is selected from -(CH 2 ) 2-4 -, methyl-substituted trimethylene, and -(CH 2 ) 2 - 3
• aminosilanes are (CH 3 0) 3 Si(CH 2 ) 3 NH(CH 2 )2NH 2 ; (CH 3 CH 2 0CH 2 CH 2 0) 3 Si(CH 2 ) 2 NH 2 ; (C 2 H 5 0)3Si(CH 2 )3 H 2 ; (CH 3 OCH 2 CH 2 0)3Si(CH 2 )3NH 2 ; (C 2 H 5 0) 3 Si(CH 2 ) 3 0(CH 2 ) 3 NH 2 ; (C 2 H 5 0) 2 C 6 H 5 Si(CH 2 ) 3 NH 2 ; (C 2 H 5 0) 3 SiCH 2 0(CH 2 ) 2 NH 2 ; (C 2 H 5 0) 3 Si(CH 2 ) 3 0(CH 2 ) 2 N H 2 ; and (C 2 H 5 0) 2 CH 3 Si(CH 2 ) 3 NH 2 .
• Illustrative examples of commercially available aminosilanes are Dynasilan AMEO (3-aminopropyltriethoxysilane) ex Degussa H ⁇ ls; KBM603 (N- ⁇ -aminoethyl- ⁇ -aminopropyltrimethoxysilane) ex Shin Etsu; etc.
• the binder phase comprises 1-60%, such as 1-30%, e.g. 1-20%, such as 1-10%, by wet weight of the aminosilane(s).
• the ratio between the hydrogen equivalents of the aminosilane(s) and the epoxy equivalents of the epoxy-functional silicon compound(s) is in the range of 20: 100 to 100: 100, such as 20: 100 to 75: 100, e.g. 20: 100 to 49: 100.
• the amino-functional silicon compound(s) is/are the combination of amino-functional polysiloxane(s) and aminosilane(s), i.e. the binder phase comprises one or more amino-functional polysiloxanes as well as one or more aminosilane(s).
• This combination can be accomplished by adding an amino-functional polysiloxane (as described above) and an aminosilane (as defined above), or by using a reaction product between an aminosilane and a polysiloxane in which a portion of the aminosilane remains unreacted.
• the binder phase typically comprises 1-60%, such as 2-60%, e.g. 5- 55%, by wet weight of the amino-functional polysiloxane(s)/aminosilane(s) (i.e. the combination of the amino-functional polysiloxane(s) and the aminosilane(s)).
• the binder phase typically comprises in the range of from [Z x 15 + (1-Z) x 1]% to [Z x 60 + (1-Z) x 30]%, such as in the range of from [Z x 20 + (1-Z) x 1]% to [Z x 40 + (1-Z) x 20]%, by wet weight of the combination of the amino-functional polysiloxane(s) and the aminosilane(s).
• the ratio between the hydrogen equivalents of the amino-functional polysiloxane/aminosilane and the epoxy equivalents of the epoxy-functional silicon compound is in the range of 20: 100 to 200: 100.
• the ratio between the hydrogen equivalents of the aminosilane(s) and the epoxy equivalents of the epoxy-functional polysiloxane(s) is in the range of 20: 100 to 75: 100.
• an epoxy-functional polysiloxa ne and/or an amino-functional polysiloxane of the binder phase comprise hydroxy- or alkoxy-functional groups (see above), e.g. hydroxyalkyl and hydroxy-Si groups, are particularly advantageous.
• the composition must comprise at least one of an epoxy-functional polysiloxane and an amino-functional polysiloxane.
• the composition comprises an epoxy-functional polysiloxane as well as an amino-functional polysiloxane.
• binder phase typically comprises 26-90%, such as 45- 90%, wet weight of polysiloxane-based constituents.
• the at least two types of polysiloxane compounds ((a) amino- functional polysiloxanes; (b) epoxy-functional polysiloxanes; (c) adhesion promoting agents selected from the group consisting of hydroxy-functional polysiloxanes, hydroxyalkyl- functional polysiloxanes and C_. 4 -alkoxy-functional polysiloxanes) are used in admixture with one or more epoxy-functional compounds of non-silicon origin and/or amino-functional compounds of non-silicon origin, e. g. constituents of an epoxy paint composition.
• the epoxy-functional compound(s) comprise(s) one or more epoxy- functional compounds of non-silicon origin
• the amino-functional compound(s) comprises(s) one or more amino-functional compounds of non-silicon origin.
• the polysiloxane type and silane type constituents typically constitute 2- 90%, or 2-50%, such as 2-30%, e. g. 2-15%, by wet weight of the binder phase and the constituents of an epoxy paint composition (i.e. one or more epoxy-functional compounds of non-silicon origin and/or amino-functional compounds of non-silicon origin) typically constitute 10-80%, or 30-80%, such as 10-55%, e.g. 30-55%, by wet weight of the binder phase.
• epoxy-functional compounds of non-silicon origin is intended to encompass typical "epoxy resin” constituents of epoxy paint compositions.
• epoxy-functional compou nds of non-silicon origin can be mentioned: Bisphenol A/bisphenol F epoxides: Epikote 235 ex. Resolution Performance Products Holland; bisphenol A epoxides: Epikote 828 EL or Epikote 1004 or Epikote 1009 or Epikote 872-X-75 ex. Resolution Performance Products Holland, Araldite GZ 7071X75CH ex. Huntsman Advanced Materials Switzerland, DER 684-EK -40 ex. Dow Chemicals USA; epoxy novolac resins: DEN 438-X 80 ex.
• amino-functional compounds of non-silicon origin is intended to encompass typical "amino"/"curing agent”/"hardener” constituents of epoxy paint compositions.
• polyamines (arylyl) Epoxy Hardener MXDA ex. Mitsubishi Gas Chemical Company Inc USA
• polyamines (aliphatic) DEAPA or DETA ex. BASF Germany
• polyamines (cycloaliphatic) Aradur 42 BD ex. Huntsman Advanced Materials Switzerland
• formulated amines Sunmide 3-230N ex. Sanwa Chemical Company Inc USA, Ancamide X2280 ex. Air Products Pic USA, HY 1207 BD ex.
• Examples of commercial epoxy paint compositions i.e. commercially relevant examples of combinations of epoxy-functional compounds of non-silicon origin and amino-functional compounds of non-silicon origin, to be used within the context of the present invention are commercially available primers to be used under the waterline for antifouling and fouling release products, e.g. Hempadur 15570, from Hempel A/S; Intershield 300 ex. International Coatings Ltd UK; Primastic Universal ex. Jotun A/S Norway; and Umeguard SX ex. CMP Coatings Inc USA.
• the epoxy-functional silicon compound(s) and the amino-functional silicon compound(s) are typically as defined for the first main embodiment.
• the epoxy functional compound(s) consist(s) of one or more epoxy- functional compounds of non-silicon origin and one or more epoxy-functional silicon compounds as defined above.
• the epoxy-functional silicon compound(s) may be epoxy-functional polysiloxane(s).
• the binder phase typically comprises 1-60%, such as 1-30%, e.g. 1-20%, by wet weight of epoxy-functional polysiloxane(s).
• the epoxy-functional silicon compound(s) may be the combination of epoxy- functional polysiloxane(s) and epoxysilane(s).
• the binder phase typically comprises 1-60%, such as 1-30%, e.g. 1-20%, by wet weight of the epoxy-functional polysiloxane(s)/epoxysilane(s).
• the amino functional compound(s) may consist of one or more amino-functional compounds of non-silicon origin and one or more amino-functional silicon compounds.
• the amino-functional silicon compound(s) may be amino-functional polysiloxane(s).
• at least one amino-functional polysiloxane is the reaction product of a polysiloxane and an aminosilane.
• the binder phase typically comprises 1-60%, such as 1- 30%, or 1-20%, by wet weight of the amino-functional polysiloxane(s).
• the amino-functional silicon compound(s) may be the combination of amino- functional polysiloxane(s) and aminosilane(s).
• the binder phase may comprise 1-60%, such as 1-30%, e.g. 1-20%, by wet weight of the amino-functional polysiloxane(s)/aminosilane(s).
• the ratio between the hydrogen equivalents of the amino-functional compound(s) and the epoxy equivalents of the epoxy-functional compound(s) is typically in the range of 20: 100 to 200: 100.
• the at least two types of polysiloxane compounds ((a) amino- functional polysiloxanes; (b) epoxy-functional polysiloxanes; (c) adhesion promoting agents selected from the group consisting of hydroxy-functional polysiloxanes, hydroxyalkyl- functional polysiloxanes and C 1-4 -alkoxy-functional polysiloxanes) are used in admixture with epoxy-functional compound(s) of non-silicon origin, e.g. the epoxy resin constituents of an epoxy paint composition.
• the polysiloxane type and silane type constituents typically constitute 2- 90%, or 2-40%, such as 2-30%, or 2-15%, by wet weight of the binder phase and epoxy- functional compound(s) of non-silicon origin typically constitute 10-70%, or 20-70%, such as 10-45%, e.g. 20-45%, by wet weight of the binder phase.
• the epoxy-functional silicon compound(s), the amino-functional silicon compound(s), and the epoxy-functional compound of non-silicon origin are typically as defined for the second main embodiment.
• the ratio between the hydrogen equivalents of the amino-functional compound(s) and the epoxy equivalents of the epoxy-functional compound(s) is typically in the range of 20:100 to 200:100.
• the polysiloxane coating applied according to the invention is typically used as a tie-coat, and it is therefore often desirable to include an adhesion promoting agent in the binder phase so as to improve the subsequent adhesion of a top-coat, e.g. fouling release coating (see below).
• the binder phase of the coating composition further comprises an adhesion promoting agent.
• adhesion promoting agent is intended to mean that the agent in question has a beneficial impact on adhesion between the tie-coat and a subsequent layer applied onto the tie-coat.
• the adhesion promoting agent is a polydiorganosiloxane of viscosity 60- 10,000 mPas, such as 60-5,000 mPas, e.g. 60-1000 mPas, at 25°C. It preferably contains silicon-bonded hydroxyl groups, for example an ⁇ , ⁇ -dihydroxypolydiorganosiloxane, or silicon-bonded hydrolysable groups, for example a polydiorganosiloxane tipped with silicon- bonded hydrolysable groups such as C ⁇ -4 -alkoxy groups (e.g. methoxy groups).
• silicon-bonded hydroxyl groups for example an ⁇ , ⁇ -dihydroxypolydiorganosiloxane
• silicon-bonded hydrolysable groups for example a polydiorganosiloxane tipped with silicon- bonded hydrolysable groups such as C ⁇ -4 -alkoxy groups (e.g. methoxy groups).
• R is selected from C 1-8 -alkyl (such as methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, n- hexyl, 2-ethyl hexyl and n-octyl), C 4 .
• Suitable ⁇ ,co-dihydroxypolydiorganosiloxanes are those of the formula HO-[Si(R) 2 0] n -H wherein each R independently is selected from methyl and phenyl, and where n is an integer in the range of 4-1000, such as 10-250.
• Suitable ⁇ , ⁇ -dimethoxypolydiorganosiloxanes are those of the formula MeO-[Si(R) 2 0] ⁇ -Me wherein each R independently is selected from methyl and phenyl, and where n is an integer in the range of 4-100, such as 10-50.
• the adhesion promoting agent is an hydroxyalkyl-functional polysiloxane.
• adhesion promoting agent examples include those selected from the group consisting of hydroxy-functional polysiloxanes, hydroxyalkyl-functional polysiloxanes and C 1- -alkoxy-functional polysiloxanes, in particular hydroxy-functional polysiloxanes and C 1-4 - alkoxy-functional polysiloxanes, e.g. those illustrated immediately above.
• Illustrative examples of commercially available polysiloxane adhesion promoting agents are Rhodorsil oil 48V100 (hydroxyl-functional polydimethylsiloxane) ex Rhodia; KF-6001 alkoxypolydimethylsiloxane ex Shin Etsu; Dow Corning 2-1273; etc.
• the binder phase comprises 0-20%, or 0.1-20%, such as 0.1-15%, e.g. 0.5-10%, by wet weight of the adhesion promoting agent(s).
• the (weight) average molecular weight of the adhesion promoting agent is less than 50,000 Dalton, or less than 25,000 Dalton, e.g. 500-50,000 Dalton, or 1000-10,000 Dalton.
• the coating composition used in the method of the invention may comprise other constituents such as pigments and fillers, as well as solvents and additives as described below under the subheading "Coating Composition”.
• the term "substrate” is intended to mean a solid material onto which the coating composition is applied.
• the substrate typically comprises a metal such as steel, iron, aluminium, or a glass-fibre.
• the substrate is a metal substrate, in particular a steel substrate.
• the substrate is a glass-fibre substrate.
• surface is used in its normal sense, and refers to the exterior boundary of an object. Particular examples of such surfaces are the surface of vessels (including but not limited to boats, yachts, motorboats, motor launches, ocean liners, tugboats, tankers, container ships and other cargo ships, submarines, and naval vessels of all types), pipes, shore and off-shore machinery, constructions and objects of all types such as piers, pilings, bridge substructures, water-power installations and structures, underwater oil well structures, nets and other aquatic culture installations, and buoys, etc.
• vessels including but not limited to boats, yachts, motorboats, motor launches, ocean liners, tugboats, tankers, container ships and other cargo ships, submarines, and naval vessels of all types
• pipes shore and off-shore machinery
• constructions and objects of all types such as piers, pilings, bridge substructures, water-power installations and structures, underwater oil well structures, nets and other aquatic culture installations, and buoys, etc.
• the surface of the substrate may either be the "native" surface (e.g. the steel surface), or the substrate may be coated, e.g. with an anticorrosive coating, so that the surface of the substrate is constituted by such a coating.
• the (anticorrosive) coating is typically applied in a total dry film thickness of 100-600 ⁇ m, such as 150-450 ⁇ m, e.g. 200- 400 ⁇ m.
• the substrate may carry a paint coat, e.g. a worn-out antifouling paint coat, or similar.
• the substrate is a metal substrate (e.g. a steel substrate) coated with an anticorrosive coating such as an anticorrosive epoxy-based coating, e.g. cured epoxy-based coating, or a shop-primer, e.g. a zinc-rich shop-primer.
• an anticorrosive coating such as an anticorrosive epoxy-based coating, e.g. cured epoxy-based coating, or a shop-primer, e.g. a zinc-rich shop-primer.
• the substrate is a glass-fiber substrate coated with an epoxy primer coating.
• applying is used in its normal meaning within the paint industry.
• “applying” is conducted by means of any conventional means, e.g. by brush, by roller, by spraying, by dipping, etc.
• the commercially most interesting way of “applying” the coating composition is by spraying.
• Spraying is effected by means of conventional spraying equipment known to the person skilled in the art.
• the coating is typically applied in a dry film thickness of 20-900 ⁇ m, such as 20-750 ⁇ m, e.g. 50-600 ⁇ m.
• the term "at least a part of the surface of said substrate” refers to the fact that the coating composition may be applied to any fraction of the surface.
• the coating composition is at least applied to the part of the substrate (e.g. a vessel) where the surface (e.g. the ship's hull), possibly after application of a fouling release layer, may come in contact with water, e.g. sea-water.
• a second coating composition is subsequently applied onto said tie-coat, whereby a polysiloxane-based coating, in particular a polysiloxane- based fouling release coating, is established on said substrate.
• the second polysiloxane-based coating may be a reaction-curable top-coat or a moisture-curable top-coat as will be evident for the person skilled in the art.
• Examples hereof are a two-component reaction-curing top-coat based on a hydroxyl-reactive polydiorganosiloxane, or a one-component moisture-curable top-coat based on a polydiorganosiloxane with alkoxy reactivity.
• the second polysiloxane-based coating is a fouling release coating.
• the fouling release coating can be established by any conventional fouling release coating composition.
• the second polysiloxane-based coating composition comprises a polydimethylsiloxane.
• the second polysiloxane-based coating is typically applied in a dry film thickness of 20- 500 ⁇ m, such as 20-400 ⁇ m, e.g. 50-300 ⁇ m.
• the second polysiloxane-based coating composition is typically applied as described above under the definition of the term "applying".
• a possible alternative embodiment of the invention is that where the fouling release coating is established using a composition comprising a fluorinated resin either alone or in combination with polysiloxanes, e.g. 50-95% of a fluoro-polymer and 5- 50% of a polysiloxane.
• a fluorinated resin either alone or in combination with polysiloxanes, e.g. 50-95% of a fluoro-polymer and 5- 50% of a polysiloxane.
• fluorinated resins are, e.g., disclosed in WO 01/094446 or WO 02/074870.
• the fluorinated resin typically includes functional groups that capable of reacting with functional groups, e.g. hydroxy groups, of the tie-coat layer.
• the present invention in one variant in particular provides the method defined above, wherein the binder phase comprises amino-functional polysiloxane(s) and epoxy-functional polysiloxane(s).
• the binder phase of the coating composition comprises amino-functional polysiloxane(s), epoxy-functional polysiloxane(s), and adhesion promoting agent(s).
• the invention provides a method as defined above of coating a metal substrate coated with an anticorrosive epoxy-based coating, the method comprising:
• a coating composition to at least a part of said anticorrosive coating thereby establishing a tie-coat on said substrate, wherein said coating composition comprises (i) 5- 45%, such as 5-40% by wet weight of pigments and fillers; and (ii) the balance of a binder phase comprising:
• the invention provides a method as defined above of coating a metal substrate coated with an anticorrosive epoxy-based coating, the method comprising:
• a coating composition to at least a part of said anticorrosive coating thereby establishing a tie-coat on said substrate, wherein said coating composition comprises (i) 5- 45%, such as 5-40% by wet weight of pigments and fillers; and (ii) the balance of a binder phase comprising:
• the invention provides a method as defined above of coating a metal substrate coated with an anticorrosive epoxy-based coating, the method comprising:
• a coating composition to at least a part of said anticorrosive coating thereby establishing a tie-coat on said substrate, wherein said coating composition comprises (i) 5- 45%, such as 5-40% by wet weight of pigments and fillers; and (ii) the balance of a binder phase comprising:
• the invention provides a method as defined above of coating a metal substrate coated with an anticorrosive epoxy-based coating, the method comprising:
• a coating composition to at least a part of said anticorrosive coating thereby establishing a tie-coat on said substrate, wherein said coating composition comprises (i) 5- 45%, such as 5-40% by wet weight of pigments and fillers; and (ii) the balance of a binder phase comprising:
• the invention provides the method defined herein, wherein the binder phase of the coating composition comprises amino-functional polysiloxane(s), epoxy- functional polysiloxane(s), and the combination of one or more amino-functional compounds of non-silicon origin and one or more epoxy-functional compounds of non-silicon origin (i.e. an epoxy paint composition).
• the binder phase of the coating composition comprises amino-functional polysiloxane(s), epoxy-functional polysiloxane(s), adhesion promoting agent(s), and the combination of one or more amino-functional compounds of non-silicon origin and one or more epoxy-functional compounds of non-silicon origin (i.e. an epoxy paint composition).
• the invention provides a method as defined above of coating a metal substrate coated with an anticorrosive epoxy-based coating, the method comprising:
• a coating composition to at least a part of said anticorrosive coating thereby establishing a tie-coat on said substrate, wherein said coating composition comprises (i) 5- 45%, such as 5-40% by wet weight of pigments and fillers; and (ii) the balance of a binder phase comprising: 2-50%, such as 2-30% by wet weight of amino-fu nctional polysiloxane(s), epoxy-functional polysiloxane(s), and optionally amino-silane(s) and epoxy-silane(s); and 10-80%, such as 30-55% by wet weight of the combination of one or more amino-functional compounds of non-silicon origin and one or more epoxy-functional compounds of non-silicon origin, wherein the ratio between the hydrogen equivalents of the amino-functional polysiloxane(s) and the epoxy equivalents of the epoxy-functional polysiloxane(s)/epoxysilane(s) is in the range of 20: 100 to 200: 100; and
• the invention provides a method as defined above of coating a metal substrate coated with an anticorrosive epoxy-based coating, the method comprising:
• a coating composition to at least a part of said anticorrosive coating thereby establishing a tie-coat on said substrate, wherein said coating composition comprises (i) 5- 45%, such as 5-40% by wet weight of pigments and fillers; and (ii) the balance of a binder phase comprising:
• the present invention in particular provides the method defined above, wherein the binder phase of the coating composition comprises amino-functional polysiloxane(s), epoxy-functional silane(s), and adhesion promoting agent(s).
• the invention provides a method as defined above of coating a metal substrate coated with an anticorrosive epoxy-based coating, the method comprising: (A) applying a coating composition to at least a part of sa id anticorrosive coating thereby establishing a tie-coat on said substrate, wherein said coating composition comprises (i) 5- 45%, such as 5-40% by wet weight of pigments and fillers; and (ii) the balance of a binder phase comprising:
• the invention provides a method as defined above of coating a metal substrate coated with an anticorrosive epoxy-based coating, the method comprising:
• a coating composition to at least a part of said anticorrosive coating thereby establishing a tie-coat on said substrate, wherein said coating composition comprises (i) 5- 45%, such as 5-40% by wet weight of pigments and fillers; and (ii) the balance of a binder phase comprising:
• the binder phase of the coating composition comprises the combination of one or more arnino-functional compounds of non- silicon origin and one or more epoxy-functional compounds of non-silicon origin (i.e. an epoxy paint composition).
• the invention provides a method as defined above of coating a metal substrate coated with an anticorrosive epoxy-based coating, the method comprising:
• a coating composition to at least a part of said anticorrosive coating thereby establishing a tie-coat on said substrate, wherein said coating composition comprises (i) 5- 45%, such as 5-40% by wet weight of pigments and fillers; and (ii) the balance of a binder phase comprising:
• the present invention in particular provides the method defined above, wherein the binder phase of the coating composition comprises amino-functional silane(s), epoxy-functional polysiloxane(s), and adhesion promoting agent(s).
• the invention provides a method as defined above of coating a metal substrate coated with an anticorrosive epoxy-based coating, the method comprising:
• a coating composition to at least a part of said anticorrosive coating thereby establishing a tie-coat on said substrate, wherein said coating composition comprises (i) 5- 45%, such as 5-40% by wet weight of pigments and fillers; and (ii) the balance of a binder phase comprising:
• the invention provides a method as defined above coating a metal substrate coated with an anticorrosive epoxy-based coating, the method comprising:
• a coating composition to at least a part of said anticorrosive coating thereby establishing a tie-coat on said substrate, wherein said coating composition comprises (i) 5- 45%, such as 5-40% by wet weight of pigments and fillers; and (ii) the balance of a binder phase comprising:
• 1-30% such as 1-20%, by wet weight of aminosilane(s), 2-90%, such as 5-85%, by wet weight of a combination of epoxy-functional polysiloxane(s) and epoxysilane(s), and
• the binder phase of the coating composition comprises the combination of one or more amino-functional compounds of non-silicon origin and one or more epoxy-functional compounds of non-silicon origin (i.e. an epoxy paint composition).
• the invention provides a method as defined above of coating a metal substrate coated with an anticorrosive epoxy-based coating, the method comprising:
• a coating composition to at least a part of said anticorrosive coating thereby establishing a tie-coat on said substrate, wherein said coating composition comprises (i) 5- 45%, such as 5-40% by wet weight of pigments and fillers; and (ii) the balance of a binder phase comprising:
• the binder phase of the coating composition comprises amino- functional polysiloxane(s), adhesion promoting agent(s), and the combination of one or more amino-functional compounds of non-silicon origin and one or more epoxy-functional compounds of non-silicon origin (i.e. an epoxy paint composition).
• the invention provides a method as defined above of coating a metal substrate coated with an anticorrosive epoxy-based coating, the method comprising:
• a coating composition to at least a part of said anticorrosive coating thereby establishing a tie-coat on said substrate, wherein said coating composition comprises (i) 5- 45%, such as 5-40% by wet weight of pigments and fillers; and (ii) the balance of a binder phase comprising:
• the binder phase of the coating composition comprises epoxy- functional polysiloxane(s), adhesion promoting agent(s), and the combination of one or more amino-functional compounds of non-silicon origin and one or more epoxy-functional compounds of non-silicon origin (i.e. an epoxy paint composition).
• the invention provides a method as defined above of coating a metal substrate coated with an anticorrosive epoxy-based coating, the method comprising: (A) applying a coating composition to at least a part of said anticorrosive coating thereby establishing a tie-coat on said substrate, wherein said coating composition comprises (i) 5- 45%, such as 5-40% by wet weight of pigments and fillers; and (ii) the balance of a binder phase comprising:
• the binder phase of the coating composition comprises amino-functional polysiloxane(s), adhesion promoting agent(s), and epoxy-functional compound(s) of non-silicon origin.
• the invention provides a method as defined above of coating a metal substrate coated with an anticorrosive epoxy-based coating, the method comprising:
• a coating composition to at least a part of said anticorrosive coating thereby establishing a tie-coat on said substrate, wherein said coating composition comprises (i) 5- 45%, such as 5-40% by wet weight of pigments and fillers; and (ii) the balance of a binder phase comprising:
• the binder phase of the coating composition comprises amino-functional polysiloxane(s), epoxy-functional polysiloxane(s), adhesion promoting agent(s), and epoxy-functional compound(s) of non-silicon origin.
• the invention provides a method as defined above of coating a metal substrate coated with an anticorrosive epoxy-based coating, the method comprising:
• a coating composition to at least a part of said anticorrosive coating thereby establishing a tie-coat on said substrate, wherein said coating composition comprises (i) 5- 45%, such as 5-40% by wet weight of pigments and fillers; and (ii) the balance of a binder phase comprising:
• amino-functional polysiloxane(s) such as 2-30% by wet weight of amino-functional polysiloxane(s), epoxy-functional polysiloxane(s), adhesion promoting agent(s), and optionally amino-silane(s) and epoxy- silane(s);
• the adhesion promoting agent(s) is/are preferably selected from the group consisting of hydroxy-functional polysiloxanes, hydroxyalkyl-functional polysiloxanes and C ⁇ -4 -alkoxy-functional polysiloxanes, in particular from hydroxy-functional polysiloxanes and C 1-4 -alkoxy-functional polysiloxanes,
• the anticorrosive epoxy-based coating may, if desirable, be substituted with another epoxy primer coating which may not necessarily have the same anticorrosive properties.
• a further aspect of the invention relates to a coating composition, said coating composition comprises (i) 0-60%, such as 0-50° , preferably 5- 45%, such as 5-40% or 5-35% by wet weight of pigments and fillers; and (ii) the balance of a binder phase comprising:
• binder phase comprises at least two types, (a), (b), (c), of polysiloxane compounds selected from the group consisting of:
• epoxy-functional polysiloxanes (b) epoxy-functional polysiloxanes; and (c) adhesion promoting agents selected from the group consisting of hydroxy-functional polysiloxanes, hydroxyalkyl-functional polysiloxanes and C ⁇ -4 -alkoxy-functional polysiloxanes.
• the ratio between the hydrogen equivalents of the amino-functional compound(s) and the epoxy equivalents of the epoxy-functional compound(s) is in the range of 20:100 to 200: 100.
• the binder phase of the coating composition comprises one or more adhesion promoting agents as defined above.
• the adhesion promoting agent(s) is/are preferably selected from the group consisting of hydroxy-functional polysiloxanes and C ⁇ -4 -alkoxy-functional polysiloxanes.
• the binder phase comprises 0.1-15% by wet weight of the adhesion promoting agent(s).
• the coating composition may further, as a part of the binder phase, comprise solvents and additives.
• solvents are aliphatic, cycloaliphatic and aromatic hydrocarbons such as white spirit, cyclohexane, toluene, octamethyltrisiloxane, xylene and naphtha solventesters such as methoxypropyl acetate, n-butyl acetate and 2-ethoxyethyl acetate; and mixtures thereof.
• epoxy-functional silicon compound is an epoxy-functional polysiloxane and the amino-functional silicon compound is an amino- functional polysiloxane
• solvent or dispersant
• water or a water/solvent mixture e.g. water/ethanol
• additives are: (i) plasticizers such as chlorinated paraffin; hydrocarbons or modified hydrocarbons, e.g. modified aromatic hydrocarbon resins such as modified phenol and alpha-methylstyrene based hydrocarbons; phthalates such as dibutyl phthalate, benzylbutyl phthalate, dioctyl phthalate, diisononyl phthalate and diisodecyl phthalate; phosphate esters such as tricresyl phosphate; sulfonamides, alkyl-p-toluene sulfonamide; adipates such as bis(Z-ethylhexyl)- adipate), diisobutyl adipate and dioctyladipate; phosphoric acid triethyl ester; butyl stearate; sorbitan trioleate; and non-reactive organopolysiloxanes;
• plasticizers such as chlorin
• surfactants such as derivatives of propylene oxide or ethylene oxide such as alkylphenol- ethylene oxide condensates; ethoxylated monoethanolamides of unsaturated fatty acids such as ethoxylated monoethanolamides of linoleic acid; sodium dodecyl sulfate; alkylphenol ethoxylates; and soya lecithin;
• defoaming agents such as silicone oils
• stabilisers such as stabilisers against light and heat, e.g. hindered amine light stabilisers
• UV-absorbers such as hydroxyphenyl benzotriazole-type and hydroxyphenyl triazine- type compounds, 2-hydroxy-4-methoxybenzophenone, 2-(5-chloro-(2H)-benzotriazol-2-yl)-
• inhibitors against corrosion such as aminocarboxylates, calcium silicophosphate, ammonium benzoate, barium/calcium/zinc/magnesium salts of alkylnaphthalene sulfonic acids, zinc phosphate; zinc metaborate;
• coalescing agents such as glycols, 2-butoxy ethanol, and 2,2,4-trimethyl-l,3- pentanediol monoisobutyrate;
• thickeners and anti-settling agents such as colloidal silica, hydrated aluminium silicate (bentonite), aluminiumtristearate, aluminiummonostearate, xanthan gum, chrysotile, pyrogenic silica, hydrogenated castor oil, organo-modified clays, polyamide waxes and polyethylene waxes; and
• (ix) dyes such as l,4-bis(butylamino)anthraquinone and other anthraquinone derivatives; toluidine dyes, etc.
• the coating composition may comprise pigments and fillers.
• Pigments and fillers are in the present context viewed in conjunction as constituents that may be added to the coating composition with only limited implications on the adhesion properties. "Pigments” are normally characterised in that they render the final paint coating non-transparent and non-translucent, whereas “fillers” normally are characterised in that they do not render the paint non-translucent and therefore do not contribute significantly to hide any material below the coating.
• pigments are grades of titanium dioxide, red iron oxide, zinc oxide, carbon black, graphite, yellow iron oxide, red molybdate, yellow molybdate, zinc sulfide, antimony oxide, sodium aluminium sulfosilicates, quinacridones, phthalocyanine blue, phthalocyanine green, black iron oxide, indanthrone blue, cobalt aluminium oxide, carbazole dioxazine, chromium oxide, isoindoline orange, bis-acetoacet-o-tolidiole, benzimidazolon, quinaphtalone yellow, isoindoline yellow, tetrachloroisoindolinone, quinophthalone yellow.
• fillers examples include calcium carbonate such as calcite, dolomite, talc, mica, feldspar, barium sulfate, kaolin, nephelin, silica, perlite, magnesium oxide, and quartz flour, etc. Fillers (and pigments) may also be added in the form of fibres, thus, apart from the before- mentioned examples of fillers, the coating composition may also comprise fibres, e.g. those generally and specifically described in WO 00/77102 which is hereby incorporated by reference.
• mineral fibres such as mineral-glass fibres, wollastonite fibres, montmorillonite fibres, tobermorite fibres, atapulgite fibres, calcined bauxite fibres, volcanic rock fibres, bauxite fibres, rockwool fibres, and processed mineral fibres from mineral wool.
• any pigments and/or fillers constitute 0-60%, such as 0-50%, preferably 5-45%, such as 5- 40% or 5-35%, by wet weight of the coating composition.
• concentration of the fibres is normally in the range of 0.1-50%, e.g. 0.1-25% by wet weight of the coating composition, such as 0.5-10% by wet weight of the coating composition.
• concentrations of fibres depending upon the type and size of the fibres, may be 1-10% or 2- 10%, such as 2-7%, or 3-10%, such as 3-8% by wet weight of the coating composition. It should be understood that the above ranges refer to the total amount of fibres, thus, in the case where two or more fibre types are utilised, the combined amounts should fall within the above ranges.
• the coating compositions may be prepared by conventional method using equipment known to the person skilled in the art, e.g. utilising mixers, ball mills, grinders, filters, etc.
• the coating compositions are typically prepared and shipped as two- or three-component systems that should be combined and thoroughly mixed immediately prior to use.
• an adhesion promoting agent is included in the coating composition, a three-component system is typically preferred.
• An example of a suitable preparation method is described in the Examples.
• Particular embodiments of the coating composition of the invention are described in the examples.
• the binder phase comprises amino- functional polysiloxane(s) and epoxy-functional polysiloxane(s).
• the binder phase of the coating composition comprises amino-functional polysiloxane(s), epoxy-functional polysiloxa ne(s), and adhesion promoting agent(s).
• the coating composition comprises (i) 5-45%, such as 5-40% by wet weight of pigments and fillers; and (ii) the balance of a binder phase comprising:
• the coating composition comprises (i) 5-4-5%, such as 5-40% by wet weight of pigments and fillers; and (ii) the balance of a binder phase comprising:
• the coating composition comprises (i) 5-45%, such as 5- 40% by wet weight of pigments and fillers; and (ii) the balance of a binder phase comprising: 15-60%, such as 15-50%, by wet weight of amino-functional polysiloxane(s), 2-90%, such as 5-85%, by wet weight of a combination of epoxy-functional polysiloxane(s) and epoxysilane(s), and
• adhesion promoting agent(s) 0-20% or 0.1-20%, such as 0.1-15%, such as 0.5-10%, by wet weight of adhesion promoting agent(s), wherein the ratio between the hydrogen equivalents of the amino-functional polysiloxane(s) and the epoxy equivalents of the epoxy-functional polysiloxane(s)/epoxysilane(s) is in the range of 40:100 to 200:100.
• the coating composition comprises (i) 5-45%, such as 5- 40% by wet weight of pigments and fillers; and (ii) the balance of a binder phase connprising:
• the binder phase of the coating composition comprises amino-functional polysiloxane(s), epoxy-functional polysiloxane(s), and the combination of one or more amino-functional compound(s) of non-silicon origin and epoxy-functional compound(s) of non-silicon origin (i.e. an epoxy paint composition).
• the binder phase of the coating composition comprises amino-functional polysiloxane(s), epoxy-functional polysiloxane(s), adhesion promoting agent(s), and the combination of one or more arnino- functional compound(s) of non-silicon origin and one or more epoxy-functional compound(s) of non-silicon origin (i.e. an epoxy paint composition).
• the coating composition comprises (i) 5-45%, such as 5-4O% by wet weight of pigments and fillers; and (ii) the balance of a binder phase comprising :
• the coating composition comprises (i) 5-45%, such as 5- 40% by wet weight of pigments and fillers; and (ii) the balance of a binder phase comprising:
• amino-functional polysiloxane(s) such as 2-30% by wet weight of amino-functional polysiloxane(s), epoxy-functional polysiloxane(s), adhesion promoting agent(s), and optionally amino-silane(s) and epoxy- silane(s);
• the binder phase of the coating composition comprises amino-functional polysiloxane(s), epoxy-functional silane(s), and adhesion promoting agent(s).
• the coating composition comprises (i) 5-45%, such as 5-40% by wet weight of pigments and fillers; and (ii) the balance of a binder phase comprising:
• the coating composition comprises (i) 5-45%, such as 5-40% by wet weight of pigments and fillers; and (ii) the balance of a binder phase comprising:
• the binder phase of the coating composition further comprises the combination of one or more amino-functional compound(s) of non-silicon origin and one or more epoxy-functional compound(s) of non-silicon origin, (i.e. an epoxy paint composition ).
• the coating composition comprises (i) 5-45%, such as 5-40% by wet weight of pigments and fillers; and (ii) the balance of a binder phase comprising:
• the binder phase of the coating composition comprises amino-functional silane(s), epoxy-functional polysiloxane(s), and adhesion promoting agent(s).
• the coating composition comprises (i) 5-45%, such as 5-40% by wet weight of pigments and fillers; and (ii) the balance of a binder phase comprising:
• 1-30% such as 1-20%, by wet weight of aminosilane(s), 25-90%, such as 30-90%, e.g. 40-90% by wet weight of epoxy-functional polysiloxane(s), and
• the coating composition comprises (i) 5-45%, such as 5-40% by wet weight of pigments and fillers; and (ii) the balance of a binder phase comprising:
• the binder phase of the coating composition further comprises the combination of one or more amino-functional compounds of non-silicon origin and one or more epoxy-functional compounds of non-silicon origin (i.e. an epoxy paint composition) .
• the coating composition comprises (i) 5-45%, such as 5-40% by wet weight of pigments and fillers; and (ii) the balance of a binder phase comprising:
• the binder phase of the coating composition comprises amino-functional polysiloxane(s), adhesion promoting agent(s), and the combination of one or more amino-functional compounds of non-silicon origin and one or more epoxy-functional compounds of non-silicon origin (i.e. an epoxy paint composition).
• the coating composition comprises (i) 5-45%, such as 5-40% by wet weight of pigments and fillers; and (ii) the balance of a binder phase comprising:
• amino-functional polysiloxane(s) such as 2-30% by wet weight of amino-functional polysiloxane(s), adhesion promoting agent(s), and optionally amino-silane(s) and epoxy-silane(s); and 10-80%, such as 30-55% by wet weight of the combination of one or more amino-functional compounds of non-silicon origin and one or more epoxy-functional compounds of non-silicon origin, wherein the ratio between the hydrogen equivalents of the amino-functional polysiloxane(s) and the epoxy equivalents of the epoxy-functional polysiloxane(s)/epoxysilane(s) is in the range of 40:100 to 200: 100.
• the binder phase of the coating composition comprises epoxy-functional polysiloxane(s), adhesion promoting agent(s), and the combination of one or more amino-functional compounds of non-silicon origin and one or more epoxy-functional compounds of non-silicon origin (i.e. an epoxy paint composition).
• the coating composition comprises (i) 5-45%, such as 5-40% by wet weight of pigments and fillers; and (ii) the balance of a binder phase comprising:
• the binder phase of the coating composition comprises amino-functional polysiloxane(s), adhesion promoting agent(s), and epoxy-functional compound(s) of non-silicon origin.
• the coating composition comprises (i) 5-45%, such as 5-40% by wet weight of pigments and fillers; and (ii) the balance of a binder phase comprising:
• the binder phase of the coating composition comprises amino-functional polysiloxane(s), epoxy-functional polysiloxane(s), adhesion promoting agent(s), and epoxy-functional compound(s) of non-silicon origin.
• the coating composition comprises (i) 5-45%, such as 5-40% by wet weight of pigments and fillers; and (ii) the balance of a binder phase comprising:
• amino-functional polysiloxane(s) such as 2-30% by wet weight of amino-functional polysiloxane(s), epoxy-functional polysiloxane(s), adhesion promoting agent(s), and optionally amino-silane(s) and epoxy- silane(s);
• the adhesion promoting agent(s) is/are preferably selected from the group consisting of hydroxy- functional polysiloxanes, hydroxyalkyl-functional polysiloxanes and C ⁇ -4 -alkoxy-functional polysiloxanes, in particular from hydroxy-functional polysiloxanes and C 1-4 -alkoxy-functional polysiloxanes,
• Another aspect of the invention relates to an article comprising a substrate, an epoxy-based coating on at least a part of the surface of said substrate, a tie-coat on said epoxy-based coating, and a fouling release coating on said tie-coat, wherein said tie-coat is as defined hereinabove.
• the coating composition, the method of establishing the coating on the substrate surface, and the characteristics of the coating follow the directions given hereinabove.
• the fouling release coating is a second polysiloxane-based coating.
• the anticorrosive layer has a total dry film thickness of 100-600 ⁇ m, such as 150-450 ⁇ m, e.g. 200-400 ⁇ m; the tie-coat has a total dry film thickness of 20-500 ⁇ m, such as 20-400 ⁇ m, e.g. 50-300 ⁇ m; and the fouling release coating has a total dry film thickness of 20-500 ⁇ m, such as 20-400 ⁇ m, e.g. 50-300 ⁇ m.
• the anticorrosive layer has a total dry film thickness of 100-600 ⁇ m, such as 150-450 ⁇ m, e.g. 200-400 ⁇ m; the tie-coat has a total dry film thickness of 50-900 ⁇ m, such as 50-750 ⁇ m, e.g. 100-600 ⁇ m or 100-400 ⁇ m; and the fouling release coating has a total dry film thickness of 20-500 ⁇ m, such as 20-400 ⁇ m, e.g. 50-300 ⁇ m.
• the anticorrosive layer is established by application of 1-3 layers of a first epoxy-based coating and 1-2 layers of a second epoxy-based coating, said first epoxy-based coating and said second epoxy-based coating not being identical.
• the coating compositions defined herein may comprise one, two or more types of the individual constituents.
• the total amount of the respective constituent e.g. aminosilanes
• compound(s) in the expressions: compound(s), polysiloxane(s), silane(s), agent(s), etc. indicates that one, two or more types of the individual constituents may be present.
• Silres 44100 is an amino functional polysiloxane from Wacker Chemie GmbH, Germany.
• SF1708 is an aminofunctionalized polysiloxane fluid of GE silicones, 260 Hudson River Road,
• Silikoftal ED is an epoxy functional polysiloxane, a product of Tego Chemie Service GmbH,
• Rhodorsil 48V100 is a hydroxy terminated fluid substantially comprising polyorganosiloxane parts, a product of Rhodia.
• DC2-1273 is a hydroxy terminated fluid substantially comprising polyorganosiloxane parts from Dow Corning, USA.
• Dynasylan AMEO is a 3-aminopropyltriethoxysilane from Degussa AG, Germany.
• Hempadur 15570 is an anticorrosive epoxy paint from Hempel A/S.
• Hempadur 45880 is an anticorrosive epoxy paint from Hempel A/S.
• Amerlock 400 is an unfilled epoxy from Valspar Corp., 1101 Third Street South, Minneapolis,
• ES-1002T is a silicone modified epoxy resin varnish from Shin-Etsu Chemical, Japan.
• AMMO solution is a mixture of Dynasylan Ammo from Degussa AG, Germany, mixed with dibutyl tinoxide, ethyl silicate, and mineral spirit.
• KE-45TS topcoat is a silicone rubber varnish from Shin-Etsu Chemical, Japan.
• Titanium dioxide Kemira X660, Kemira Pigments OY, Finland.
• Percipitated barium sulphate Blanc Fixe Super F, Sachtleben Germany.
• Graphite AF96/97, Graphitmaschine Kropfm HL AG, Germany.
• Talc Luzenac 20 MO, Talc De Luzenac, France.
• Bentonite Bentone SD-2, Elementis Specialities, UK. Black Iron oxide Bayferrox 318M, Bayer, Germany.
• Extender pigment aluminium, potassium, sodium silicate Minex S 20, North Cape Nefelin A/S, Norway.
• Mineral fibres synthetic silicate fibres, MS 600; Lapinus Fibres BV, Holland.
• Epicoat 1001 is a bisphenol A type epoxy resin varnish (NV70%) from Badish Oil Company.
• KBM 603 is an amino silane coupling agent from Shin-Etsu Chemical, Japan.
• Sunmide X-2800 is a polyamide resin varnish from Sanwa Chemical Industry Co, Ltd, Japan.
• Araldite GZ 7071X75CH is a bisphenol A epoxide ex. Huntsman Advanced Materials, Switzerland. Solvents from local suppliers.
• Tin panels (210x300x0.3 mm) were first coated with 75-100 ⁇ m (dry film thickness, DFT) of a commercial anticorrosive epoxy paint (Hempadur 15570, from Hempel A/S) applied by air spraying or by a doctor blade hand applicator. After 24 hours of drying in the laboratory at the specified conditions, the anticorrosive paint was covered by the model paint, applied in 100-200 ⁇ m (dry film thickness, DFT) by air spraying or by a doctor blade hand applicator.
• DFT dry film thickness
• Hempadur 15570 commercial anticorrosive epoxy paint
• a topcoat (either Hempasil 77100 from Hempel A/S or KE-45TS from Shin- Etsu Chemical) was applied in 100-200 ⁇ m (dry film thickness, DFT) by air spraying or by a doctor blade hand applicator after the specified time of drying at the specified conditions. The panels were dried the specified time at the specified conditions. The paint coats were allowed to dry and cure at 20°C unless otherwise specified (Example 1).
• the adhesion of a coating formulation is tested by a finger peel test according to the following procedure.
• the tester attempts to remove the coating from the substrate/previous paint layer by peeling it off with the finger nail.
• the coating is considered to pass the test if there is only a cohesive failure in the layer to be tested and no adhesive failure between the layer and the substrate/previous layer.
• the coating is considered to fail if there is an adhesive failure between any layer and another layer or between the layer and the substrate.
• the adhesion of a coating formulation is tested in accordance with ISO 2812-1, method 3 (spotting method).
• the final coat of a painted system is subjected to an appropriate number of drops of the test liquid (either acetyl acetone or xylene), each approximately 0.1 ml in volume.
• the panels are left for the specified time, allowing air free access to it.
• the adhesion of the area is tested by means of the adhesion test described above.
• a mixture of additives included 6.7% by wet weight of a non-functional polydimethylsiloxane as a defoaming agent.
• the mill base (60 w/w% of the Silikoftal ED, black iron oxide pigment, extender pigment, synthetic silicate fibres, levelling agent, defoaming agent, 35 w/w% of the solvent) was premixed on a Diaf dissolver equipped with an impeller disc (70 mm. in diameter) in a 1 litre can for 15 minutes at 1000 rpm.
• the impeller disc was substituted with a Teflon disc (70 mm. in diameter).
• 500 grams of 3 mm. glass beads were added to the mill base and grinding was performed for 20 minutes at 2000 rpm.
• the rest of the raw materials (the remaining 40 w/w% of the Silikoftal ED, plastisizer, the remaining 65 w/w% of the solvent) were added and the composition was mixed at 1000 rpm. for 15 minutes.
• the paint base was separated from the glass beads by filtration.
• the amino-functional silicon compound and the adhesion promoting agent (hydroxyl-functional silicone oil) were added.
• Model paints weight of the Droplet topcoat Hempasil weight of binder phase binder phase of binder phase binder phase equivalents: Adhesion (polysiloxane binder phase of test 77100) pigments of epoxy- amino- of amino- of adhesion Epoxy 24h compounds) epoxy-functional (acetyl acetone) recoat interval 24h and fillers functional functional functional promoting equivalents polysiloxane compounds polysiloxane compounds agent

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• 2004
  • 2004-06-15 JP JP2006529641A patent/JP5165892B2/ja not_active Expired - Fee Related
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