US20150307745A1 - Siloxane-urethane foul release coatings - Google Patents

Siloxane-urethane foul release coatings Download PDF

Info

Publication number
US20150307745A1
US20150307745A1 US14/795,088 US201514795088A US2015307745A1 US 20150307745 A1 US20150307745 A1 US 20150307745A1 US 201514795088 A US201514795088 A US 201514795088A US 2015307745 A1 US2015307745 A1 US 2015307745A1
Authority
US
United States
Prior art keywords
composition
weight
curable composition
percent based
isocyanate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US14/795,088
Inventor
Paul J. Popa
Yanxiang Li
Hongyu Chen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Global Technologies LLC
Original Assignee
Dow Global Technologies LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Global Technologies LLC filed Critical Dow Global Technologies LLC
Priority to US14/795,088 priority Critical patent/US20150307745A1/en
Publication of US20150307745A1 publication Critical patent/US20150307745A1/en
Abandoned legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/7806—Nitrogen containing -N-C=0 groups
    • C08G18/7843—Nitrogen containing -N-C=0 groups containing urethane 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
    • 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
    • C09D183/10—Block or graft copolymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of 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; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • 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
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/007—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/61—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/458—Block-or graft-polymers containing polysiloxane sequences containing polyurethane sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/08—Polyurethanes from polyethers
    • 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
    • C09D183/14—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • 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
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/269—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension including synthetic resin or polymer layer or component
    • 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]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]

Definitions

  • This invention relates to two-part moisture curable coating compositions capable of forming polyurethane-polysiloxane networks.
  • the coating compositions are useful in the field of marine antifouling coatings.
  • Bio-fouling occurs everywhere in the marine environment and is a significant problem for marine objects, such as ships.
  • One approach to limit fouling microorganisms from accumulating is to use self-cleaning foul releasing coatings based on silicone elastomers.
  • Polydimethylsiloxane (PDMS) based silicone elastomer foul release coatings have a rubbery elasticity, a low surface energy and a smooth surface; making it easier for marine organisms to detach from the coating surface under shear stress generated by hydrodynamic drag.
  • PDMS is soft, easily wears off, and requires frequent reapplications; thereby costing time and money to maintain.
  • PU polyurethane
  • U.S. Pat. No. 8,299,200 discloses a polysiloxane-modified polyurethane coating prepared by reacting a mixture comprising polyisocyanate; polyol; and polysiloxane having functional groups capable of reacting with the polyisocyanate.
  • the functional groups capable of reacting with the polyisocyanate are attached to only a single end of the polyorganosiloxane chain. It is theorized that coatings that have a polysiloxane tethered at only one end, can result is a highly mobile surface and may permit easier release of fouling organisms.
  • U.S. Pat. No. 5,820,491 discloses a two-part urethane topcoat including a polyol component, an isocyanate component and a hydroxyl functional, polyether-modified polysiloxane copolymer component. Coatings prepared with this system fail to exhibit all the required performance parameters of coatings in a marine environment. What is needed is an alternative, inexpensive, simple and uniform coating composition that blends the properties of both PDMS and PU and meets or exceeds the required performance parameters of coatings in a marine environment.
  • the present invention provides a two-part moisture curable composition
  • a two-part moisture curable composition comprising: (a) a first part comprising at least one multifunctional polyol; (b) a second part comprising: (i) at least one polysiloxane polymer with at least two isocyanate functional groups and (ii) at least one isocyanate functional organic compound; and (c) solvent.
  • the present invention further provides a method of coating a substrate comprising: (a) forming a two-part moisture curable composition comprising: (i) a first part comprising at least one multifunctional polyol; (ii) a second part comprising: (A) at least one polysiloxane polymer with at least two isocyanate functional groups and (B) at least one isocyanate functional organic compound; and (iii) solvent; (b) optionally blending in one or more of pigments, dyes, gloss reducing additives, cure catalysts, flow and leveling agents, degassing additives, adhesion promoters, dispersion aids, flame-retardant agents, heat stabilizers, light stabilizers, antioxidants, plasticizers, antistatic agents, ultraviolet (UV) absorbers, lubricants or combinations thereof; and (c) applying the composition of steps (a) and (b) to a substrate and curing the composition.
  • a two-part moisture curable composition comprising: (i) a first part
  • the present invention further provides a two-part moisture curable composition
  • a two-part moisture curable composition comprising: (a) a first part comprising: (i) at least one multifunctional polyol and (ii) at least one polysiloxane polymer with at least two mercapto functional groups; (b) a second part comprising at least one isocyanate functional organic compound; and (c) solvent.
  • the present invention further provides a method of coating a substrate comprising: (a) forming a two-part moisture curable composition comprising: (i) a first part comprising: (A) at least one multifunctional polyol and (B) at least one polysiloxane polymer with at least two mercapto functional groups; (ii) a second part comprising at least one isocyanate functional organic compound; and (iii) solvent; (b) optionally blending in one or more of pigments, dyes, gloss reducing additives, cure catalysts, flow and leveling agents, degassing additives, adhesion promoters, dispersion aids, flame-retardant agents, heat stabilizers, light stabilizers, antioxidants, plasticizers, antistatic agents, ultraviolet (UV) absorbers, lubricants or combinations thereof; and (c) applying the composition of steps (a) and (b) to a substrate and curing the composition.
  • a two-part moisture curable composition comprising: (i) a first part
  • polyol is an alcohol molecule containing multiple hydroxyl groups.
  • multifunctional polyol means a polyol that has more than one reactive site capable of cross-linking.
  • polyurethane means a resin in which the polymer units are linked by urethane linkages, i.e., —O—CO—NH—, and/or one or more urea linkages, i.e., —NH—CO—NH—.
  • isocyante means a functional group with the formula —N ⁇ C ⁇ O.
  • mercapto means a functional group with the formula —SH, which may also be referred to as a thiol group.
  • the polysiloxane polymer of the present invention has the formula:
  • each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , or R 10 group is independently selected from substituted or unsubstituted C 1 to C 60 hydrocarbon radicals, provided that (i) at least one of the R 1 through R 10 groups is substituted with an isocyanate functional group or a mercapto group and (ii) the polysiloxane polymer has at least two isocyante or mercapto functional groups.
  • at least one of the R 1 through R 10 groups is substituted with an isocyanate functional group and the polysiloxane polymer has at least two isocyante functional groups.
  • the isocyanate functional polysiloxane has a number average molecular weight in the range of from 4,000 to 15,000, more preferably from 6,000 to 10,000.
  • the number average molecular weight is determined by GPC Viscotek VE2001 using a Mixed D column and polystyrene standard.
  • suitable isocyanate functional polysiloxanes include without limitation, Silmer® Di-50 and D-100 materials from Siltech Corp., which are linear-difunctional polysiloxanes represented by the formula:
  • the polysiloxane polymer of the present invention makes up from 2 to 40 weight percent based on the total solids weight of the curable composition (i.e. excluding the solvent used in the curable composition).
  • the polysiloxane polymer is from 5 to 30 weight percent based on the total solids weight of the curable composition and most preferably from 10 to 25 weight percent based on the total solids weight of the curable composition.
  • the multi-functional polyol of the present invention may be selected from acrylic polyols, natural oil polyols, polyester polyols, polyether polyols, polycarbonate polyols, and blends thereof.
  • Acrylic polyols are preferred.
  • Suitable acrylic polyols include acrylic polymers that range in Tg from 0-45° C. preferably from 10-40° C., and most preferably 20-35° C. and have number average molecular weights (Mn) in the range of 2,000-25,000 g/mol, preferably 3,000-15,000 g/mol and most preferably 4,000-8,000 g/mol.
  • the multi-functional polyol of the present invention makes up from 35 to 60 weight percent based on the total weight of the curable composition.
  • the multi-functional polyol is from 40 to 55 weight percent based on the total weight of the curable composition and most preferably from 40 to 50 weight percent based on the total weight of the curable composition.
  • the glass transition temperature (“Tg” herein) of the acrylic polymers are measured using a DSC from TA Instruments Model Q100 V9.8 Build 296 with a standard Cell FC.
  • Suitable natural oil polyols include non-modified NOPs, such as, for example, natural seed oil diol monomers; and modified NOPs, such as, for example, commercially available Gen 1 NOP DWD 2080 from The Dow Chemical Company, which are reconstructed NOP molecules with the monomers of saturated, mono-hydroxyl, bi-hydroxyl and tri-hydroxyl methyl esters at a weight ratio of approximately 32%, 38%, 28% and 2%.
  • Gen 1 NOP DWD 2080 from The Dow Chemical Company
  • Gen 4 NOP is obtained by reacting UnoxolTM diol and seed oil diol monomers which are separated from seed oil monomer.
  • UnoxolTM diol is a mixture of cis, trans-1,3- and cis, trans-1,4-cyclohexane dimethanol, and is available from The Dow Chemical Company.
  • Gen 4 NOP has following structure with the hydroxyl equivalent weight of 170 g/mol.
  • the natural oil derived polyols are polyols based on or derived from renewable feedstock resources such as natural and/or genetically modified plant vegetable seed oils and/or animal source fats.
  • oils and/or fats are generally comprised of triglycerides, that is, fatty acids linked together with glycerol.
  • Preferred are vegetable oils that have at least about 70 percent unsaturated fatty acids in the triglyceride.
  • the natural product may contain at least about 85 percent by weight unsaturated fatty acids.
  • Examples of preferred vegetable oils include, but are not limited to, for example, those from castor, soybean, olive, peanut, rapeseed, corn, sesame, cotton, canola, safflower, linseed, palm, grapeseed, black caraway, pumpkin kernel, borage seed, wood germ, apricot kernel, pistachio, almond, macadamia nut, avocado, sea buckthorn, hemp, hazelnut, evening primrose, wild rose, thistle, walnut, sunflower, jatropha seed oils, or a combination thereof.
  • oils obtained from organisms such as algae may also be used.
  • animal products include lard, beef tallow, fish oils and mixtures thereof.
  • a combination of vegetable and animal based oils/fats may also be used.
  • the average hydroxyl functionality of the NOP is in the range of from 1 to 10; preferably in the range of from 2 to 6.
  • the NOP may have a number average molecular weight in the range of from 100 to 3,000; preferably from 300 to 2,000; and more preferably from 350 to 1,500.
  • Suitable isocyanate functional organic compounds include aliphatic or cycloaliphatic polyisocyanates such as hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), methylene bis(p-cyclohexyl isocyanate) (H 12 MDI), meta-tetramethylxylene diisocyanate (m-TMXDI), cyclohexyl diisocyanate (CHDI), 1,3-bis(isocyanatomethyl)cyclohexane and 1,4-bis(isocyanatomethyl)cyclohexane; trimers of diisocyanates such as the trimer of hexamethylene diisocyanate (HDI) sold under the trademark Desmodur®N-3390 from Bayer MaterialScience AG, the trimer of isophorone diisocyanate (IPDI) sold under the tradename Tolanate® IDT-70 from Perstorp Polyols, Inc., and blends thereof.
  • the isocyanate functional organic compounds are trimers of hexmethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI); and most preferably trimers of hexamethylene diisocyanate (HDI).
  • the isocyanate functional organic compounds of the present invention make up from 8 to 30 weight percent based on the total weight of the curable composition.
  • isocyanate functional organic compounds are from 10 to 30 weight percent based on the total weight of the curable composition and most preferably from 15 to 25 weight percent based on the total weight of the curable composition.
  • Suitable urethane grade solvents include aromatic hydrocarbons such as xylene, toluene; ketones such as methyl isobutyl ketone, methyl amyl ketone, or acetone, esters such as butyl acetate, or hexyl acetate; glycol ether esters such as propylene glycol monomethyl ether acetate; esters such as propyl propionate or butyl propionate, and blends thereof.
  • the solvent makes up from 10 to 60 weight percent based on the total weight of the curable composition.
  • solvent is from 15 to 50 weight percent based on the total weight of the curable composition and most preferably from 20 to 40 weight percent based on the total weight of the curable composition.
  • the curable compositions are useful as coatings and may include various additives ordinarily incorporated in compositions of this type.
  • additional additives include, but are not limited to, pigments, dyes, gloss reducing additives, cure catalysts, flow and leveling agents, degassing additives, adhesion promoters, dispersion aids, flame-retardant agents, heat stabilizers, light stabilizers, antioxidants, plasticizers, antistatic agents, ultraviolet (UV) absorbers, lubricants or combinations including one or more of the foregoing additives.
  • Suitable adhesion promoters include silane adhesion promoters, such as 3-glycidoxypropyl trimethoxysilane, which can enhance the wet adhesion of the fouling release top coat without the need for a mid or tie coat.
  • silane adhesion promoter is in the range of from 0.5 to 3 weight percent based on the total weight of the curable composition, more preferably from 1 to 3 weight percent based on the total weight of the curable composition, and most preferably from 1.5 to 3 weight percent based on the total weight of the curable composition.
  • Curable coating compositions of the present invention can be un-pigmented transparent clear coats, or pigmented systems for primer, basecoat and topcoat applications.
  • the pigment may be any typical organic or inorganic pigment. Several different pigments may be needed to achieve a desirable color for a particular application. Examples of suitable pigments include without limitation, titanium dioxide, barytes, clay, calcium carbonate, red iron oxide, CI Pigment Yellow 42, CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4 (copper phthalocyanines), CI Pigment Red 49:1, CI Pigment Red 57:1 and carbon black.
  • the resulting coating compositions can be applied onto a substrate using techniques known in the art; e.g. by spraying, draw-down, roll-coating.
  • the nominal dry film thickness (DFT) of the coating is greater than or equal to 2 mils, preferably greater than 2.5 mils and more preferably greater than 3 mils.
  • substrates that may be coated include without limitation, plastics, wood, metals such as aluminum, steel or galvanized sheeting, tin-plated steel, concrete, glass, composites, urethane elastomers, primed (painted) substrates, and the like.
  • the coatings can be cured at room temperature or at an elevated temperature in a forced air oven or with other types of heating sources.
  • Acrylic Polyol A comprises by weight, in Polyol Synthesized in polymerized form, 42% methyl methacrylate laboratory. (MMA), 30% hydroxyethylmethacrylate (HEMA) and 28% butyl acrylate (BA), with a Tg of 31° C., a solution hydroxyl equivalent weight of 552 at 80.3% solids and a Mn of 4600.
  • Acrylic Polyol B comprises by weight, in Polyol Synthesized in polymerized form, 30% MMA, 30% HEMA and laboratory. 40% BA, with a Tg of 14° C., a solution hydroxyl equivalent weight of 551 at 76.4% solids and a Mn of 3800.
  • Acrylic Polyol C comprises by weight, in Polyol Synthesized in polymerized form, 16% MMA, 30% HEMA and laboratory. 54% BA, with a Tg of ⁇ 3° C., a solution hydroxyl equivalent weight of 557 at 73.1% solids and a Mn of 5000.
  • Acrylic Polyol D is the same composition as Polyol Synthesized in Acrylic Polyol A, but with a solution hydroxyl laboratory. equivalent weight of 610 at 77.5% solids and a Mn of 3500.
  • Polyester 1 Natural Oil Polyol
  • Polyester 2 (CAPA TM 3091 polycaprolactone), Polyol Perstorp Polyols, CAS Number 37625-56-2 with a molecular Inc. weight of 900.
  • Polyester 3 (CAPA TM 3050 polycaprolactone), Polyol Perstorp Polyols, CAS Number 37625-56-2 with a molecular Inc. weight of 540.
  • Siloxane 1 MCR-C62 mono-dicarbinol Hydroxy functional Gelest, Inc. terminated polydimethylsiloxane
  • PDMS molecular weight 5,000 Siloxane 2 (Dow Corning ® 54 Additive dimethyl, Hydroxy functional Dow Corning methyl(polypropylene oxide) siloxane), CAS siloxane Corporation Number 68957-00-6, Siloxane 3 (Dow Corning ® 29 Additive Hydroxy functional Dow Corning octamethylcyclotetrasiloxane and siloxane Corporation decamethylcyclopentasiloxane), CAS Numbers 556-67-2 and 541-02-6 n-Butyl Propionate Solvent The Dow Chemical Company n-Propyl Propionate Solvent The Dow Chemical Company Methyl Isobutyl Ketone (MIBK) Solvent Honeywell Burdick- Jackson, a subsidiary of Honeywell International, Inc. Z-6040 silane (glycidoxy
  • the test was carried out according to a modified procedure as described in reference (Kohl JG& Singer IL, Pull-off behavior of epoxy bonded to silicone duplex coatings, Progress in Organic Coatings, 1999, 36:15-20) using an Instron machine under the trade designation InstronTM Model 1122.
  • Ten-millimeter diameter aluminum studs were used and glued to the surface of the coated panels using an epoxy adhesive (Hysol® 1C from Henkel Loctite Americas, www.loctite.com). The excessive epoxy was trimmed after about one hour cure.
  • the epoxy adhesive was then allowed to harden for at least three days at room temperature.
  • the stud was then pulled off using an Instron machine until the stud detached from the coating surface.
  • the threshold of pseudo-barnacle pull off strength was 0.6 MPa.
  • the water contact angle of the coatings was measured using a VCA Optima contact angle measuring device from AST Products, Inc. A water droplet, 0.5-1 ⁇ l was placed on the coating surface. After the equilibrium time the contact angle was measured. A higher contact angle means the coating surface is hydrophobic. For a fouling release coating the contact angle should be ⁇ 100°.
  • the impact resistance of the coating was determined by using a Gardner impact tester according to ASTM D2794. This test involves dropping a weight onto an indenter which is resting on the surface of the coating. The weight is dropped from a known height and the indenter forms a dimple in the coated panel. The coating is observed for cracking or delaminating on or around the dimple. The force to produce cracking/delaminating is recorded in inch-pounds (in-lb). The highest force that does not result in coating failure up to 160 in-lbs is recorded. The test is performed by impacting the coating directly (direct), coating facing upward. The threshold of impact resistance was 80 in-lbs.
  • Cross hatch adhesion was measured according to ASTM D3359. A rating of 4B or 5B is considered an acceptable level of adhesion.
  • the cured panels were immersed in hot water (80° C.) for 5 days. Upon completion the panels were removed from the hot water bath, dried and allowed to cool to ambient lab temperatures. The coatings were visually inspected for delaminating, blistering, bubbling, etc. in the scribed area from the cross-hatch adhesion test. If no damage was observed, the top coat was rated as a pass for adhesion.
  • Coatings were applied to 4 inch by 12 inch aluminum chromate pre-treated and steel phosphate pre-treated panels using a wire wound rod or a 8 path wet film applicator.
  • the panels were pre-cleaned by wiping with a lint free cloth and IPA to remove oils and dried with compressed air or nitrogen.
  • the coated panels were allowed to cure for a minimum of 7 days at 50% relative humidity (RH) and ambient laboratory temperatures ( ⁇ 24° C.) prior to testing.
  • RH relative humidity
  • ambient laboratory temperatures ⁇ 24° C.
  • the coating formulations were prepared in a FlackTek SpeedMixwerTM (Model DAC 150 FV-K, FlackTek, Inc.) dual asymmetric centrifuge.
  • the formulations were prepared as follow:
  • a solvent blend was prepared from equal parts by weight of MIBK, n-butyl propionate, and n-propyl propionate unless another solvent was specified in the formulation tables 2.
  • a 1% catalyst solution was prepared using the above solvent blend and 1% DBTDL 3.
  • the polyols, solvents, and catalyst solution, and adhesion promoter (if present in formulation) were charged to a SpeedMixer cup 4.
  • the blend was mixed for 30 seconds at ⁇ 3000 rpm 5.
  • the isocyanate functional components were added to the SpeedMixer cup 6.
  • the blend was mixed for 30 seconds at ⁇ 3000 rpm 7. Panels were coated and allowed to cure as described above
  • isocyanate functional PDMS provide tough coatings (impact resistance) and good release properties.
  • the range of isocyanate functional PDMS in these formulations is between 5-20% based on total solids in the formulation. They also highlight that different MW isocyanate functional PDMS polymers can be used: Silmer NCO Di-50 (MW 4300 g/mol) and Silmer NCO Di-100 (MW 8000 g/mol).
  • the range of isocyanate functional PDMS in these formulations is between 20-30% of the totals solids in the formulation.
  • Example Example 18 19 Material Solids Eq Wt G G G Polyester 1 100 165 7.2 0 Polyester 2 100 306.6 0 8 Desmodur N3390 90 214 9.5 5.6 Silmer NCO Di-100 100 3950 5.4 4.4 1% DBTDL 1 0.3 0.3 Solvent Blend 0 13.1 10.9
  • Examples 20-25 demonstrate that a tie or mid coat layer is not required to achieve acceptable fouling release properties and adhesion to the primer.
  • Examples 20-25 were prepared as described above and applied to treated metal panels that were primed with a commercial marine epoxy primer (Interguard 264 manufacturer by International Paint) per the manufacturer's recommendations. The primer was applied to the panels and allowed to cure for 24, 48, 72, 96, and 168 hours respectively (Ex 20-25—examples 24 & 25 applied after 168 hours—different levels of silicone) and allowed to cure as described above.
  • Examples 26-29 demonstrate that a silane adhesion promoter can be used to further enhance the wet adhesion of the fouling release top coat without the need for a mid or tie coat.
  • Examples 24-27 were prepared as described above and applied to treated metal panels that were primed with a commercial marine epoxy primer (Interguard 264 manufacturer by International Paint) per the manufacturer's recommendations.
  • the primer was applied to the panels and allowed to cure for 24, 48, 72 or 96 hours respectively (Ex 24-27).
  • the nominal dry film thickness (DFT) of the primer was between 4-4.5 mils.
  • the top coat was applied to achieve a DFT of >2.5 mils and allowed to cure as described above.
  • the comparative examples below are 2K urethane systems. However they are differentiated from the present invention in performance and in cured coating composition.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

A two-part moisture curable coating compositions capable of forming polyurethane-polysiloxane networks is provided. The coating compositions which are useful in marine antifouling coatings provide a two-part moisture curable composition comprising: (a) a first part comprising at least one multifunctional polyol; (b) a second part comprising: (i) at least one polysiloxane polymer with at least two isocyanate or mercapto functional groups and (ii) at least one isocyanate functional organic compound; and (c) solvent. Also provided are methods of coating substrates with the curable composition and articles produced from such coated substrates.

Description

  • This invention relates to two-part moisture curable coating compositions capable of forming polyurethane-polysiloxane networks. The coating compositions are useful in the field of marine antifouling coatings.
  • Bio-fouling occurs everywhere in the marine environment and is a significant problem for marine objects, such as ships. One approach to limit fouling microorganisms from accumulating is to use self-cleaning foul releasing coatings based on silicone elastomers. Polydimethylsiloxane (PDMS) based silicone elastomer foul release coatings have a rubbery elasticity, a low surface energy and a smooth surface; making it easier for marine organisms to detach from the coating surface under shear stress generated by hydrodynamic drag. However, PDMS is soft, easily wears off, and requires frequent reapplications; thereby costing time and money to maintain.
  • One effective approach to improve the mechanical properties of PDMS based silicone coating is to blend PDMS with other polymers with better mechanical properties, such as polyurethane (PU). Polysiloxanes and polyurethanes possess very different, but highly useful, physical and mechanical properties which have led to their widespread use. Polyurethanes stand out by virtue of mechanical strength, elasticity, adhesion resistance and abrasion resistance when combined with polydimethylsiloxane in foul releasing coatings. However uniform physical blends of polysiloxanes and polyurethanes are difficult to obtain, due to incompatible properties of these resins and their pronounced tendency to undergo phase separation following initial admixture.
  • U.S. Pat. No. 8,299,200 (claiming priority to the international patent published as WO2009/025924) discloses a polysiloxane-modified polyurethane coating prepared by reacting a mixture comprising polyisocyanate; polyol; and polysiloxane having functional groups capable of reacting with the polyisocyanate. The functional groups capable of reacting with the polyisocyanate are attached to only a single end of the polyorganosiloxane chain. It is theorized that coatings that have a polysiloxane tethered at only one end, can result is a highly mobile surface and may permit easier release of fouling organisms. However, such siloxanes are expensive and coatings prepared with this system fail to exhibit all the required performance parameters of coatings in a marine environment. U.S. Pat. No. 5,820,491 discloses a two-part urethane topcoat including a polyol component, an isocyanate component and a hydroxyl functional, polyether-modified polysiloxane copolymer component. Coatings prepared with this system fail to exhibit all the required performance parameters of coatings in a marine environment. What is needed is an alternative, inexpensive, simple and uniform coating composition that blends the properties of both PDMS and PU and meets or exceeds the required performance parameters of coatings in a marine environment.
  • The present invention provides a two-part moisture curable composition comprising: (a) a first part comprising at least one multifunctional polyol; (b) a second part comprising: (i) at least one polysiloxane polymer with at least two isocyanate functional groups and (ii) at least one isocyanate functional organic compound; and (c) solvent. The present invention further provides a method of coating a substrate comprising: (a) forming a two-part moisture curable composition comprising: (i) a first part comprising at least one multifunctional polyol; (ii) a second part comprising: (A) at least one polysiloxane polymer with at least two isocyanate functional groups and (B) at least one isocyanate functional organic compound; and (iii) solvent; (b) optionally blending in one or more of pigments, dyes, gloss reducing additives, cure catalysts, flow and leveling agents, degassing additives, adhesion promoters, dispersion aids, flame-retardant agents, heat stabilizers, light stabilizers, antioxidants, plasticizers, antistatic agents, ultraviolet (UV) absorbers, lubricants or combinations thereof; and (c) applying the composition of steps (a) and (b) to a substrate and curing the composition.
  • The present invention further provides a two-part moisture curable composition comprising: (a) a first part comprising: (i) at least one multifunctional polyol and (ii) at least one polysiloxane polymer with at least two mercapto functional groups; (b) a second part comprising at least one isocyanate functional organic compound; and (c) solvent. The present invention further provides a method of coating a substrate comprising: (a) forming a two-part moisture curable composition comprising: (i) a first part comprising: (A) at least one multifunctional polyol and (B) at least one polysiloxane polymer with at least two mercapto functional groups; (ii) a second part comprising at least one isocyanate functional organic compound; and (iii) solvent; (b) optionally blending in one or more of pigments, dyes, gloss reducing additives, cure catalysts, flow and leveling agents, degassing additives, adhesion promoters, dispersion aids, flame-retardant agents, heat stabilizers, light stabilizers, antioxidants, plasticizers, antistatic agents, ultraviolet (UV) absorbers, lubricants or combinations thereof; and (c) applying the composition of steps (a) and (b) to a substrate and curing the composition.
  • The term “polyol” is an alcohol molecule containing multiple hydroxyl groups. The term “multifunctional polyol” means a polyol that has more than one reactive site capable of cross-linking. The term “polyurethane” means a resin in which the polymer units are linked by urethane linkages, i.e., —O—CO—NH—, and/or one or more urea linkages, i.e., —NH—CO—NH—. The term “isocyante” means a functional group with the formula —N═C═O. The term “mercapto” means a functional group with the formula —SH, which may also be referred to as a thiol group.
  • The polysiloxane polymer of the present invention has the formula:
  • Figure US20150307745A1-20151029-C00001
  • wherein each R1, R2, R3, R4, R5, R6, R7, R8, R9, or R10 group is independently selected from substituted or unsubstituted C1 to C60 hydrocarbon radicals, provided that (i) at least one of the R1 through R10 groups is substituted with an isocyanate functional group or a mercapto group and (ii) the polysiloxane polymer has at least two isocyante or mercapto functional groups. Preferably, at least one of the R1 through R10 groups is substituted with an isocyanate functional group and the polysiloxane polymer has at least two isocyante functional groups. Each of m and n is independently an integer from 0 and above, provided that m+n≧1. Preferably, the isocyanate functional polysiloxane has a number average molecular weight in the range of from 4,000 to 15,000, more preferably from 6,000 to 10,000. The number average molecular weight is determined by GPC Viscotek VE2001 using a Mixed D column and polystyrene standard. Examples of suitable isocyanate functional polysiloxanes include without limitation, Silmer® Di-50 and D-100 materials from Siltech Corp., which are linear-difunctional polysiloxanes represented by the formula:
  • Figure US20150307745A1-20151029-C00002
  • where a ≧1 and Silmer® C50 from Siltech Corp., a multi-functional polysiloxane represented by the formula:
  • Figure US20150307745A1-20151029-C00003
  • where a≧1 and b>1.
  • The polysiloxane polymer of the present invention makes up from 2 to 40 weight percent based on the total solids weight of the curable composition (i.e. excluding the solvent used in the curable composition). Preferably the polysiloxane polymer is from 5 to 30 weight percent based on the total solids weight of the curable composition and most preferably from 10 to 25 weight percent based on the total solids weight of the curable composition.
  • The multi-functional polyol of the present invention may be selected from acrylic polyols, natural oil polyols, polyester polyols, polyether polyols, polycarbonate polyols, and blends thereof. Acrylic polyols are preferred. Suitable acrylic polyols include acrylic polymers that range in Tg from 0-45° C. preferably from 10-40° C., and most preferably 20-35° C. and have number average molecular weights (Mn) in the range of 2,000-25,000 g/mol, preferably 3,000-15,000 g/mol and most preferably 4,000-8,000 g/mol. Examples of commercially available suitable acrylic polyols include Paraloid™ AU-750 from The Dow Chemical Company, Paraloid™ AU-830 from The Dow Chemical Company, Desmophen® A365 from Bayer Material Science AG, and Joncryl® 500 from BASF Corporation. The multi-functional polyol of the present invention makes up from 35 to 60 weight percent based on the total weight of the curable composition. Preferably the multi-functional polyol is from 40 to 55 weight percent based on the total weight of the curable composition and most preferably from 40 to 50 weight percent based on the total weight of the curable composition. The glass transition temperature (“Tg” herein) of the acrylic polymers are measured using a DSC from TA Instruments Model Q100 V9.8 Build 296 with a standard Cell FC.
  • Suitable natural oil polyols (NOPs) include non-modified NOPs, such as, for example, natural seed oil diol monomers; and modified NOPs, such as, for example, commercially available Gen 1 NOP DWD 2080 from The Dow Chemical Company, which are reconstructed NOP molecules with the monomers of saturated, mono-hydroxyl, bi-hydroxyl and tri-hydroxyl methyl esters at a weight ratio of approximately 32%, 38%, 28% and 2%. In another example, a commercially available Gen 4 NOP is obtained by reacting Unoxol™ diol and seed oil diol monomers which are separated from seed oil monomer. Unoxol™ diol is a mixture of cis, trans-1,3- and cis, trans-1,4-cyclohexane dimethanol, and is available from The Dow Chemical Company. The Gen 4 NOP has following structure with the hydroxyl equivalent weight of 170 g/mol.
  • Figure US20150307745A1-20151029-C00004
  • The natural oil derived polyols are polyols based on or derived from renewable feedstock resources such as natural and/or genetically modified plant vegetable seed oils and/or animal source fats. Such oils and/or fats are generally comprised of triglycerides, that is, fatty acids linked together with glycerol. Preferred are vegetable oils that have at least about 70 percent unsaturated fatty acids in the triglyceride. The natural product may contain at least about 85 percent by weight unsaturated fatty acids. Examples of preferred vegetable oils include, but are not limited to, for example, those from castor, soybean, olive, peanut, rapeseed, corn, sesame, cotton, canola, safflower, linseed, palm, grapeseed, black caraway, pumpkin kernel, borage seed, wood germ, apricot kernel, pistachio, almond, macadamia nut, avocado, sea buckthorn, hemp, hazelnut, evening primrose, wild rose, thistle, walnut, sunflower, jatropha seed oils, or a combination thereof.
  • Additionally, oils obtained from organisms such as algae may also be used. Examples of animal products include lard, beef tallow, fish oils and mixtures thereof. A combination of vegetable and animal based oils/fats may also be used.
  • The average hydroxyl functionality of the NOP is in the range of from 1 to 10; preferably in the range of from 2 to 6. The NOP may have a number average molecular weight in the range of from 100 to 3,000; preferably from 300 to 2,000; and more preferably from 350 to 1,500.
  • Suitable isocyanate functional organic compounds include aliphatic or cycloaliphatic polyisocyanates such as hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), methylene bis(p-cyclohexyl isocyanate) (H12MDI), meta-tetramethylxylene diisocyanate (m-TMXDI), cyclohexyl diisocyanate (CHDI), 1,3-bis(isocyanatomethyl)cyclohexane and 1,4-bis(isocyanatomethyl)cyclohexane; trimers of diisocyanates such as the trimer of hexamethylene diisocyanate (HDI) sold under the trademark Desmodur®N-3390 from Bayer MaterialScience AG, the trimer of isophorone diisocyanate (IPDI) sold under the tradename Tolanate® IDT-70 from Perstorp Polyols, Inc., and blends thereof. Preferably the isocyanate functional organic compounds are trimers of hexmethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI); and most preferably trimers of hexamethylene diisocyanate (HDI). The isocyanate functional organic compounds of the present invention make up from 8 to 30 weight percent based on the total weight of the curable composition. Preferably isocyanate functional organic compounds are from 10 to 30 weight percent based on the total weight of the curable composition and most preferably from 15 to 25 weight percent based on the total weight of the curable composition.
  • Suitable urethane grade solvents include aromatic hydrocarbons such as xylene, toluene; ketones such as methyl isobutyl ketone, methyl amyl ketone, or acetone, esters such as butyl acetate, or hexyl acetate; glycol ether esters such as propylene glycol monomethyl ether acetate; esters such as propyl propionate or butyl propionate, and blends thereof. The solvent makes up from 10 to 60 weight percent based on the total weight of the curable composition. Preferably solvent is from 15 to 50 weight percent based on the total weight of the curable composition and most preferably from 20 to 40 weight percent based on the total weight of the curable composition.
  • The curable compositions are useful as coatings and may include various additives ordinarily incorporated in compositions of this type. Examples of additional additives include, but are not limited to, pigments, dyes, gloss reducing additives, cure catalysts, flow and leveling agents, degassing additives, adhesion promoters, dispersion aids, flame-retardant agents, heat stabilizers, light stabilizers, antioxidants, plasticizers, antistatic agents, ultraviolet (UV) absorbers, lubricants or combinations including one or more of the foregoing additives.
  • Suitable adhesion promoters include silane adhesion promoters, such as 3-glycidoxypropyl trimethoxysilane, which can enhance the wet adhesion of the fouling release top coat without the need for a mid or tie coat. Preferably the silane adhesion promoter is in the range of from 0.5 to 3 weight percent based on the total weight of the curable composition, more preferably from 1 to 3 weight percent based on the total weight of the curable composition, and most preferably from 1.5 to 3 weight percent based on the total weight of the curable composition.
  • Curable coating compositions of the present invention can be un-pigmented transparent clear coats, or pigmented systems for primer, basecoat and topcoat applications. The pigment may be any typical organic or inorganic pigment. Several different pigments may be needed to achieve a desirable color for a particular application. Examples of suitable pigments include without limitation, titanium dioxide, barytes, clay, calcium carbonate, red iron oxide, CI Pigment Yellow 42, CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4 (copper phthalocyanines), CI Pigment Red 49:1, CI Pigment Red 57:1 and carbon black.
  • The resulting coating compositions can be applied onto a substrate using techniques known in the art; e.g. by spraying, draw-down, roll-coating. The nominal dry film thickness (DFT) of the coating is greater than or equal to 2 mils, preferably greater than 2.5 mils and more preferably greater than 3 mils. Examples of substrates that may be coated include without limitation, plastics, wood, metals such as aluminum, steel or galvanized sheeting, tin-plated steel, concrete, glass, composites, urethane elastomers, primed (painted) substrates, and the like. The coatings can be cured at room temperature or at an elevated temperature in a forced air oven or with other types of heating sources.
  • The following examples are illustrative of the invention.
    • Experimental Methods
  • The raw materials used in the Examples are described below.
    • Raw Materials
  • Material Function Supplier
    Acrylic Polyol A comprises by weight, in Polyol Synthesized in
    polymerized form, 42% methyl methacrylate laboratory.
    (MMA), 30% hydroxyethylmethacrylate (HEMA)
    and 28% butyl acrylate (BA), with a Tg of 31° C., a
    solution hydroxyl equivalent weight of 552 at
    80.3% solids and a Mn of 4600.
    Acrylic Polyol B comprises by weight, in Polyol Synthesized in
    polymerized form, 30% MMA, 30% HEMA and laboratory.
    40% BA, with a Tg of 14° C., a solution hydroxyl
    equivalent weight of 551 at 76.4% solids and a
    Mn of 3800.
    Acrylic Polyol C comprises by weight, in Polyol Synthesized in
    polymerized form, 16% MMA, 30% HEMA and laboratory.
    54% BA, with a Tg of −3° C., a solution hydroxyl
    equivalent weight of 557 at 73.1% solids and a
    Mn of 5000.
    Acrylic Polyol D is the same composition as Polyol Synthesized in
    Acrylic Polyol A, but with a solution hydroxyl laboratory.
    equivalent weight of 610 at 77.5% solids and a
    Mn of 3500.
    Polyester 1 (Natural Oil Polyol) with a solution Polyol The Dow Chemical
    hydroxyl equivalent weight of 170 at 77.5% Company
    solids
    Polyester 2 (CAPA ™ 3091 polycaprolactone), Polyol Perstorp Polyols,
    CAS Number 37625-56-2 with a molecular Inc.
    weight of 900.
    Polyester 3 (CAPA ™ 3050 polycaprolactone), Polyol Perstorp Polyols,
    CAS Number 37625-56-2 with a molecular Inc.
    weight of 540.
    Silmer ® NCO Di-50, molecular weight of 4300 Isocyanate Siltech Corp.
    g/mol according to manufacturer functional PDMS
    Silmer ® NCO Di-100, molecular weight of 8000 Isocyanate Siltech Corp.
    g/mol according to manufacturer functional PDMS
    Silmer ® NCO C-50, molecular weight of 12,400 Isocyanate Siltech Corp.
    g/mol according to the manufacturer functional PDMS
    Desmodur ® N3390 aliphatic polyisocyanate (HDI Isocyanate Bayer
    Trimer 90% solids in butyl acetate) functional organic MaterialScience AG
    compound
    Tolanate ® IDT-70 aliphatic polyisocyante (IPDI Isocyanate Perstorp Polyols,
    Trimer 70% Solids in butyl acetate) functional organic Inc.
    compound
    Siloxane 1 (MCR-C62 mono-dicarbinol Hydroxy functional Gelest, Inc.
    terminated polydimethylsiloxane), with a PDMS
    molecular weight of 5,000
    Siloxane 2 (Dow Corning ® 54 Additive dimethyl, Hydroxy functional Dow Corning
    methyl(polypropylene oxide) siloxane), CAS siloxane Corporation
    Number 68957-00-6,
    Siloxane 3 (Dow Corning ® 29 Additive Hydroxy functional Dow Corning
    octamethylcyclotetrasiloxane and siloxane Corporation
    decamethylcyclopentasiloxane), CAS Numbers
    556-67-2 and 541-02-6
    n-Butyl Propionate Solvent The Dow Chemical
    Company
    n-Propyl Propionate Solvent The Dow Chemical
    Company
    Methyl Isobutyl Ketone (MIBK) Solvent Honeywell Burdick-
    Jackson, a subsidiary
    of Honeywell
    International, Inc.
    Z-6040 silane (glycidoxypropyl trimethoxy- Silane adhesion Dow Corning
    silane) promoter Corporation
    Dibutytin dilaurate (DBTDL) Catalyst Sigma-Aldrich Co.
    • Test Procedures: Pseudo-Barnacle Pull Off Strength Test
  • The test was carried out according to a modified procedure as described in reference (Kohl JG& Singer IL, Pull-off behavior of epoxy bonded to silicone duplex coatings, Progress in Organic Coatings, 1999, 36:15-20) using an Instron machine under the trade designation Instron™ Model 1122. Ten-millimeter diameter aluminum studs were used and glued to the surface of the coated panels using an epoxy adhesive (Hysol® 1C from Henkel Loctite Americas, www.loctite.com). The excessive epoxy was trimmed after about one hour cure. The epoxy adhesive was then allowed to harden for at least three days at room temperature. The stud was then pulled off using an Instron machine until the stud detached from the coating surface. For each test, at least two and preferably three replicate samples were employed and the average value for pull off strength (measured in MPa units) was recorded. The threshold of pseudo-barnacle pull off strength was 0.6 MPa.
    • Contact Angle Test
  • The water contact angle of the coatings was measured using a VCA Optima contact angle measuring device from AST Products, Inc. A water droplet, 0.5-1 μl was placed on the coating surface. After the equilibrium time the contact angle was measured. A higher contact angle means the coating surface is hydrophobic. For a fouling release coating the contact angle should be ≧100°.
    • Impact Resistance
  • The impact resistance of the coating was determined by using a Gardner impact tester according to ASTM D2794. This test involves dropping a weight onto an indenter which is resting on the surface of the coating. The weight is dropped from a known height and the indenter forms a dimple in the coated panel. The coating is observed for cracking or delaminating on or around the dimple. The force to produce cracking/delaminating is recorded in inch-pounds (in-lb). The highest force that does not result in coating failure up to 160 in-lbs is recorded. The test is performed by impacting the coating directly (direct), coating facing upward. The threshold of impact resistance was 80 in-lbs.
    • Cross Hatch Adhesion
  • Cross hatch adhesion was measured according to ASTM D3359. A rating of 4B or 5B is considered an acceptable level of adhesion.
    • Adhesion—Hot Water Immersion
  • The cured panels were immersed in hot water (80° C.) for 5 days. Upon completion the panels were removed from the hot water bath, dried and allowed to cool to ambient lab temperatures. The coatings were visually inspected for delaminating, blistering, bubbling, etc. in the scribed area from the cross-hatch adhesion test. If no damage was observed, the top coat was rated as a pass for adhesion.
    • Coating Application & Cure
  • Coatings were applied to 4 inch by 12 inch aluminum chromate pre-treated and steel phosphate pre-treated panels using a wire wound rod or a 8 path wet film applicator. The panels were pre-cleaned by wiping with a lint free cloth and IPA to remove oils and dried with compressed air or nitrogen. The coated panels were allowed to cure for a minimum of 7 days at 50% relative humidity (RH) and ambient laboratory temperatures (˜24° C.) prior to testing.
    • Formulations: EXAMPLES 1-29 & COMPARATIVE EXAMPLES 1-3
  • The coating formulations were prepared in a FlackTek SpeedMixwer™ (Model DAC 150 FV-K, FlackTek, Inc.) dual asymmetric centrifuge. The formulations were prepared as follow:
  • 1. A solvent blend was prepared from equal parts by weight of MIBK, n-butyl propionate, and n-propyl propionate unless another solvent was specified in the formulation tables
    2. A 1% catalyst solution was prepared using the above solvent blend and 1% DBTDL
    3. The polyols, solvents, and catalyst solution, and adhesion promoter (if present in formulation) were charged to a SpeedMixer cup
    4. The blend was mixed for 30 seconds at ˜3000 rpm
    5. The isocyanate functional components were added to the SpeedMixer cup
    6. The blend was mixed for 30 seconds at ˜3000 rpm
    7. Panels were coated and allowed to cure as described above
  • Examples
    1 2 3 4 5 6
    Material Solids Eq Wt G G G G G G
    Acrylic Polyol A 80.3 552 11 11
    Acrylic Polyol B 76.4 551 12 12
    Acrylic Polyol C 73.1 557 12 12
    Desmodur N3390 90 214 4.4 4.8 4.8 4.4 4.8 4.8
    Silmer NCO C-50 100 4133 1.5 1.5 1.5
    Silmer NCO Di-100 100 3950 1.4 1.5 1.5
    1% DBTDL 1 0.3 0.3 0.3 0.3 0.3 0.3
    Solvent Blend 0 4.7 4.3 3.7 4.6 4.4 3.6
    • Testing Results for Examples 1-6
  • Pseudo-Barnacle Impact
    Contact Adhesion Direct Indirect
    Example Angle MPa In-lbs In-lbs
    1 107° 0.18 >160 >160
    2 109° 0.23 >160 >160
    3 106° 0.23 >160 >160
    4 106° 0.11 >160 >160
    5 106° 0.12 >160 >160
    6 106° 0.16 >160 >160
  • These results illustrate that acrylic polyols of different glass transition temperatures yield coatings with excellent toughness as illustrated by the impact resistance results and release properties. They also illustrate that different level of isocyanate functionality on the PDMS polymers (Silmer C-50 is a tri-functional whereas Silmer Di-100 is di-functional) provide the same results. The level of isocyanate functional PDMS in these examples is 10% based on total solids in the formulation.
  • Examples
    7 8 9 10 11 12
    Material Solids Eq Wt G G G G G G
    Acrylic Polyol A 80.3 552 13 12.5 11 13.1 12.4 11
    Desmodur N3390 90 214 5.2 4.9 4.2 5.3 5 4.3
    Silmer NCO Di-50 100 2150 0.8 1.6 3.1
    Silmer NCO Di-100 100 3950 0.8 1.6 3.2
    1% DBTDL 1 0.4 0.4 0.3 0.4 0.4 0.3
    Solvent Blend 0 4.2 5.2 6.9 4.2 5.2 7.1
    • Testing Results for Examples 7-12
  • Pseudo-Barnacle Impact
    Contact Adhesion Direct Indirect
    Example Angle MPa In-lbs In-lbs
    7 103° 0.24 >160 >160
    8 103° 0.3 >160 >160
    9 109° 0.24 >160 >160
    10 105° 0.23 >160 >160
    11 103° 0.16 >160 >160
    12 100° 0.08 >160 >160
  • These results illustrate that different level of the isocyanate functional PDMS provide tough coatings (impact resistance) and good release properties. The range of isocyanate functional PDMS in these formulations is between 5-20% based on total solids in the formulation. They also highlight that different MW isocyanate functional PDMS polymers can be used: Silmer NCO Di-50 (MW 4300 g/mol) and Silmer NCO Di-100 (MW 8000 g/mol).
  • Examples
    13 14 15
    Material Solids Eq Wt G G G
    Acrylic Polyol A 80.3 552 10.2 9.2 11
    Desmodur N3390 90 214 3.9 3.5 4.4
    Silmer NCO Di-100 100 3950 3.9 4.5 3.2
    1% DBTDL 1 0.3 0.3 0.3
    Solvent Blend 0 7.9 8.6 7.1
    • Testing Results for Examples 13-15
  • Pseudo-Barnacle Impact
    Contact Adhesion Direct Indirect
    Example Angle MPa In-lbs In-lbs
    13 102° 0.1 >160 120
    14 101° 0.11 >160 80
    15 100° 0.13 >160 100
  • These results further expand the level of the isocyanate functional PDMS to provide tough coatings (impact resistance) and good release properties. The range of isocyanate functional PDMS in these formulations is between 20-30% of the totals solids in the formulation.
  • Examples
    16 17
    Material Solids Eq Wt G G
    Acrylic Polyol D 80.27 552 10.2 11
    Desmodur N3390 90 214 3.6 3.9
    Silmer NCO Di-100 100 3950 3.7 3
    1% DBTDL 1 0.3 0.3
    Solvent Blend 0 6.9 6.8
    • Testing Results for Examples 16 and 17
  • Pseudo-Barnacle Impact
    Contact Adhesion Direct Indirect
    Example Angle MPa in/lbs in/lbs
    16 103° 0.24 >160 >160
    17 101° 0.26 >160 >160
  • This data confirms the earlier data at 20 and 25% isocyanate functional PDMS in the formulations using a new lot of Acrylic Polyol A, labeled Acrylic Polyol D (slightly higher OH equivalent weight) still illustrating excellent toughness (impact resistance) and release properties.
  • Example Example
    18 19
    Material Solids Eq Wt G G
    Polyester 1 100 165 7.2 0
    Polyester 2 100 306.6 0 8
    Desmodur N3390 90 214 9.5 5.6
    Silmer NCO Di-100 100 3950 5.4 4.4
    1% DBTDL 1 0.3 0.3
    Solvent Blend 0 13.1 10.9
    • Testing Results for Examples 18 and 19
  • Pseudo-Barnacle Impact
    Contact Adhesion Direct
    Example Angle MPa in/lbs
    18 105° 0.2 >160
    19 121° 0.57 >160
  • This data confirms that polyols other than acrylic can be used. However, acrylic polyols are preferred.
  • Examples
    20 21 22 23 24 25
    Material Solids Eq Wt G G G G G G
    Acrylic Polyol D 77.5 609.7 4.5 4.5 4.5 4.5 11 10.2
    Desmodur N3390 90 214 1.6 1.6 1.6 1.6 3.9 3.6
    Silmer NCO Di-100 100 3950 1.7 1.7 1.7 1.7 3 3.7
    1% DBTDL 1 0.1 0.1 0.1 0.1 0.3 0.3
    Solvent Blend 0 3.1 3.1 3.1 3.1 6.8 6.9
    • Testing Results for Examples 20-25
  • Overcoat Pseudo-Barnacle
    Interval Adhesion Cross Hatch Hot Water
    Example Hours MPa Adhesion Adhesion
    20 24 0.32 5B Pass
    21 48 0.29 5B Pass
    22 72 0.23 5B Pass
    23 96 0.31 5B Pass
    24 168 0.2 5B Fail
    25 168 0.23 5B Fail
  • Examples 20-25 demonstrate that a tie or mid coat layer is not required to achieve acceptable fouling release properties and adhesion to the primer. Examples 20-25 were prepared as described above and applied to treated metal panels that were primed with a commercial marine epoxy primer (Interguard 264 manufacturer by International Paint) per the manufacturer's recommendations. The primer was applied to the panels and allowed to cure for 24, 48, 72, 96, and 168 hours respectively (Ex 20-25—examples 24 & 25 applied after 168 hours—different levels of silicone) and allowed to cure as described above.
  • These examples demonstrate that excellent release properties can be achieved without the use of a tie or mid coat applied between a primer and the fouling release top coat. These results also show a preferred over coat window between applying the top coat over the primer between 24 and 144 hours, preferably between 24 and 120 hours, and more preferably between 48-96 hours with excellent adhesion as demonstrated by the hot water adhesion test.
  • Examples
    26 27 28 29
    Material Solids Eq Wt G G G G
    Acrylic Polyol D 77.5 609.7 4.2 4.2 4.2 4.2
    Desmodur N3390 90 214 1.4 1.5 1.5 1.5
    Silmer NCO Di-100 100 3950 1.6 1.6 1.6 1.6
    Z-6040 100 0.2 0.2 0.2 0.2
    1% DBTDL 1 0.1 0.1 0.1 0.1
    Solvent Blend 0 3.1 3.0 3.0 3.0
    • Testing Results for Examples 26-29
  • Overcoat Pseudo-Barnacle
    Interval Adhesion Cross Hatch Hot Water
    Example Hours MPa Adhesion Adhesion
    26 24 0.32 5B Pass
    27 48 0.24 5B Pass
    28 72 0.26 5B Pass
    29 96 0.25 5B Pass
  • Examples 26-29 demonstrate that a silane adhesion promoter can be used to further enhance the wet adhesion of the fouling release top coat without the need for a mid or tie coat.
  • Examples 24-27 were prepared as described above and applied to treated metal panels that were primed with a commercial marine epoxy primer (Interguard 264 manufacturer by International Paint) per the manufacturer's recommendations. The primer was applied to the panels and allowed to cure for 24, 48, 72 or 96 hours respectively (Ex 24-27). The nominal dry film thickness (DFT) of the primer was between 4-4.5 mils. The top coat was applied to achieve a DFT of >2.5 mils and allowed to cure as described above.
  • These examples demonstrate that excellent release properties can be achieved without the use of a tie or mid coat applied between a primer and the fouling release top coat with excellent adhesion as demonstrated by the hot water adhesion test when a silane adhesion promoter is added to the top coat formulation. Visually the panels for examples 26-29 looked better after the hot water adhesion test than those of examples 20-23. The range of silane adhesion promoter should be between 0.5-3% based on weight, preferably between 1-3% % based on weight, and more preferably between 1.5-3% based on weight.
    • Comparative Examples
  • The comparative examples below are 2K urethane systems. However they are differentiated from the present invention in performance and in cured coating composition.
  • Comparative Examples
    1 2 3
    Material Solids Eq Wt G G G
    Polyester 3 90 201 5.5 5.5 5.5
    Tolanate IDT 70 70 343 10.50 10.6 10.8
    Siloxane 1 100 2500 1.40 0 0
    Siloxane 2 100 2000 0 1.4 0
    Siloxane 3 100 1200 0 0 1.4
    1% DBTDL 1 0.3 0.3 0.3
    n-butyl acetate 0 3.4 3.4 3.5
    • Results for Comparative Examples 1-3
  • Pseudo-Barnacle
    Comparative Contact Adhesion Cross Hatch Hot Water
    Example Angle MPa Adhesion Adhesion
    1 91° 0.06 5B Fail
    2 74° 0.13 5B Fail
    3 50° 0.02 5B Fail
  • None of the contact angles met the threshold for a fouling release coating exhibiting a water contact angle of ≧100°. The coating quality for each of the comparative examples was extremely poor due to severe blooming of the siloxane component that could be easily wiped from the surface. Although the pseudo-barnacle adhesion meets the requirement, none of the coatings passed the hot water adhesion test after immersion—all of the coating severely delaminated from the substrate and cracked. These comparative examples highlight the performance advantages of the present invention compared to other 2K urethane fouling release technologies, by exhibiting better adhesion without a mid or tie coat and better coating quality.

Claims (13)

1. A two-part moisture curable composition comprising:
(a) a first part comprising: (i) at least one multifunctional polyol and (ii) at least one polysiloxane polymer with at least two mercapto functional groups;
(b) a second part comprising at least one isocyanate functional organic compound; and
(c) solvent.
2. The composition of claim 1 wherein the polysiloxane polymer has a number average molecular weight in the range of from 4,000 to 15,000.
3. The composition of claim 1 wherein the polysiloxane polymer is from 2 to 40 weight percent based on the total solids weight of the curable composition.
4. The composition of claim 1 wherein the multifunctional polyol is selected from the group consisting of acrylic polyols, natural oil polyols, polyester polyols, polyether polyols, polycarbonate polyols, and blends thereof.
5. The composition of claim 1 wherein the multifunctional polyol is an acrylic polymer with a Tg in the range of from 0° C. to 45° C. and a number average molecular weight in the range of from 2,000 g/mol to 25,000 g/mol.
6. The composition of claim 1 wherein the multifunctional polyol is from 35 to 60 weight percent based on the total weight of the curable composition.
7. The composition of claim 1 wherein the isocyanate functional organic compound is selected from the group consisting of hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), methylene bis(p-cyclohexyl isocyanate) (H12MDI), meta-tetramethylxylene diisocyanate (m-TMXDI), cyclohexyl diisocyanate (CHDI), 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, trimers of diisocyanates, and blends thereof.
8. The composition of claim 1 wherein the isocyanate functional organic compound is from 8 to 30 weight percent based on the total weight of the curable composition.
9. The composition of claim 1 further comprising one or more of pigments, dyes, gloss reducing additives, cure catalysts, flow and leveling agents, degassing additives, adhesion promoters, dispersion aids, flame-retardant agents, heat stabilizers, light stabilizers, antioxidants, plasticizers, antistatic agents, ultraviolet (UV) absorbers, lubricants or combinations thereof.
10. The composition of claim 9 wherein the adhesion promoter is 3-glycidoxypropyl trimethoxysilane.
11. The composition of claim 1 wherein:
(a) the polysiloxane polymer is from 2 to 40 weight percent based on the total solids weight of the curable composition and has a number average molecular weight in the range of from 4,000 to 15,000;
(b) the multifunctional polyol is from 35 to 60 weight percent based on the total weight of the curable composition and is an acrylic polymer with a Tg in the range of from 0° C. to 45° C. and a number average molecular weight in the range of from 2,000 g/mol to 25,000 g/mol; and
(c) the isocyanate functional organic compound is from 8 to 30 weight percent based on the total weight of the curable composition and is selected from the group consisting of hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), methylene bis(p-cyclohexyl isocyanate) (H12MDI), meta-tetramethylxylene diisocyanate (m-TMXDI), cyclohexyl diisocyanate (CHDI), 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, trimers of diisocyanates, and blends thereof.
12. A method of coating a substrate comprising:
(a) forming a two-part moisture curable composition comprising:
(i) a first part comprising: (A) at least one multifunctional polyol and (B) at least one polysiloxane polymer with at least two mercapto functional groups;
(ii) a second part comprising at least one isocyanate functional organic compound; and
(iii) solvent;
(b) optionally blending in one or more of pigments, dyes, gloss reducing additives, cure catalysts, flow and leveling agents, degassing additives, adhesion promoters, dispersion aids, flame-retardant agents, heat stabilizers, light stabilizers, antioxidants, plasticizers, antistatic agents, ultraviolet (UV) absorbers, lubricants or combinations thereof;
(c) applying the composition of steps (a) and (b) to a substrate and curing the composition.
13. A coated article made by the method of claim 12.
US14/795,088 2012-12-31 2015-07-09 Siloxane-urethane foul release coatings Abandoned US20150307745A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US14/795,088 US20150307745A1 (en) 2012-12-31 2015-07-09 Siloxane-urethane foul release coatings

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CN201210599271.4A CN103910853B (en) 2012-12-31 2012-12-31 The stained desorption coating of siloxanes-carbamate groups
CN201210599271.4 2012-12-31
US14/132,119 US9145500B2 (en) 2012-12-31 2013-12-18 Siloxane-urethane foul release coatings
US14/795,088 US20150307745A1 (en) 2012-12-31 2015-07-09 Siloxane-urethane foul release coatings

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US14/132,119 Division US9145500B2 (en) 2012-12-31 2013-12-18 Siloxane-urethane foul release coatings

Publications (1)

Publication Number Publication Date
US20150307745A1 true US20150307745A1 (en) 2015-10-29

Family

ID=49816851

Family Applications (2)

Application Number Title Priority Date Filing Date
US14/132,119 Active 2034-03-25 US9145500B2 (en) 2012-12-31 2013-12-18 Siloxane-urethane foul release coatings
US14/795,088 Abandoned US20150307745A1 (en) 2012-12-31 2015-07-09 Siloxane-urethane foul release coatings

Family Applications Before (1)

Application Number Title Priority Date Filing Date
US14/132,119 Active 2034-03-25 US9145500B2 (en) 2012-12-31 2013-12-18 Siloxane-urethane foul release coatings

Country Status (6)

Country Link
US (2) US9145500B2 (en)
EP (2) EP2927255A1 (en)
JP (1) JP6235329B2 (en)
KR (1) KR102104265B1 (en)
CN (1) CN103910853B (en)
BR (1) BR102013032886B8 (en)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9392841B2 (en) 2014-08-27 2016-07-19 Nike Innovate C.V. Article of footwear with soil-shedding performance
US10070686B2 (en) 2014-08-27 2018-09-11 Nike, Inc. Soil-shedding article of footwear, components thereof, and methods of making the article
US10314364B2 (en) 2014-08-27 2019-06-11 Nike, Inc. Soil-shedding article of footwear, and method of using the same
US10362834B2 (en) 2016-03-02 2019-07-30 Nike, Inc. Hydrogel connection
US10405604B2 (en) 2014-08-27 2019-09-10 Nike, Inc. Article of footwear with soil-shedding performance
US10455893B2 (en) 2016-03-02 2019-10-29 Nike, Inc. Hydrogel with mesh for soil deflection
US10463105B2 (en) 2014-08-27 2019-11-05 Nike, Inc. Articles of footwear, apparel, and sports equipment with soil-shedding properties
US10531705B2 (en) 2016-03-02 2020-01-14 Nike, Inc. Hydrogel tie layer
US10675609B2 (en) 2016-03-02 2020-06-09 Nike, Inc. Articles with soil-shedding performance
US10919257B2 (en) 2017-10-19 2021-02-16 Nike, Inc. Composite materials, methods of making, methods of use, and articles incorporating the composite materials
EP3822297A1 (en) * 2019-11-15 2021-05-19 Covestro Deutschland AG Polysiloxane functionalized polyurethanes for enhancing hydrophobisation of surfaces
US11084239B2 (en) 2017-08-01 2021-08-10 Nike, Inc. Method of manufacturing a component of an outsole for use in an article of footwear

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10835905B2 (en) 2011-05-25 2020-11-17 Cidra Corporate Services Inc. Recovery media for mineral processing
CA2941109A1 (en) * 2014-03-12 2015-09-17 Rust-Oleum Corporation Vegetable oil-modified, hydrophobic polyurethane dispersions
PT3067402T (en) * 2015-03-09 2017-07-28 SWISS KRONO Tec AG Binder composition and use of same in wooden boards
KR102057847B1 (en) 2015-04-28 2019-12-20 에이치피 인디고 비.브이. Coating system
CN105400405B (en) * 2015-10-30 2018-06-22 华南理工大学 A kind of selfreparing organic silicon polyurethane/polyureas anti-fouling material and its method and application
CA3010306C (en) * 2016-01-07 2022-11-08 Cidra Corporate Services Llc Open cell or reticulated foam functionalized open-network structure for selective separation of mineral particles in an aqueous system
WO2017202692A1 (en) * 2016-05-24 2017-11-30 Basf Coatings Gmbh Coating agents and coatings produced therefrom with improved resistance to soiling and (self)cleaning properties and use thereof
KR101854047B1 (en) * 2016-11-14 2018-05-02 주식회사 케이씨씨 Antifouling paint compositions
CN108920891A (en) * 2018-07-10 2018-11-30 哈尔滨理工大学 Polyethylene and montmorillonite trap level evaluation method based on density functional theory
CN110511671B (en) * 2019-08-07 2021-11-30 安徽海德化工科技有限公司 Cracking-resistant heat-resistant coating for petroleum distillation tower
CN110511672B (en) * 2019-08-15 2021-05-04 广东普赛达密封粘胶有限公司 Bottom-coating active siloxane composition and preparation method and application thereof
CN110791193A (en) * 2019-11-18 2020-02-14 上海君子兰新材料股份有限公司 Water-based bi-component bright white paint with excellent comprehensive performance and preparation method thereof
CN111808515A (en) * 2020-06-24 2020-10-23 中国船舶重工集团公司第七二五研究所 Preparation method of degradable amphiphilic fouling-resistant antifouling resin
CN113583557B (en) * 2021-09-09 2022-04-01 斯博锐精细化学品(广东)有限公司 Preparation method of polypropylene-polyurethane weather-resistant paint
CN114106690B (en) * 2021-10-28 2022-06-21 吉林大学 Microphase separation type marine antifouling anticorrosive coating and preparation method thereof
CN114409869B (en) * 2022-01-12 2023-07-11 万华化学集团股份有限公司 Multi-curing isocyanate prepolymer and preparation method and application thereof

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4002794A (en) * 1975-07-18 1977-01-11 Nashua Corporation Adhesive material and articles incorporating same
US4234697A (en) * 1979-01-18 1980-11-18 Dow Corning Corporation Method of preparing cross-linked polydiorganosiloxane using organic isocyanates and products prepared therefrom
US4684538A (en) * 1986-02-21 1987-08-04 Loctite Corporation Polysiloxane urethane compounds and adhesive compositions, and method of making and using the same
US4902767A (en) 1987-05-28 1990-02-20 Lord Corporation High slip urethane-siloxane coatings
EP0404895A4 (en) 1988-12-14 1991-05-15 Bramite Limited Silicone modified polyurethanes
DE4004628A1 (en) * 1990-02-15 1991-08-22 Beutelrock Geb Wehrmann Caroli MEDIUM FOR PAINT-REPELLENT COATING OF SUBSTRATES
GB9127171D0 (en) 1991-12-20 1992-02-19 Courtaulds Coatings Holdings Coating compositions
JP3073915B2 (en) * 1995-06-27 2000-08-07 信越化学工業株式会社 Method for producing thermoplastic silicone-modified polyurethane resin
US5820491A (en) 1996-02-07 1998-10-13 Ppg Industries, Inc. Abrasion resistant urethane topcoat
TW415952B (en) * 1998-12-14 2000-12-21 Chung Shan Inst Of Science A modifier and a method for improving the flexibility of a cured epoxy resin
US6545114B1 (en) * 2001-08-09 2003-04-08 Chung-Shan Institute Of Science & Technology Polysiloxaneurethane-poly(acrylic acid)/polyacrylate copolymer and method for making the same
KR100542428B1 (en) * 2003-12-31 2006-01-11 주식회사 케이씨씨 Urethane paints composition for 1-coating
US8062729B2 (en) * 2005-01-14 2011-11-22 Ndsu Research Foundation Polymeric material with surface microdomains
EP1913060A4 (en) 2005-07-29 2008-11-26 Ndsu Res Foundation Functionalized polysiloxane polymers
ATE519798T1 (en) * 2006-08-14 2011-08-15 Bayer Materialscience Llc LOW SURFACE ENERGY POLYISOCYANATES AND THEIR USE IN TWO-COMPONENT COATING COMPOSITIONS
US8299200B2 (en) 2007-06-11 2012-10-30 Ndsu Research Foundation Anchored polysiloxane-modified polyurethane coatings and uses thereof
EP2058355A1 (en) * 2007-11-08 2009-05-13 Bayer MaterialScience AG Polysiloxane modified polyisocyanate
JP4798396B2 (en) 2008-07-07 2011-10-19 信越化学工業株式会社 Underwater biological adhesion prevention coating composition and underwater structure using the same
CN102757719B (en) * 2011-04-25 2014-08-20 陶氏环球技术有限公司 Dual-packaging moisture-curable coating compound
US8450242B2 (en) * 2011-04-26 2013-05-28 Eastman Kodak Company Thermal transfer donor element
US8716396B2 (en) * 2012-04-19 2014-05-06 Arrowstar Llc Nonfluorinated polyurethanes and methods of making and using thereof

Cited By (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10076159B2 (en) 2014-08-27 2018-09-18 Nike, Inc. Soil-shedding article of footwear, and method of using the same
US10051913B2 (en) 2014-08-27 2018-08-21 Nike, Inc. Article of footwear with soil-shedding performance
US10076154B2 (en) 2014-08-27 2018-09-18 Nike, Inc. Article of footwear with soil-shedding performance
US10064447B2 (en) 2014-08-27 2018-09-04 Nike, Inc. Article of footwear with soil-shedding performance
US10070685B2 (en) 2014-08-27 2018-09-11 Nike, Inc. Article of footwear with soil-shedding performance
US10070686B2 (en) 2014-08-27 2018-09-11 Nike, Inc. Soil-shedding article of footwear, components thereof, and methods of making the article
US10076155B2 (en) 2014-08-27 2018-09-18 Nike, Inc. Article of footwear with soil-shedding performance
US10076157B2 (en) 2014-08-27 2018-09-18 Nike, Inc. Article of footwear with soil-shedding performance
US10085513B2 (en) 2014-08-27 2018-10-02 Nike, Inc. Article of footwear with soil-shedding performance
US10076158B2 (en) 2014-08-27 2018-09-18 Nike, Inc. Article of footwear with soil-shedding performance
US11178933B2 (en) 2014-08-27 2021-11-23 Nike, Inc. Article of footwear with soil-shedding performance
US9456654B2 (en) 2014-08-27 2016-10-04 Nike, Inc. Article of footwear with soil-shedding performance
US10076156B2 (en) 2014-08-27 2018-09-18 Nike, Inc. Article of footwear with soil-shedding performance
US10092062B2 (en) 2014-08-27 2018-10-09 Nike, Inc. Article of footwear with soil-shedding performance
US10130140B2 (en) 2014-08-27 2018-11-20 Nike, Inc. Article of footwear with soil-shedding performance
US10314364B2 (en) 2014-08-27 2019-06-11 Nike, Inc. Soil-shedding article of footwear, and method of using the same
US9392841B2 (en) 2014-08-27 2016-07-19 Nike Innovate C.V. Article of footwear with soil-shedding performance
US10405604B2 (en) 2014-08-27 2019-09-10 Nike, Inc. Article of footwear with soil-shedding performance
US11517071B2 (en) 2014-08-27 2022-12-06 Nike, Inc. Article of footwear with soil-shedding performance
US10463105B2 (en) 2014-08-27 2019-11-05 Nike, Inc. Articles of footwear, apparel, and sports equipment with soil-shedding properties
US11445782B2 (en) 2014-08-27 2022-09-20 Nike, Inc. Articles of footwear, apparel, and sports equipment with soil-shedding properties
US11103026B2 (en) 2014-08-27 2021-08-31 Nike, Inc. Article of footwear with soil-shedding performance
US10362834B2 (en) 2016-03-02 2019-07-30 Nike, Inc. Hydrogel connection
US10675609B2 (en) 2016-03-02 2020-06-09 Nike, Inc. Articles with soil-shedding performance
US10531705B2 (en) 2016-03-02 2020-01-14 Nike, Inc. Hydrogel tie layer
US10455893B2 (en) 2016-03-02 2019-10-29 Nike, Inc. Hydrogel with mesh for soil deflection
US11540591B2 (en) 2016-03-02 2023-01-03 Nike, Inc. Hydrogel tie layer
US11084239B2 (en) 2017-08-01 2021-08-10 Nike, Inc. Method of manufacturing a component of an outsole for use in an article of footwear
US11840036B2 (en) 2017-08-01 2023-12-12 Nike, Inc. Method of manufacturing a component of an outsole for use in an article of footwear
US11001031B2 (en) 2017-10-19 2021-05-11 Nike, Inc. Composite materials, methods of making, methods of use, and articles incorporating the composite materials
US10919257B2 (en) 2017-10-19 2021-02-16 Nike, Inc. Composite materials, methods of making, methods of use, and articles incorporating the composite materials
US11130309B2 (en) 2017-10-19 2021-09-28 Nike, Inc. Color change materials, methods of making, methods of use, and articles incorporating the color change materials
US11975517B2 (en) 2017-10-19 2024-05-07 Nike, Inc. Color change materials, methods of making, methods of use, and articles incorporating the color change materials
EP3822297A1 (en) * 2019-11-15 2021-05-19 Covestro Deutschland AG Polysiloxane functionalized polyurethanes for enhancing hydrophobisation of surfaces
WO2021094229A1 (en) * 2019-11-15 2021-05-20 Covestro Intellectual Property Gmbh & Co. Kg Polysiloxane-functionalized polyurethanes for boosting the hydrophobicity of surfaces

Also Published As

Publication number Publication date
KR102104265B1 (en) 2020-04-24
BR102013032886B8 (en) 2021-08-24
US20140186621A1 (en) 2014-07-03
JP2014129524A (en) 2014-07-10
BR102013032886B1 (en) 2021-07-06
BR102013032886A2 (en) 2019-10-15
EP2927255A1 (en) 2015-10-07
JP6235329B2 (en) 2017-11-22
CN103910853A (en) 2014-07-09
EP2749583A2 (en) 2014-07-02
EP2749583B1 (en) 2018-11-21
US9145500B2 (en) 2015-09-29
EP2749583A3 (en) 2014-11-05
CN103910853B (en) 2016-05-18
KR20140088011A (en) 2014-07-09

Similar Documents

Publication Publication Date Title
US9145500B2 (en) Siloxane-urethane foul release coatings
US8722815B2 (en) Two-component moisture curable coating compositions
US20140088219A1 (en) Moisture curable compositions and low surface energy coating compositions made therefrom
US10759950B2 (en) Non-isocyanate siloxane-modified glycidyl carbamate resins and coatings containing them
CN100471921C (en) Coating composition and multilayered coating film forming method and coated article using this coating composition
US8652568B2 (en) Coating composition
JP2018177844A (en) Coating material composition and multilayer coated film formation method
AU2015316771B2 (en) Composition
CN103540250A (en) Coating compound for plastic
US11518906B2 (en) Coating composition comprising polysiloxane-modified polyurethane for soft-feel, stain resistant coatings
MX2010011493A (en) Coating composition containing polytrimethylene ether diol.
JP2019137856A (en) Polyisocyanate composition, coating composition, method for producing coating film, and coating film
EP2288660A1 (en) Polyester and polytrimethylene ether diol based coating composition
JP5441239B2 (en) Resin composition
WO2019188574A1 (en) Coated body
JP7435117B2 (en) Modified polyisocyanate composition
KR20170088464A (en) High glossy paint composition for interial parts
TW202018026A (en) Coating composition comprising polysiloxane-modified polyurethane for soft-feel, stain resistant coatings
JP2010043179A (en) Resin composition

Legal Events

Date Code Title Description
STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION