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WO2025216918A1 - Compositions de revêtement de polysiloxane pour substrats souples - Google Patents

Compositions de revêtement de polysiloxane pour substrats souples

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Publication number
WO2025216918A1
WO2025216918A1 PCT/US2025/022424 US2025022424W WO2025216918A1 WO 2025216918 A1 WO2025216918 A1 WO 2025216918A1 US 2025022424 W US2025022424 W US 2025022424W WO 2025216918 A1 WO2025216918 A1 WO 2025216918A1
Authority
WO
WIPO (PCT)
Prior art keywords
coating composition
astm
functional polysiloxane
composition
determined
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.)
Pending
Application number
PCT/US2025/022424
Other languages
English (en)
Inventor
Manish Kr MISHRA
Ian Michael Jones
Allison Brooks DOMHOFF
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.)
PPG Industries Ohio Inc
Original Assignee
PPG Industries Ohio Inc
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 PPG Industries Ohio Inc filed Critical PPG Industries Ohio Inc
Publication of WO2025216918A1 publication Critical patent/WO2025216918A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • 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
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups

Definitions

  • VOCs volatile organic components
  • the present disclosure provides a water-dispensable, silicone-based coating composition including a vinyl functional polysiloxane; a hydride functional polysiloxane; a catalyst; a solvent; and a non-ionic triblock surfactant.
  • the non-ionic triblock surfactant is of any one of the following formulae: H-[A]x-[B]y-[C]z-OH; H-[B]y-[A]x- [C]z-OH; and H-[C]z -[B]y-[A]x -OH; wherein A is derived from an ethylene glycol monomer, B is derived from a propylene glycol monomer, C is derived from an ethylene glycol monomer, x is 1 to 110, y is 1 to 80, and z is 1 to 110.
  • the coating composition is in the form of an emulsion including particles of the vinyl and hydride functional polysiloxanes emulsified by the non-ionic triblock surfactant.
  • the present disclosure further provides a coating composition, provided as a two-component composition, including: a first composition component and a second composition component.
  • the first composition component includes a vinyl functional polysiloxane; a catalyst; and a solvent.
  • the second composition component includes a hydride functional polysiloxane; and a solvent.
  • first composition component and the second composition component includes a non-ionic triblock surfactant of any one of the following formulae: H-[A] x -[B] y -[C] z -OH; H-[B]y-[A]x- [C]z-OH; and H-[C] z -[B] y -[A] x -OH; wherein A is derived from an ethylene glycol monomer, B is derived from a propylene glycol monomer, C is derived from an ethylene glycol monomer, x is 1 to 110, y is 1 to 80, and z is 1 to 110.
  • the present disclosure provides a substrate coated with a cured coating, the cured coating including: a reaction product of a vinyl functional polysiloxane and a hydride functional polysiloxane in the presence of a platinum catalyst and a non-ionic triblock surfactant.
  • non-ionic surfactant of any one of the following formulae: H-[A]x-[B]y-[C]z-OH; H-[B] y -[A] x - [C] z -OH; and H-[C]z -[B]y-[A]x -OH; wherein A is derived from an ethylene glycol monomer, B is derived from a propylene glycol monomer, C is derived from an ethylene glycol monomer, x is 1 to 110, y is 1 to 80, and z is 1 to 110.
  • the present disclosure provides a water-based silicone coating composition including a vinyl functional polysiloxane, a hydride functional polysiloxane, and a non-ionic triblock surfactant, as further described below.
  • a water-based silicone coating composition including a vinyl functional polysiloxane, a hydride functional polysiloxane, and a non-ionic triblock surfactant, as further described below.
  • a range of "1 to 10" is intended to include all sub-ranges from (and including) the recited minimum value of 1 to the recited maximum value of 10, that is, having a minimum value equal to or greater than 1 and a maximum value of equal to or less than 10.
  • the use of the singular includes the plural and plural encompasses singular, unless specifically stated otherwise.
  • the use of “or” means “and/or” unless specifically stated otherwise, even though “and/or” may be explicitly used in certain instances.
  • “Wet” coating composition as used herein refers to a liquid, or uncured coating composition which includes water and/or volatile components.
  • “Dry” coating composition as used herein refers to a cured coating composition which essentially lacks water and/or volatile components.
  • “Substrate” and “article” as used herein refers to an object or other item with a surface onto which a coating composition may be applied. The substrate may be an underlying layer to multiple coatings, such as a thermoplastic coating and the polysiloxane coating composition of the present disclosure.
  • “Solids” refers to the non-volatile components present in a composition of volatile and non-volatile components. As used herein, a weight percentage based on “solids” refers to an amount of a component based on a total weight of the pre-condensed silicone resin.
  • Resin solids refers to the solid components that make up the binder or film- forming components of the composition. As used herein, a weight percentage based on “resin solids” refers to an amount of a component based on a total weight of the binder or film-forming components of a composition.
  • Siloxane monomer and siloxane polymer refer to a monomer or polymer, respectively, containing alternating silicon-oxygen linkages, e.g., O-Si-O and/or Si-O-Si linkages.
  • Emulsion refers to a fine dispersion of one liquid within another liquid.
  • a “silicone resin coating emulsion” refers to an emulsion comprising silicone resin coating composition dispersed into a solvent.
  • an “emulsion solution” refers to a diluted emulsion comprising silicone resin coating composition dispersed into a solvent.
  • VOCs or “volatile organic compounds” as used herein refers to any organic compound with a boiling point less than or equal to 250 °C (482 °F ) measured at a standard atmospheric pressure of 101.3 kPa .
  • “Aqueous” as used herein refers to a solution wherein the solvent comprises at least 50 wt. % water.
  • the coating composition of the present disclosure may comprise at least two polysiloxane resins, a catalyst, a solvent, and a non-ionic triblock surfactant.
  • the at least two polysiloxane resins may comprise a vinyl functional polysiloxane and a hydride functional polysiloxane, as discussed below.
  • the coating composition may be prepared as a 1K composition, where each individual component is mixed together into a singular composition.
  • the coating composition may be prepared as a 2K, or two-component, composition.
  • the two- component composition may comprise a first composition and a second composition.
  • the first composition may comprise the vinyl functional polysiloxane, catalyst, solvent and non- ionic triblock surfactant.
  • the second composition may comprise the hydride functional polysiloxane, vinyl functional polysiloxane, solvent, and non-ionic triblock surfactant.
  • the first composition and the second composition may be mixed together to form the coating composition.
  • the coating composition may be diluted with water to control the viscosity of the composition.
  • the coating composition may be diluted such that the solids of the coating composition comprise an amount from 20 wt. %, 30 wt. %, 40 wt.
  • a polysiloxane resin is a silicone polymer comprising silicon, oxygen, carbon, and hydrogen atoms.
  • the polysiloxane resin may be formed as the reaction product of multiple siloxane monomers, such as three siloxane monomer units.
  • the siloxane monomers may be described according to the degree of oxygen substitution, or functionality, on the central silicon, as shown in Table A.
  • Table A Siloxane Monomer Types Structural formula Functionality Symbol
  • the coating composition may include hydride functional polysiloxanes and vinyl functional polysiloxanes.
  • the coating composition may comprise a greater number of hydride groups than vinyl groups from the polysiloxanes.
  • the molar ratio of hydride groups of the hydride functional polysiloxane to vinyl groups of the vinyl functional polysiloxane may be from 2, 2.5, 3 to 4, 4.5, or 5, or any range using any of the foregoing values as endpoints, such as 2 to 5, 2.5 to 2.5 or 3 to 4, based on the total moles of hydride and vinyl functional groups.
  • a hydride functional polysiloxane may be a silicone polymer that comprises hydride (Si-H) R groups along the chain of siloxane monomers that make up the polysiloxane.
  • Suitable hydride functional polysiloxanes include HMS-031, HMS-151, HMS- 301, HMS-501, HMS-991, HMS-992, HMS-993 from Gelest, Inc.
  • the hydride functional polysiloxane may have a molecular weight of 1,000 g/mol, 5,000 g/mol, 10,000 g/mol to 15,000 g/mol, 20,000 g/mol, or 25,000 g/mol, or any range using any of the foregoing values as endpoints, such as 1,000 g/mol to 25,000 g/mol, 5,000 g/mol to 20,000 g/mol, or 10,000 g/mol to 15,000 g/mol, as determined using GPC calibrated by polystyrene standards according to ASTM D6474 (2020).
  • the hydride functional polysiloxane may have a viscosity of 25 cSt, 50 cSt, 100 cSt to 250 cSt, 500 cSt, or 1000 cSt, or any range using any of the foregoing values as endpoints, such as 25 cSt to 1000 cSt, 50 cSt to 500 cSt, or 100 cSt to 250 cSt, as determined according to ASTM D2983 (2023).
  • the coating composition may comprise an amount of hydride functional polysiloxane from 0.5 wt. %, 1 wt. %, 2 wt. % to 3 wt. %, 4 wt.
  • the cured coating may comprise an amount of hydride functional polysiloxane from 1 wt. %, 1.5 wt. %, 2 wt. % to 2.5 wt. %, 3 wt. %, or 4 wt. %, or any range using any of the foregoing values as endpoints, such as 1 wt.
  • Suitable vinyl functional polysiloxanes include DMS-V31, DMS-V33, DMS-V35, DMS- V41, DMS-V42, DMS-V46, DMS-V51, DMS-V52 from Gelest, Inc and Andisil VS 1000, Andisil VS 2000, Andisil VS 4000, Andisil VS 5000, Andisil VS 10,000, Andisil VS 20,000, Andisil VS 65,000, Andisil VS 80,000, Andisil VS 100,000, Andisil VS 165,000 from AB Specialty Silicones.
  • the vinyl functional polysiloxane may have a molecular weight of 20,000 g/mol, 50,000 g/mol, 100,000 g/mol to 150,000 g/mol, 200,000 g/mol, or 300,000 g/mol, or any range using any of the foregoing values as endpoints, such as 20,000 g/mol to 300,000 g/mol, 50,000 g/mol to 200,000 g/mol, or 100,000 g/mol to 150,000 g/mol, as determined using GPC calibrated by polystyrene standards according to ASTM D6474 (2020).
  • the vinyl functional polysiloxane may have a viscosity of 1,000 cSt, 5,000 cSt, 10,000 cSt to 100,000 cSt, 500,000 cSt, or 1,000,000 cSt, or any range using any of the foregoing values as endpoints, such as 1,000 cSt to 1,000,000 cSt, 5,000 cSt to 500,000 cSt, or 10,000 cSt to 100,000 cSt, as determined according to ASTM D2983 (2023).
  • the coating composition may comprise an amount of vinyl functional polysiloxane from 30 wt. %, 33 wt. %, 35 wt. % to 40 wt. %, 43 wt.
  • the cured coating may comprise an amount of vinyl functional polysiloxane from 87 wt. %, 88 wt. %, 89 wt. % to 90 wt. %, 91 wt. %, or 92 wt.
  • the coating composition may comprise a platinum catalyst.
  • the platinum catalyst may be used in hydosilylation reactions, particularly in the curing or cross-linking of silicone materials.
  • the platinum catalyst may facilitate the reaction between compounds containing silicon-hydrogen (Si-H) bonds (such as the hydride functional polysiloxane) and compounds containing unsaturated carbon-carbon double bonds (e.g., vinyl groups) (such as the vinyl functional polysiloxane) in a process known as hydrosilylation, shown in reaction Mechanism I below.
  • Si-H silicon-hydrogen
  • vinyl groups unsaturated carbon-carbon double bonds
  • Suitable platinum catalysts include polysiloxane-coordinated platinum catalysts, such as Karsted’s catalyst, and Ashby’s catalyst.
  • the amount of platinum catalyst in the coating composition can affect the cure response at a given temperature. A greater amount of catalyst may decrease the necessary temperature for curing the coating composition.
  • the catalyst may comprise a concentration of platinum metal from 10 ppm, 100 ppm, 500 ppm to 1,000 ppm, 5,000 ppm, or 10,000 ppm, or any range using any of the foregoing values as endpoints, such as 10 ppm to 10,000 ppm, 100 ppm to 5,000 ppm, or 500 ppm to 1,000 ppm.
  • the coating composition may comprise an amount of catalyst from 0.1 wt. %, 1 wt. %, 2 wt. % to 3 wt. %, 4 wt. %, or 5 wt.
  • the cured coating may comprise an amount of catalyst from 0.007 wt. %, 0.009 to 0.011 wt. %, or 0.015 wt. %, or any range using any of the foregoing values as endpoints, such as 0.007 wt. % to 0.015 wt. %, or 0.009 wt. % to 0.011 wt.
  • the coating composition may comprise at least one solvent.
  • the solvent may be used to create the emulsions or adjust the viscosity of the final coating composition.
  • Suitable solvents may include water, xylene, toluene, acetone, and other suitable solvents.
  • the coating composition may be an aqueous composition such that water makes up 50%, 55 %, 60% to 65%, 70%, or 75% of the total amount of solvent in the coating composition.
  • the composition may comprise an amount of solvent from 40 wt. %, 45 wt. %, 50 wt. % to 55 wt.
  • Non-ionic Triblock Surfactant may be added to the coating composition to enable the vinyl and hydride functional polysiloxane to emulsify.
  • Non-ionic triblock surfactants may include, but are not limited to the following: ethlylene oxide-propylene oxide-ethylene oxide block copolymers , and propylene oxide-ethylene oxide-propylene oxide block copolymers.
  • Non-ionic triblock surfactants in the coating composition may be triblock copolymers.
  • a structural unit of triblock copolymer-based non-ionic surfactant refers to any one of a compound of Formula I, a compound of Formula II, and a compound of Formula III, below.
  • a non-ionic triblock surfactant of Formula I may have a hydrophilic-lipophilic balance (HLB) value from 18, 20, 22 to 24, 26, or 27, or any range of HLB value using any two of the foregoing values as end points, as determined by using Griffin’s method or Davies Method as described in the National Journal of Pharmaceutical Sciences 2021; 1(2): 23-24.
  • HLB hydrophilic-lipophilic balance
  • the non-ionic triblock surfactant of Formula I may have an average molecular weight from 8000 g/mol, 10000 g/mol, 12000 g/mol to 14000 g/mol, 14600 g/mol, 15000 g/mol, or any range including any two of the foregoing values as end points, such as 8000 to 15000 g/mol, 10000 to 14600 g/mol, or 12000 to 14000 g/mol, as determined by gel permeation chromatography using polystyrene polymer beads for calibration standards.
  • the coating composition may comprise a weight percentage of non-ionic triblock surfactants from 0.1 wt. %, 0.5 wt. %, 0.1 wt.
  • the cured coating may comprise an amount of non-ionic triblock surfactant from 6 wt. %, 7 wt. %, 8 wt. % to 9 wt. %, 10 wt. %, or 11 wt.
  • the coating composition may comprise additives such as other surfactants, leveling agents rheology modifiers, solid fillers, color pigments, soft touch additives, preservatives, and other additives known to someone skilled in the art.
  • Suitable other surfactants may include ethyoxylated alkyl alcohols, ethoxylated aklyl phenols, ethoxylated sorbitans and their propoxylated or ethoxylated- propoxylated analogs, and polyvinyl alcohols.
  • the other surfactants may be used in conjunction with the non-ionic tri block surfactant discussed above.
  • the coating composition may comprise a weight percentages of additives from 0 wt. %, 0.5 wt. %, 0.1 wt. % to 1 wt. %, 2 wt. %, 5 wt.
  • the cured coating may comprise an amount of additives from 0 wt. %, 7 wt. %, 8 wt. % to 9 wt. %, 10 wt. %, or 11 wt. %, or any range using any of the foregoing values as endpoints, such as 0 wt.
  • the coating composition may be substantially free of VOCs, reaction inhibitors, and adhesion promotors; have an average particle size less than 3 ⁇ m; and have a cloud point of 50-100 o C.
  • A. Volume Average Particle Size may describe the size distribution of particles within the coating composition. The volume average particle size provides a measure that represents the average size of particles based on their volume.
  • Particles of the coating composition may have a volume average particle size of less than 10 ⁇ m, less than 9 ⁇ m, less than 7 ⁇ m, less than 5 ⁇ m, less than 3 ⁇ m, or less than 1 ⁇ m, or any range using any of the foregoing values as endpoints, such as 10 ⁇ m to 1 ⁇ m, 9 ⁇ m to 3 ⁇ m, or 7 ⁇ m to 5 ⁇ m, based on the total volume of each particle, as determined by ASTM E3338 (2022).
  • “cloud point” refers to the temperature at which a coating material undergoes a phase separations, leading to the formation of a cloudy or hazy appearance.
  • the cloud point temperature may determine the temperature wherein certain components may become less soluble or may separate from the rest of the composition, resulting in haziness or cloudiness of the composition.
  • the coating composition may have a cloud point of 50 o C, 60 o C, 70 o C to 80 o C, 90 o C, or 100 o C, or any range using any of the foregoing values as endpoints, such as 50 o C to 100 o C, 60 o C to 90 o C, or 70 o C to 80 o C, as measured according to ASTM D2500 (2023).
  • a reaction inhibitor is a substances used to control or prevent the curing or polymerization of a coating composition.
  • Suitable reaction inhibitors may include any compound that reversibly coordinates the Pt metal such as cyclic vinyl siloxanes, alkynyl groups, bulky heteroatoms, such as N-heterocyclic carbene.
  • the coating composition may be essentially free, substantially free, or completely free of reaction inhibitors.
  • essentially free of reaction inhibitors it is meant that the coating composition comprises less than 2 wt. % of reaction inhibitors based on the total weight of the “wet” coating composition.
  • substantially free of reaction inhibitors it is meant that the coating composition comprises less than 1 wt. % of reaction inhibitors based on the total weight of the “wet” coating composition.
  • completely free of reaction inhibitors it is meant that the coating composition comprises less than 0.1 wt.
  • An adhesion promoter is a substance that improves adhesion of the coating to a substrate.
  • the adhesion promotor may modify the surface properties of the substrate, making it more receptive to the coating.
  • Adhesion promotors may include any compound that reacts with both the coating composition and the substrate.
  • the coating composition may be essentially free, substantially free, or completely free of adhesion promotors. By essentially free of adhesion promotors it is meant that the coating composition comprises less than 2 wt. % of adhesion promotors based on the total weight of the “wet” coating composition.
  • VOC Value In many locations, there are environmental standards to limit the level of VOCs that can be present in coating compositions. VOC are compounds that have a high vapor pressure, generally 10 Pa or more at 20 o C, and low water solubility. High levels of VOCs in coating compositions can cause not only environmental issues, but also health effects on those exposed to such compounds.
  • the coating composition of the present disclosure may comprise a level of VOCs that is compliant with VOC restrictions of some states.
  • the coating composition may comprise an amount of VOCs from less than 370 g/liter, less than 300 g/liter, less than 250 g/liter, less than 200 g/liter, less than 150 g/liter, or less than 100 g/liter, or within any range including any two of the foregoing values as end points, such as 100 g/liter to 370 g/liter, 150 g/liter to 300 g/liter, or 200 g/liter to 250 g/liter, as determined by VOC ISO 11890-2 Liquid Paint-Water. [0086] IV.
  • the coating composition may be coated onto a flexible substrate, such as a silicone substrates or substrates coated with thermoplastic materials.
  • Suitable silicone substrates include silicone rubber and silicone polyester.
  • Flexibility can be quantified by flexural modulus which is measured using ASTM D790-17. Suitable flexibilities enable the function of consumer articles, such as wearable bands or cases, or enable the ability to post-form a substrate coated with a thermoplastic material that is coated with the coating composition.
  • Post-forming can include bending or deep drawing the substrate coated with a thermoplastic, particularly bending or deep drawing to create a pan or pot.
  • the flexural modulus of the silicone substate or substrate coated with a thermoplastic material is preferably less than 100 GPa, less than 80 GPa, less than 70 GPa, less than 60 GPa, less than 50 GPa, or less than 10 GPa, or any range using any two of the foregoing values as endpoints, such as 10 to 100 GPa, 50 to 80 GPa, or 60 to 70 GPa.
  • Suitable thermoplastic materials may include a crystalline thermoplastic polymer having a melting point of about 200oC or greater, about 210oC or greater, about 220oC or greater, or about 250oC or greater, or any range using any two of the foregoing values as endpoints, such as 200oC to 250oC, or 210oC to 220oC, as determined by differential scanning calorimetry (DSC) according to ASTM E794 – 06(2018).
  • Suitable thermoplastic materials may include polycarbonate, polyphenylene sulfide, polyetheretherketone, polysulfone, polyimide, polyamide, and fluoropolymers.
  • the thermoplastic material may be an amorphous thermoplastic polymer having a glass transition temperature (Tg) of about 90oC or greater, about 100oC or greater, about 120oC or greater, about 150oC or greater, about 170oC or greater, or about 200oC or greater, or any range using any two of the foregoing values as endpoints, such as 90oC to 200oC, or 100oC to 170oC, or 120oC to 150oC, as determined by differential scanning calorimetry (DSC) according to ASTM E1356 – 08(2014), for example.
  • Tg glass transition temperature
  • the thermoplastic material may include polymers having a heat deflection/distortion temperature (HDT) of about 100 o C or greater, about 120 o C or greater, about 150 o C or greater, about 170 o C or greater, about 185 o C or greater, or about 200oC or greater, or any range using any two of the foregoing values as endpoints, such as 100oC to 200oC, or 120oC to 185oC, or 150oC to 170oC, as determined by ASTM D648.
  • HDT heat deflection/distortion temperature
  • the above described properties may contribute, either individually or in combination, to a coating having a continuous use temperature greater than 200 o C.
  • the thermoplastic material may be polyphenylene sulfide (PPS), polyethersulfone (PES), polyether ether ketone (PEEK), polyphenylsulfone (PPSU), polyamide-imides (PAI), polyetherimides (PEI), polyimide (PI), liquid crystalline polymers and combinations thereof.
  • the thermoplastic material may be applied to a substrate.
  • the substrate is not particularly limited.
  • the thermoplastic material can be applied to the substrate by spray or drawdown, silk screen, or roller coating.
  • the substrate coated with thermoplastic material can be heated at a temperature from 120 o C, 150 o C, or 175 o C to 200 o C, 250 o C, or 280oC, or any range using any two of the foregoing values as endpoints, such as 120oC to 280oC, or 150oC to 250oC, or 175oC to 200oC, to solvent and allow the thermoplastic material to flow and adhere to the substrate.
  • the substrate can be abraded to promote the adhesion of the thermoplastic material.
  • the substrate may also be annealed at temperatures high before application of the thermoplastic material.
  • the annealing should be high enough so that the flexural modulus of the substrate is reduced to enable post-forming.
  • the polysiloxane-based coating may entangle, or interact, with the silicone substrate or thermoplastic coating material, leading to adhesion.
  • the coating composition may be applied to the flexible substrate via spray application.
  • the emulsions may be diluted form a sprayable coating composition.
  • Spray application may comprise using a spray of particles or droplets of the coating composition to deposit the coating composition onto the substrate.
  • the silicone substrate or substrate coated with thermoplastic material may be passed under the spray or otherwise exposed to the spray of the coating composition for a predetermined amount of time to deposit a desired amount of coating composition.
  • the coating composition may be cured at a temperature of 120 o C, 160 o C, 170 o C to 180 o C, 190 o C, or 200 o C, or any range using any of the foregoing values as endpoints, such as 120-200 o C, 160-190 o C, or 170-180 o C.
  • the coating may be cured for an amount of time from 30 min, 50 min, 70 min to 90 min, 110 min, or 120 min, or any range using any of the foregoing values as endpoints, such as 30 min to 120 min, 50 min to 110 min, or 70 min to 90 min.
  • the silicone substrate or substrate coated with a thermoplastic material maybe shaped or post formed.
  • the cured coating composition may be flexible, exhibit anti-stain properties, have good adhesion to substrates, and have a smooth, soft-touch feel.
  • Print free coating compositions refer to the ability of a coated substrate to repel undesirable imprints, marks, or impressions when subjected to a certain temperature.
  • a substrate coated with the coating composition of the present disclosure may be print free cure temperature of 120 o C, 140 o C, 150 o C to 160 o C, 180 o C, or 200 o C, or any range using any of the foregoing values as endpoints, such as 120 o C to 200 o C, 140 o C to 180 o C, or 150 o C, to 160 o C, as determined according to ASTM D1640 (2022).
  • Lower cure temperatures may prevent damage to the substrate and reduce energy costs. However, higher cure temperatures may allow for faster curing of the coating. It was determined that 200 o C is the highest the substrate can tolerate and 120 o C is the minimum temperature to remove water in a timely fashion and induce coating cure.
  • Adhesion of the cured coating may be evaluated using ASTM D3359 (2023) method B.
  • the adhesion test involves making incisions in the cured coating, applying pressure-sensitive adhesive tape to the cut area, removing the tape, and inspecting the cut area after tape removal. Adhesion is rated on a scale from 0 to 5, with 0 indicating greater than 65% adhesion loss and 5 indicating perfect adhesion.
  • the coating composition may have an adhesion from 2, 3 to 4, or 5 on silicone substrates, as determined according to ASTM D3359 (2023).
  • Example 1 Preparation of Emulsion 1, Emulsion 2, and Coating Composition 1, 3, and 4 [0106] Emulsion 1 and Emulsion 2 were prepared according to the formulation of Table 1. Table 1: Emulsion 1 and Emulsion 2 Formulation Sample Component Mass (parts) Vinyl functional 01 7 7 1 3 1 1 1 7 1 8 [0107] Pr epa a o o u s o [0108] The vinyl functional polysiloxane and the catalyst were mixed with a solvent using a saw tooth blade.
  • Coating Composition 1 Preparation of Coating Composition 1 [0112] Emulsion 1 (85.7 g) and Emulsion 2 (5.62 g) were added together under mixing by an impeller blade to form Coating Composition 1. Water (8.68 g) was added to adjust viscosity. [0113] Coating Composition 1 was applied by spray or drawdown application on Q- A412 panels available from Q-Lab, silicone rubber, Q-A412 panels coated with silicone polyester, polyamideimide, or polyphenylenesulfide and cured at 120, 150 or 200 oC for 30 - 90 min.
  • Cure was determined by print free as described in ASTM D1640 (2022). [0114] Preparation of Coating Composition 3 [0115] Emulsion 1 (88.5 g) and Emulsion 2 (2.6 g) were added together under mixing by a vortexer to form Coating Composition 3. [0116] Coating Composition 3 was applied by spray or drawdown application on Q- A412 panels, silicone rubber, Q-A412 panels coated with silicone polyester, polyamideimide, or polyphenylenesulfide and cured at 120, 150 or 200 oC for 30 - 90 min. Cure was determined by print free as described in ASTM D1640 (2022).
  • Emulsion 1 (85.2 g) and Emulsion 2 (6.2 g) were added together under mixing by a vortexer to form Coating Composition 4.
  • Coating Composition 4 was applied by spray or drawdown application on Q- A412 panels, silicone rubber, or Q-A412 panels coated with silicone polyester, polyamideimide, or polyphenylenesulfide and cured at 120, 150 or 200 oC for 30 - 90 min. Cure was determined by print free as described in ASTM D1640 (2022).
  • Example 2 Preparation of Emulsion 3, Emulsion 4, and Coating Composition 2
  • Emulsion 3 and Emulsion 4 were prepared according to the formulations in Table 2.
  • Emulsion 3 and Emulsion 4 Formulation Sample Component Mass (Parts) Vin l f n ti n l 0 9 9 8 1 1 3 1 Sample Component Mass (Parts) Non-ionic t i l k f t t 2 9 7
  • Em ethod as Emulsions 1 and 2, respectively.
  • Preparation of the Coating Composition 2 [0123] Emulsion 3 (85.7 g) and Emulsion 4 (5.62 g) were added together under mixing by an impeller blade to form Coating Composition 2. Water (8.68 g) was added to adjust viscosity.
  • Coating Composition 2 was applied by spray application or draw down application on Q-A412 panels, silicone rubber, Q-A412 panels coated with silicone polyester, polyamideimide, or polyphenylenesulfide, and cured at 120, 150, or 200oC for 90 min. Cure was determined by print free as described in ASTM D1640 (2022).
  • Example 3 Preparation of Comparative Emulsion 1, Comparative Emulsion 2, and Comparative Coating Composition 1 [0125] Comparative Emulsion 1 and Comparative Emulsion 2 were prepared according to the formulation of Table 3.
  • Table 3 Comparative Emulsion 1 and Comparative Emulsion 2 Formulation Sample Component Mass (parts) Vin l functional 3 8 3 2 2 8 3 8 4 8 Sample Component Mass (parts) Viscosity t t W t 1263
  • Example 4 P Emulsion 4, and Comparative Coating Composition 2
  • Comparative Emulsion 3 and Comparative Emulsion 4 were prepared according to the formulation of Table 4.
  • Table 4 Comparative Emulsion 3 and Comparative Emulsion 4 Formulation Sample Component Mass (parts) Vinyl functional 6 7 8 8 2 7 2 8 4 7 5
  • Comparative Emulsion 1 and Comparative Emulsion 2 were prepared according to the same method as Emulsions 1 and 2, respectively.
  • Comparative Coating Composition 1 and 2 [0128] Preparation of Comparative Coating Composition 1 and 2 [0129] Comparative Emulsion 1 (85.7 g) and Comparative Emulsion 2 (5.62 g) were added together under mixing by an impeller blade to form Comparative Coating Composition 1. Water (12.63 g) was added to adjust viscosity. Comparative Coating Composition 2 was prepared by adding Comparative Emulsion 3 (85.7 g) and Comparative Emulsion 4 (5.62 g) under mixing as stated above. Water (12.63 g) was added to adjust viscosity.
  • Comparative Coating Compositions 1 and 2 were applied by spray or drawdown application on Q-A412 panels, silicone rubber, Q-A412 panels coated with silicone polyester, polyamideimide, or polyphenylenesulfide and cured at 120, 150 or 200 oC for 30 - 90 min. Cure was determined by print free as described in ASTM D1640 (2022).
  • Example 5 Properties of Coating Compositions 12, 3, and 4 and Comparative Compositions 1 and 2 [0131] The properties of each of the coating compositions are shown in Table 5.
  • Coating composition 1, coating composition 2, and comparative coating composition 1 are shown in Table 6.
  • Table 6 Testing Results for Coating Composition 1, Coating Composition 2, and Comparative Coating Composition 1
  • Formulation Substrate Hydride Water- 120 150 200 oC 300 Adhesion to vinyl dilutable oC oC Print free oC molar Print Print Print Formulation Substrate Hydride Water- 120 150 200 oC 300 Adhesion to vinyl dilutable oC oC Print free oC molar Print Print Print 3Polyphenylenesulfide PPS B-100-C available from DIC dispersed in water, using tergitol 15- S-9 surfactant and 5% carbon black pigment [0136]
  • Coating Composition 1 Coating Composition 2, Coating Composition 3 and Coating Composition 4 show that emulsions with the non-ionic triblock surfactant can cure over aluminum or silicone rubber or substrates coated thermoplastic materials.
  • Coating Composition 1 and Coating Composition 2, 3 and 4 have acceptable adhesion to silicone rubber silicone polyester and the substrates coated thermoplastic materials without an adhesion promoter but have no adhesion to aluminum. Without wishing to be bound by theory, one explanation for this is the entanglement of the silicone-based coating with the silicone or thermoplastic materials, leading to adhesion.
  • the waterborne compositions (Coating Compositions 1 and 2) may adhere to silicone or substrates coated thermoplastic materials without adhesion promoters.
  • Comparing Coating Composition 1, 3, 4 and Comparative Coating Composition 1 the importance of the higher hydride to vinyl molar ratio is clear.
  • a ratio below 2 provides no cure at 200 oC over aluminum or silicone rubber but increasing the ratio to 2 - 5 provides a print free coating at 200 oC. This can also be observed by comparing the cure response at 200 oC of Coating Composition 2 and Comparative Coating Composition 2 when applied over substrates coated thermoplastic materials.
  • ASPECTS [0140] is a water-dispensable, silicone-based coating composition, comprising: a vinyl functional polysiloxane; a hydride functional polysiloxane; a catalyst; a solvent; and a non-ionic triblock surfactant of any one of the following formulae: H-[A] x -[B] y -[C] z -OH; H-[B]y-[A]x- [C]z-OH; and H-[C] z -[B] y -[A] x -OH; wherein A is derived from an ethylene glycol monomer; B is derived from a propylene glycol monomer; C is derived from an ethylene glycol monomer; x is 1 to 110; y is 1 to 80; and
  • Aspect 2 is the coating composition of Aspect 1, wherein the non-ionic triblock surfactant comprises a hydrophobic-lipophobic balance (HLB) from 18 to 27 as determined according to Davies Method as described in the National Journal of Pharmaceutical Sciences 2021; 1(2): 23-24.
  • Aspect 3 is the coating composition of either Aspect 1 or Aspect 2, wherein the composition comprises a cloud point of at least 50 o C, according to ASTM D2500 (2023).
  • Aspect 4 is the coating composition of any one of Aspects 1-3, wherein the composition comprises a cloud point of at least 100 o C, according to ASTM D2500 (2023).
  • Aspect 5 is the coating composition of any one of Aspects 1-4, wherein a mole ratio of hydride groups of the hydride functional polysiloxane to vinyl groups of the vinyl functional polysiloxane is from 2 to 5, based on the total moles of hydride and vinyl functional groups.
  • Aspect 6 is the coating composition of any one of Aspects 1-5, wherein the catalyst comprises a platinum-based catalyst; and wherein the catalyst comprises 10ppm to 10,000ppm of platinum metal, based on the total mass of the coating composition.
  • Aspect 7 is the coating composition of any one of Aspects 1-6, wherein the coating composition comprises less than 1 wt.
  • Aspect 8 is the coating composition of any one of Aspects 1-7, having a water free VOC value of less than 300 g/L as determined by VOC ISO 11890-2 (Liquid Paint- Water).
  • Aspect 9 is the coating composition of any one of Aspects 1-8, wherein the hydride functional polysiloxane comprises: a molar mass of 1,000 g/mol to 25,000 g/mol, as determined by ASTM D6474 (2020); and a viscosity of 25 cSt to 100 cSt, as determined by ASTM D2983 (2023).
  • Aspect 10 is the coating composition of any one of Aspects 1-9, wherein the vinyl functional polysiloxane comprises: a molar mass of 20,000 g/mol to 300,000 g/mol, as determined by ASTM D6474 (2020); and a viscosity of 1,000 cSt to 1,000,000 cSt, as determined by ASTM D2983 (2023).
  • Aspect 11 is the coating composition of any one of Aspects 1-10, in combination with water to form a diluted coating composition, wherein the solids of the coating composition comprise between 20 wt. % and 60 wt. % by weight of the diluted coating composition, based on the total weight of the diluted coating composition, as determined by ASTM D2369 (2024).
  • Aspect 12 is the coating composition of any one of Aspects 1-11, further comprising: 0.5-5 wt. % of hydride functional polysiloxane; 30-45 wt. % of vinyl functional polysiloxane; 0.1-5 wt. % of catalyst; 0.5-5 wt. % of non-ionic triblock surfactant; and 40-60 wt. % of solvent.
  • Aspect 13 is a coating composition, provided as a two-component composition, comprising: a first composition component comprising: a vinyl functional polysiloxane; a catalyst; a solvent; and a second composition component comprising a hydride functional polysiloxane; a solvent; and wherein in at least one or both of the first composition component and the second composition component comprises a non-ionic triblock surfactant of any one of the following formulae: H-[A] x -[B] y -[C] z -OH; H-[B]y-[A]x- [C]z-OH; and H-[C] z -[B] y -[A] x -OH; wherein A is derived from an ethylene glycol monomer; B is derived from a propylene glycol monomer; C is derived from an ethylene glycol monomer; x is 1 to 110; y is 1 to 80; and z is 1 to 110.
  • Aspect 14 is the coating composition of Aspect 13, wherein the non-ionic triblock surfactant comprises a hydrophobic-lipophobic balance (HLB) from 18 to 27 as determined according to Davies Method as described in the National Journal of Pharmaceutical Sciences 2021; 1(2): 23-24.
  • Aspect 15 is the coating composition of either Aspect 13 or Aspect 14, wherein the composition comprises a cloud point of at least 50 o C, according to ASTM D2500 (2023).
  • Aspect 16 is the coating composition of any one of Aspects 13-15, wherein the composition comprises a cloud point of at least 100 o C, according to ASTM D2500 (2023).
  • Aspect 17 is the coating composition of any one of Aspects 13-16, wherein a mole ratio of hydride groups of the hydride functional polysiloxane to vinyl groups of the vinyl functional polysiloxane is from 2 to 5, based on the total moles of hydride and vinyl functional groups.
  • Aspect 18 is the coating composition of any one of Aspects 13-17, wherein the catalyst comprises a platinum-based catalyst; and wherein the catalyst comprises 10ppm to 10,000ppm of platinum metal, based on the total mass of the catalyst.
  • Aspect 19 is the coating composition of any one of Aspects 13-18, wherein the coating composition comprises less than 1 wt.
  • Aspect 20 is the coating composition of any one of Aspects 13-19, having a water free VOC value of less than 300 g/L as determined by VOC ISO 11890-2 (Liquid Paint-Water).
  • Aspect 21 is the coating composition of any one of Aspects 13-20, wherein the hydride functional polysiloxane comprises: a molar mass of 1,000 g/mol to 25,000 g/mol, as determined by ASTM D6474 (2020); and a viscosity of 25 cSt to 100 cSt, as determined by ASTM D2983 (2023).
  • Aspect 22 is the coating composition of any one of Aspects 13-21, wherein the vinyl functional polysiloxane comprises: a molar mass of 20,000 g/mol to 300,000 g/mol, as determined by ASTM D6474 (2020); and a viscosity of 1,000 cSt to 1,000,000 cSt, as determined by ASTM D2983 (2023).
  • Aspect 23 is the coating composition of any one of Aspects 13-22, in combination with water to form a diluted coating composition, wherein the solids of the coating composition comprise between 20 wt. % and 60 wt. % by weight of the diluted coating composition, based on the total weight of the diluted coating composition, as determined by ASTM D2369 (2024).
  • Aspect 24 is the coating composition of any one of Aspects 13-23, further comprising: 0.5-5 wt. % of hydride functional polysiloxane; 30-45 wt. % of vinyl functional polysiloxane; 0.1-5 wt. % of catalyst; 0.5-5 wt. % of non-ionic triblock surfactant; and 40-60 wt. % of solvent.
  • Aspect 25 is a substrate coated with a cured coating, the cured coating comprising: a reaction product of a vinyl functional polysiloxane and a hydride functional polysiloxane in the presence of a platinum catalyst and a non-ionic triblock surfactant of any one of the following formulae: H-[A]x-[B]y-[C]z-OH; H-[B] y -[A] x - [C] z -OH; and H-[C]z -[B]y-[A]x -OH; wherein A is derived from an ethylene glycol monomer; B is derived from a propylene glycol monomer; C is derived from an ethylene glycol monomer; x is 1 to 110; y is 1 to 80; and z is 1 to 110.
  • Aspect 26 is the substrate of Aspect 25, wherein the substrate is either a silicone substrate or a substrate coated with a thermoplastic material; wherein the substrate has a flexural modulus of less than 100 GPa, as determined by ASTM D790-17.
  • Aspect 27 is the substrate of either Aspect 25 or Aspect 26, wherein the cured coating has an adhesion of 5B on the substrate, according to ASTM D3359 (2023) method B.
  • Aspect 28 is the substrate of any one of Aspects 25-27, wherein the cured coating composition has a print free temperature of 120 o C to 150 o C, according to ASTM D1640 (2022).
  • Aspect 29 is the substrate of any one of Aspects 25-28, wherein the cured coating further comprises: 1-4 wt. % of hydride functional polysiloxane; 88-92 wt. % of vinyl functional polysiloxane; 0.007-0.011 wt. % of catalyst; and 6-11 wt. % of non-ionic triblock surfactant.

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  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
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Abstract

La présente divulgation concerne une composition de revêtement comprenant un polysiloxane à fonction hydrure, un polysiloxane vinylique, un tensioactif tribloc non ionique, un catalyseur et un solvant. Le catalyseur est un catalyseur au platine. La composition de revêtement se présente sous la forme d'une émulsion comprenant des particules des polysiloxanes à fonction vinyle et hydrure émulsifiés par le tensioactif tribloc non ionique. Un rapport molaire des groupes hydrure du polysiloxane à fonction hydrure par rapport aux groupes vinyle du polysiloxane à fonction vinyle est de 2 à 5, sur la base des moles totales des groupes à fonction vinyle et hydrure.
PCT/US2025/022424 2024-04-09 2025-04-01 Compositions de revêtement de polysiloxane pour substrats souples Pending WO2025216918A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10385212B2 (en) * 2014-07-23 2019-08-20 Dow Silicones Corporation Silicone emulsions
WO2020228363A1 (fr) * 2019-05-16 2020-11-19 华南理工大学 Gel de silice liquide bicomposant pour impression 3d et son procédé d'impression
US20210355324A1 (en) * 2018-10-29 2021-11-18 Shin-Etsu Chemical Co., Ltd. Silicone emulsion composition
US20220235230A1 (en) * 2019-06-21 2022-07-28 Dow Toray Co., Ltd. Aqueous coating-film-forming composition for forming lubricating coating film, and air bag using said composition
WO2023146708A1 (fr) * 2022-01-28 2023-08-03 Dow Silicones Corporation Émulsion de revêtement antiadhésif en silicone, procédé pour sa préparation et son utilisation pour du papier de boulangerie

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10385212B2 (en) * 2014-07-23 2019-08-20 Dow Silicones Corporation Silicone emulsions
US20210355324A1 (en) * 2018-10-29 2021-11-18 Shin-Etsu Chemical Co., Ltd. Silicone emulsion composition
WO2020228363A1 (fr) * 2019-05-16 2020-11-19 华南理工大学 Gel de silice liquide bicomposant pour impression 3d et son procédé d'impression
US20220235230A1 (en) * 2019-06-21 2022-07-28 Dow Toray Co., Ltd. Aqueous coating-film-forming composition for forming lubricating coating film, and air bag using said composition
WO2023146708A1 (fr) * 2022-01-28 2023-08-03 Dow Silicones Corporation Émulsion de revêtement antiadhésif en silicone, procédé pour sa préparation et son utilisation pour du papier de boulangerie

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
NATIONAL JOURNAL OF PHARMACEUTICAL SCIENCES, vol. 1, no. 2, 2021, pages 23 - 24

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