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WO2024126494A1 - Revêtements - Google Patents

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Publication number
WO2024126494A1
WO2024126494A1 PCT/EP2023/085361 EP2023085361W WO2024126494A1 WO 2024126494 A1 WO2024126494 A1 WO 2024126494A1 EP 2023085361 W EP2023085361 W EP 2023085361W WO 2024126494 A1 WO2024126494 A1 WO 2024126494A1
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WO
WIPO (PCT)
Prior art keywords
intumescent coating
intumescent
layer
binder
epoxy
Prior art date
Application number
PCT/EP2023/085361
Other languages
English (en)
Inventor
Celine ABADIE
Original Assignee
Jotun A/S
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 Jotun A/S filed Critical Jotun A/S
Publication of WO2024126494A1 publication Critical patent/WO2024126494A1/fr

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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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • 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
    • C09D5/02—Emulsion paints including aerosols
    • 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
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • C09D5/185—Intumescent paints

Definitions

  • This invention relates to a multilayer intumescent coating system comprising an intumescent coating layer A and an adjacent non-intumescent coating layer B.
  • the intumescent coating system of the invention significantly reduces char failure and therefore offers improved fire protection.
  • the invention also relates to a process for applying the coating system to a substrate.
  • the invention also relates to a substrate coated with the intumescent coating system.
  • An intumescent coating is defined as a coating that swells in the case of a fire to produce a carbon based insulating char and has many advantages over other available forms of passive fire protection, such as their light weight and environmental durability.
  • a problem that arises with intumescent coatings is that the char can be brittle leading to cracks which leave the substrate exposed. The substrate will then reach the critical temperature earlier than if the char had not cracked leading to earlier collapse of the structural integrity of the substrate. Certain structures such as hollow section are more difficult to protect. On hollow sections of a substrate, almost all intumescent products show signs of stress caused by expansion and contraction leading to long tears or cracks in the char which can result in the steel being exposed and limiting performance. This cracking of the char can happen, for example, in hydrocarbon pool fires or jet fires or cellulosic fires.
  • a mesh such as a fabric mesh or a metal mesh is often embedded within the intumescent coating to hold the char together and extend the performance of the coating.
  • the weaknesses formed by the cracks and movement can be contained by the mesh.
  • the mesh can be applied around the entire section or sometimes just around flanges or joints.
  • Solvent is also used on the rollers to ease rolling which can cause issues with VOC emissions. Applying the mesh is a very resource intensive process and requires the applicators to be trained to avoid the mesh being applied improperly.
  • the present invention seeks to avoid the use of a mesh.
  • the multilayer intumescent coating system of the invention does not comprise a mesh layer .
  • US5989706 describes the use of two different intumescent layers with different densities of the char.
  • the first component forms a rigid char which protects the substrate from breakthrough and the second component forms an insulative char which protects the substrate from conductive, radiant and/or convective heating by the fire conditions.
  • WO2022/117878 describes intumescent coating systems which comprise an intumescent coating layer comprising: an epoxy binder and a curing agent for the binder; and a top coat layer comprising an acrylic-based binder, a polyurethane binder or a silicone-based binder obtained from waterborne starting materials. There is no non-intumescent coating layer comprising a binder and fibres.
  • US2011/274863 describes a thermal insulating tape composition with a fire protection function for use in aircraft construction. This document does not refer to coatings or the application of coatings to a substrate.
  • the inventors have now discovered that by applying a non-intumescent coating composition comprising fibres on top of an intumescent coating layer, the char formed from the intumescent coating layer is stabilised and prevented from cracking or detaching.
  • the intumescent coating system allows the efficiency of existing or new products to be improved through the use of the non-intumescent coating layer instead of optimising the intumescent coating layer itself.
  • the intumescent coating system described herein is easier to apply than coating systems which employ a traditional mesh and performs better than known coatings.
  • the fibres that are required in the non-intumescent layers act as a “mesh” within the coating layer which supports the char in the intumescent layer and prevents the char from cracking.
  • the invention provides a multilayer intumescent coating system comprising an intumescent coating layer A and a non- intumescent coating layer B directly thereon, wherein:
  • coating layer A comprises a) a binder
  • coating layer B comprises, such as consists of, or is formed from a non- intumescent coating composition comprising a) a binder; and b) fibres.
  • the invention provides a multilayer intumescent coating system comprising an intumescent coating layer A and a non-intumescent coating layer B directly thereon, wherein:
  • coating layer A comprises, such as consists of, or is formed from an intumescent coating composition comprising a) a binder; b) an acid generating agent; and c) an expansion agent; and
  • coating layer B comprises, such as consists of, or is formed from a non- intumescent coating composition comprising a) a binder; and b) fibres.
  • the invention provides a multilayer intumescent coating system comprising an intumescent coating layer A and a non-intumescent coating layer B directly thereon, wherein:
  • coating layer A comprises, or is formed from, a) a binder; b) an acid generating agent; and c) an expansion agent; and
  • coating layer B comprises, or is formed from, a) a binder; and b) fibres.
  • the multilayer intumescent coating system comprises a second intumescent coating layer C which is applied directly on layer B.
  • coating layer C comprises such as consists of, (or is formed from) an intumescent coating composition C comprising a) a binder; b) an acid generating agent; and c) an expansion agent.
  • coating layer C has the same composition as coating layer A.
  • Coating layer B is coated directly on coating layer A and optional coating layer C is coated directly on coating layer B. There are no intermediate layers therefore between layers A, B and C. Coating layer A should be closest to the substrate being coated.
  • Coating layer B is non-intumescent and hence does not expand significantly and does not from a carbonaceous char when exposed to heat or fire. It is preferably free therefore of the components that form an intumescent coating, i.e. the combination of an acid generating agent and expansion agent.
  • the multilayer intumescent coating system does not comprise a mesh.
  • the invention provides a substrate coated with an intumescent coating system as hereinbefore defined.
  • the substrate may be provided with a primer coating as is known in the art.
  • the invention provides a process for the application of a multilayer intumescent coating system as hereinbefore defined to a substrate comprising applying coating layer A to a substrate and applying coating layer B directly on top of layer A.
  • the invention provides a process for the application of a multilayer intumescent coating system as hereinbefore defined to a substrate comprising applying an intumescent coating composition A to a substrate and optionally allowing that composition to cure so as to form a coating layer A; and applying a non-intumescent coating composition B directly onto coating layer A and optionally allowing that composition to cure so as to form a coating layer B.
  • the invention provides use of an intumescent coating system as hereinbefore defined to protect a substrate from fire.
  • the invention relates to an intumescent coating system.
  • the term intumescent coating system defines a multilayer coating system which comprises at least an intumescent coating layer A and a non-intumescent coating layer B.
  • the intumescent coating system may also comprise a third layer C which is intumescent.
  • the intumescent coating system of the invention may therefore comprise at least 2 or 3 layers.
  • a top coat may be applied over the intumescent coating system of the invention, e.g. for aesthetic reasons.
  • intumescent coating composition defines the composition used to prepare the intumescent coating layer A and optional layer C.
  • non- intumescent coating composition defines the composition used to prepare the non- intumescent coating layer B. It will be appreciated therefore that coating layers A, B and C ideally consist of the components of corresponding intumescent coating compositions A, B and C. It will also be appreciated that in a final multilayer intumescent coating system, any organic solvent or water that is present to allow application of the intumescent coating compositions A, B and C to a substrate will evaporate. The layers of the intumescent coating system may also cure. Where therefore wt% are given herein for the intumescent or non-intumescent coating compositions these percentages also apply to the intumescent or non-intumescent coating layers as these layers are formed from the corresponding composition.
  • the intumescent coating composition contains components to ensure intumescence.
  • the intumescent components are the acid generating agent and the expansion agent.
  • the coating composition comprises a specific carbon- source as an intumescent component.
  • intumesce means to char and expand.
  • components in an intumescent coating chemically react to produce gases and a cellular carbonaceous char that expands into a foam when the gases become trapped within the char.
  • Intumescent coatings thus form a relatively thick and thermally insulative foam barrier on the surfaces of coated substrates exposed to the heat from a fire.
  • expansion is used in relation to an intumescent coating to refer to a measure of the increase in the volume of a coating after contact with heat from a fire. It is preferably determined by measuring the char depth using a char depth gauge/hydrocone.
  • Non-intumescent coating layer derived from the non-intumescent coating composition does not expand significantly upon contact with heat from a fire and does not form a carbonaceous char.
  • Non-intumescent layers should not comprise a combination of an acid generating agent and an expansion agent. They do not expand when exposed to the heat from a fire.
  • expansion agent is used interchangeably with the term blowing agent herein.
  • acid generating compound might also be called acid catalyst herein.
  • binder refers to a polymer which forms a continuous film on a substrate surface when applied thereto.
  • the binder may be physically drying or cured using curing agents and optionally crosslinkers.
  • epoxy-based binder system refers to the combination of epoxy resin(s) and curing agent(s), and optionally reactive epoxy diluents, silanes, accelerators and hydrocarbon resins.
  • curing agent refers to compound which, when mixed with a binder, e.g. epoxy-based binder, produces a cured or hardened coating by generating crosslinks within the polymer. Sometimes curing agents are referred to as hardeners.
  • (meth)acrylate encompasses both methacrylate and acrylate.
  • dispersion refers to both particles and droplets (emulsions) dispersed in water.
  • the intumescent coating system is overcoated with a top coat.
  • the topcoat may provide the desired colour to the substrate and enhance the durability of the intumescent coating system.
  • a clear top-coat may also be suitable.
  • Top coats are preferably free of fibres. They are thus readily distinguishable from the non-intumescent layer B.
  • the intumescent coating system is not overcoated with a top coat.
  • the intumescent coating layer A is present directly on a substrate. In another embodiment the intumescent coating layer A is present over an anticorrosive primer layer, e.g. epoxy layer on the substrate.
  • This invention relates to an intumescent coating system for a substrate such as a metal substrate or a composite material or cellulosic substrate, preferably a steel substrate. That substrate can be present on any object on which the coating system of the invention might be useful.
  • the substrate may be an off-shore or on-shore oil and gas facility, wind turbine, chimney, power station or other industrial unit, bridge, crane, high value infrastructure such as hotels, hospitals, airports, stadiums, office blocks and so on.
  • the substrate may be provided with a conventional anti-corrosive primer coating to which the intumescent coating layer A adheres.
  • suitable primer layers are coatings based on epoxy, modified epoxy (such as modified with polyvinyl butyral), polyurethane, acrylic, vinyl and chlorinated rubber.
  • the primer layer is an epoxy-based primer or a zinc-rich epoxy-based primer.
  • the dry film thickness of the primer is ideally in the range of 15-500 pm.
  • the intumescent coating layer A may also be applied directly on the substrate, e.g. direct to a metal.
  • the intumescent coating system (i.e. layers A and B or layers A, B and C as defined herein) may be applied in high dry film thickness to ensure good fire protection.
  • the dry film thickness of the intumescent layer A is preferably 150 pm - 10 000 pm, preferably 200 pm - 8000 pm, more preferably 500 pm to 4000 pm.
  • the dry film thickness of non-intumescent layer B is preferably less than 2000 pm, more preferably less than 1500 pm, more preferably less than 1000 pm. In some embodiments, the dry film thickness of non-intumescent layer B is more than 25 pm, preferably more than 50 pm, more preferably more than 100 pm. The dry film thickness of non-intumescent layer B is preferably 100 pm to 1500 pm, more preferably 200 pm to 1000 pm.
  • the dry film thickness of non-intumescent layer B is preferably less than 500 pm, more preferably less than 400 pm, further preferred less than 300 pm.
  • the dry film thickness of the non- intumescent layer B is less than 200 pm.
  • the ratio between the dry film thickness of the intumescent layer A and the non-intumescent layer B may be 1 : 1 to 1 :0.05, preferably 1:0.6 to 1 :0.1.
  • Optional intumescent layer C is preferably 150 pm to 10000 pm, more preferably 200 pm to 8000 pm in dry film thickness.
  • the total dry film thickness of intumescent layer A, non-intumescent layer B and optional intumescent layer C is preferably 500 pm to 20000 pm, more preferably 1000 pm to 16000 pm.
  • the dry film thickness of intumescent layer C is 0.2 to 3.0 times the thickness of intumescent layer A.
  • Non-intumescent layer B may be a different colour to intumescent coating layer A. The presence of layer B will then easily be identified and the DFT (dry film thickness) of the non-intumescent layer B is therefore easily verifiable with a standard DFT gauge.
  • the top coat used for overcoating the intumescent coating system may be based on polyurethane, polysiloxane, epoxy, alkyd, acrylic, vinyl and chlorinated rubber.
  • the top coat is acrylic, polysiloxane or polyurethane based.
  • the top coat is not based on vinyl ester, especially not a vinyl acetate.
  • the thickness of the decorative topcoat can vary from 15 pm to 250 pm. Preferably the thickness should be in the range from 25 pm to 100 pm, as too high a thickness of topcoat may inhibit the intumescent reactions.
  • the intumescent coating system does not comprise a top coat.
  • the intumescent coating system of the invention is designed to protect substrates to critical core temperatures ranging from 200-750 °C depending on the nature of the substrate, degree of load and particular requirements of the specific structure being protected.
  • the critical core temperature is typically defined as the temperature when a specific substrate has lost load bearing capacity to such a degree that the structure is at immediate risk of a critical collapse.
  • the intumescent coating layer A is prepared through the application of an intumescent coating composition to the substrate.
  • the intumescent coating layer C is prepared through the application of an intumescent coating composition to layer B.
  • This layer C may be the same or different to layer A but the description which follows for the intumescent coating composition applies to both layers A and C.
  • layer C has the same composition as layer A.
  • the intumescent coating composition comprises a binder.
  • the intumescent coating composition comprises a binder, intumescent components and may comprise conventional intumescent coating components such as pigments, fillers and standard additives.
  • the intumescent components include an acid-generating agent which typically decomposes at elevated temperatures (e.g. greater than 200 °C) and produces an acid that reacts with a carbon donor compound to produce a carbonaceous char.
  • the intumescent components also include an expansion agent that decomposes at elevated temperatures (e.g. greater than 200° C) and produces a gas that volumetrically expands the carbonaceous char and produces a carbonaceous foam.
  • Intumescent coating compositions of the invention can comprise a specific carbon donor compound which functions as a charring agent or the binder may act as a carbon donor.
  • the intumescent coating composition comprises a specific carbon donor compound as specified below.
  • the acidgenerating agent decomposes to provide an acid.
  • the carbon donor compound reacts with the acid to form a carbonaceous char.
  • an ammonium polyphosphate acid-generating agent decomposes at about 240 °C to form ammonia and phosphoric acid.
  • the phosphoric acid can function as an acid for dehydration reactions of organic polyol compounds such as starch, cellulose, non-polymeric sugars (e.g., glucose, fructose, sucrose, and the like), pentaerythritol, dipentaerythritol, or tripentaerythritol, or combinations of any thereof, which function as carbon donor compounds.
  • organic polyol compounds such as starch, cellulose, non-polymeric sugars (e.g., glucose, fructose, sucrose, and the like), pentaerythritol, dipentaerythritol, or tripentaerythritol, or combinations of any thereof, which function as carbon donor compounds.
  • the phosphoric acid reacts with the hydroxyl groups to form heat-unstable phosphate esters, which decompose to release carbon dioxide and regenerate the phosphoric acid.
  • the dehydrated carbon donor and/or the binder system forms the carbonaceous char, and the carbon dioxide expands the char into a foam.
  • the expansion agent likewise decomposes at elevated temperatures (e.g., greater than 200° C.) and produces additional gas that volumetrically expands the carbonaceous char and produces the carbonaceous foam.
  • the intumescent coating composition of the invention comprises an acid-generating agent, an expansion agent and optionally a specific carbon donor compound.
  • the binder can also act as the carbon donor.
  • the intumescent coating composition can be solvent free, solvent-borne or water-borne.
  • any organic solvent or water evaporates to leave a dried multilayer intumescent coating system in which layer A contains the solid components of intumescent coating composition, layer B contains the solid components of non- intumescent coating composition and so on.
  • the intumescent coating composition of the invention adheres well to both the substrate or a primer layer on that substrate and offers good water resistance and rapid hardness.
  • the intumescent coating layer preferably expands by more than 1.5 times the volume of the coating layer when exposed to heat from a fire, such as at least 5 time, times, e.g. 6 to 80 times.
  • the intumescent coating composition preferably comprises 11 wt.% or more of an acid generating agent based on the total dry weight of the coating composition, further preferably 15 wt.% or more.
  • the intumescent coating composition preferably comprises 1.5 wt.% or more of an expansion agent.
  • the intumescent coating composition preferably comprises 11 wt.% or more of an acid generating agent based on the total dry weight of the coating composition in combination with 1.5 wt.% or more of an expansion agent based on the total dry weight of the coating composition.
  • the non-intumescent coating layer B is prepared through the application of a non-intumescent coating composition B to coating layer A.
  • the non-intumescent coating composition comprises a binder and fibres. It will be appreciated that the non-intumescent coating composition B is different from the intumescent coating composition A. It will be appreciated that the non-intumescent coating layer B is different from the intumescent coating layer A.
  • the non-intumescent coating layer preferably expands by less than 1.5 times the volume of the coating layer when exposed to heat from a fire, preferably less than 1.3 times, more preferably less than 1.1 times.
  • the non-intumescent coating layer does not expand when exposed to the heat from a fire.
  • the non-intumescent coating composition preferably comprises less than 10 wt.% of an acid generating agent, more preferably less than 5 wt.%, further preferred less than 2.5 wt.% based on the total dry weight of the coating composition.
  • the non-intumescent coating composition preferably comprises less than 1.5 wt.% of an expansion agent, more preferably less than 1.0 wt.% of an expansion agent, further preferred less than 0.5 wt.% of an expansion agent based on the total dry weight of the coating composition.
  • the non-intumescent coating composition preferably comprises less than 10 wt.% of an acid generating agent in combination with less than 1.5 wt.% of an expansion agent, preferably less than 5 wt.% of an acid generating agent in combination with less than 1.0 wt.% of an expansion agent based on the total dry weight of the coating composition.
  • the non-intumescent coating composition does not comprise a combination of an acid generating agent and an expansion agent.
  • the non-intumescent coating may comprise conventional coating components such as pigments, fillers and standard additives.
  • the non-intumescent coating composition can be solvent free, solvent-borne or water-borne.
  • the non-intumescent coating composition of the invention adheres well to the intumescent coating composition. It is a particular feature of the invention that the interlayer adhesion between the layers is strong.
  • any suitable binder can be used in the intumescent or non-intumescent coating.
  • the skilled person can adapt the intumescent and non-intumescent coating compositions accordingly depending on the binder used, e.g. whether a curing agent is required.
  • Suitable binders are vinyl-based binders, polyvinyl ester-based binders, polyurethane-based binders, polyurea-based binders, polycarbonate-based binders, polyether-based binders, polysulphone-based binders, polysulphide, polysiloxane-based binders, polyamide-based binders, chlorinated olefine-based binders, melamine-formaldehyde or urea-formaldehyde based binders, polyester- based binders, acrylic-based binders or epoxy-based binders or mixtures or copolymers thereof.
  • the binder is a polyvinyl ester-based binder such as a vinyl acetate-based binder, an acrylate-based binder such as a styrene-acrylate co-polymer or an epoxy-based binder.
  • the intumescent or non-intumescent coating composition comprises one or more binders.
  • non-intumescent coating layer B has the same binder or at least the same type of binder as intumescent coating layer A and optionally intumescent coating layer C.
  • binder type is meant that for example, both binders are epoxy based or both binders are polyvinyl ester-based, (meth)acrylate-based etc.
  • An advantage of layer A and layer B and optionally layer C comprising the same type of binder is that adhesion and compatibility are improved. When binder systems with different properties are used the cohesion can be weak.
  • both the intumescent and non-intumescent coating compositions comprise polyvinyl ester-based binders, (meth)acrylic-based binders and/or epoxy-based binders.
  • Vinyl ester-based binders such as vinyl acetate-based binders and epoxy-based binders are especially preferred.
  • the binder can be soluble in an organic solvent.
  • the liquid carrier for the intumescent or non-intumescent coating composition can be an organic solvent, including, but not limited to, ketones, esters, alcohols, aromatics and hydrocarbons. More preferably, the binder can be soluble or disperseable in water.
  • the liquid carrier for the intumescent or non-intumescent coating composition can be water.
  • the binder may also be solvent free and used in intumescent or non- intumescent coating compositions that are solvent free.
  • the binder may be present in the intumescent coating composition in the range of 10 to 70 wt%, such as 10 to 50 wt% based on the total coating composition. In one embodiment, the binder may be present in the intumescent coating composition in the range of 10 to 50 by dry wt% of the total coating composition. It therefore follows that the binder may be present in the intumescent coating layer A in the range of 10 to 50 by dry wt%.
  • the binder may be present in the non-intumescent coating composition in the range of 5.0 to 80 wt%, such as 7.0 to 70 wt% based on the total weight of the coating composition.
  • the binder may be present in the non-intumescent coating composition in the range of 10 to 70 by dry wt%, such as 10 to 60 by dry wt% of the coating composition. It therefore follows that the binder may be present in the intumescent coating layer B in the range of 10 to 70 by dry wt%, such as 10 to 60 by dry wt%.
  • Any known polyvinyl ester-based binders can be used to prepare the intumescent or non-intumescent coating composition.
  • the use of a polyvinyl acetate-based binder is especially preferred.
  • the polyvinyl ester-based binder is a polyvinyl ester based homopolymer, such as a polyvinyl acetate based homopolymer.
  • the polyvinyl ester-based binder is a copolymer derived from vinyl ester monomers, such as vinyl acetate, and at least one of ethylene, vinyl chloride, a different vinyl ester (e.g. a vinyl ester of one or more long-chain branched carboxylic acids), di-n-butyl maleate, (meth)acrylic acid and (meth)acrylic ester.
  • Co-polymers of vinyl acetate and ethylene are particularly preferred.
  • the polyvinyl ester-based binder is a copolymer derived from vinyl acetate and vinyl versatate.).
  • the polyvinyl ester-based binder may also be a terpolymer such as a terpolymer derived from ethylene, vinyl acetate and (meth)acrylate.
  • Suitable polyvinyl ester-based binders are commercially available.
  • the polyvinyl ester-based binder may be solvent-borne or water-borne. Preferably the polyvinyl ester-based binder is water-borne.
  • the polyvinyl ester-based binder is preferably dispersed in water.
  • the polyvinyl ester-based binder is typically present in the dispersion in the form of particles or droplets with an average size of 4 to 1000 nm, preferably 25 to 400 nm, more preferably 50 to 350 nm, such as 100 to 300 nm.
  • the polyvinyl ester-based droplets or particles preferably form 10 to 80 wt% of the dispersion, relative to the total weight of the dispersion as a whole.
  • Typical wt% ranges may be 35 to 60 wt%, such as 40 to 60 wt%, relative to the total weight of the dispersion as a whole.
  • the polyvinyl ester-based dispersions may in addition to water also comprise polar organic solvents such as acetone, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, 2-methoxyethanol, 2- eth oxyethanol, 2-butoxyethanol, l-methoxy-2-propanol, l-ethoxy-2-propanol, diacetone alcohol, dioxane, ethylene glycol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol monomethyl ether (Dowanol DPM), ethylene glycol monopropyl ether, and ethylene glycol monohexyl ether.
  • polar organic solvents such as acetone, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, 2-methoxyethanol,
  • the polyvinyl ester-based dispersion may be prepared by any suitable known method in the art.
  • the polyvinyl ester-based dispersion may also comprise surfactants, antifoaming agents, rheology modifiers, pH adjusting agents and biocides. These components are described further under additives.
  • the content of organic solvent is preferably low, such as less than 5.0 wt% solvent, especially less than 2.0 wt% organic solvent, more especially less than 1.0 wt% organic solvent, e.g. 0.5 wt% or less.
  • the VOC content of the intumescent and non-intumescent coating composition comprising a water-borne polyvinyl ester-based binder is preferably less than 250 g/L, more preferably less than 100 g/L, most preferably less than 50 g/L. In some embodiments, the VOC content might be 25 g/L or less, such as 10 g/L or less.
  • volatile organic compounds include benzyl alcohol.
  • (Meth)acrylic-based binder Any known (meth)acrylic based binder can be used to prepare the intumescent or non-intumescent coating composition.
  • (meth)acrylic-based binders of interest are those prepared using one or more monomers such as (meth)acrylic acids or esters such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxy ethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3- hydroxypropyl (meth)acrylate, 2-hydroxy- 1 -methylethyl (meth)acrylate, 4- hydroxybutyl (meth)acrylate and hydroxyisobutyl (meth)acrylat, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, 2-(2- ethoxyethoxy)ethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isoprop
  • (Meth)acrylic-based binders of use in the intumescent or non-intumescent coating composition may be ones based on monomers containing two or more polymerizable ethylenically unsaturated bonds.
  • monomers containing two or more polymerizable ethylenically unsaturated bonds include monomers such as 1,2-ethanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,3-glycerol di(meth)acrylate, methacrylic anhydride, zinc di(meth)acrylate, and trimethylolpropane tri(meth)acrylate.
  • the monomers listed above may be combined with other non-(meth)acrylic monomers to prepare the desired polymer such as styrene and acrylonitrile.
  • the (meth)acrylic-based binder is a styrene- (meth)acrylate co-polymer.
  • the (meth)acrylic-based binder may be a physically drying binder.
  • the (meth)acrylic binder may also be cured by radical polymerization using azo or peroxide initiators such as described in WO2021/180488 Al and W02005/000975 Al.
  • Crosslinking agents such as difunctional or trifunctional (meth)acrylates or triallyl cyanurates may be present.
  • the (meth)acrylic-based binder may be dissolved in an organic solvent or dispersed in water.
  • the water-borne (meth)acrylic based binder dispersions may also comprise surfactants, antifoaming agents, rheology modifiers, pH adjusting agents and biocides. These components are described further under additives.
  • any known epoxy-based binder can be used to prepare the intumescent or non-intumescent coating composition.
  • the epoxy-based binder is cured with at least one curing agent.
  • Other components such as reactive diluents, accelerators, silanes and hydrocarbon resins may also be part of the epoxy-based binder system.
  • the intumescent or non-intumescent coating composition is typically supplied in kit form and shortly before application of the intumescent or non-intumescent coating composition to a substrate, a first composition comprising the epoxy binder is mixed with a second composition comprising the curing agent to form the intumescent or non-intumescent coating composition. After application, that intumescent or non-intumescent coating composition then cures on the substrate to form an intumescent or non-intumescent coating layer.
  • the intumescent or non-intumescent coating composition may be water-borne, solvent-borne or solvent free.
  • the intumescent or non-intumescent coating composition comprising the epoxy-based binder may have a high solids content and thereby a low content of volatile organic compounds (VOC) present.
  • the intumescent or non-intumescent coating composition comprising an epoxy-based binder preferably has a solids content of at least 90 wt%, such as at least 95 wt%, more preferably at least 99 wt%, especially 100 wt.%.
  • the intumescent or non-intumescent coating composition comprising an epoxy-based binder may contain a very low organic solvent content such as less than 5.0 wt% solvent, especially less than 2.0 wt% organic solvent, more especially less than 1.0 wt% organic solvent, e.g. 0.5 wt% or less.
  • the VOC content of the intumescent or non-intumescent coating composition comprising an epoxy-based binder is preferably less than 250 g/L, more preferably less than 100 g/L, most preferably less than 50 g/L. In some embodiments, the VOC content might be 25 g/L or less, such as 10 g/L or less.
  • volatile organic compounds include benzyl alcohol.
  • the epoxy-based binder preferably comprises one or more epoxy-based binders selected from aromatic or aliphatic epoxy-based binders preferably comprising more than one epoxy group per molecule.
  • the epoxy-groups may be in an internal or terminal position on the epoxy-based binder or on a cyclic structure incorporated into the epoxy-based binder.
  • the epoxy-based binder comprises at least two epoxy group so that a crosslinked network can be formed.
  • epoxy-based binders of the present invention also encompass binders that have the traditional epoxy backbones but where the epoxy end-groups have been modified with acrylic or methacrylic functional groups that can be cured with the same curing agents as the epoxy-groups.
  • Suitable aliphatic epoxy-based binders include epoxy and modified epoxy binders selected from cycloaliphatic epoxy such as hydrogenated bisphenol A, hydrogenated bisphenol A novolac and dicyclopentadiene based binders, glycidyl ethers such as polyglycidyl ethers of polyhydric alcohols, epoxy functional acrylic resins or any combinations thereof.
  • Suitable aromatic epoxy-based binders include epoxy and modified epoxy binders selected from bisphenol type epoxy-based binders such as bisphenol A, bisphenol F and bisphenol S, resorcinol diglycidyl ether (RDGE), novolac type epoxy-based binders such as phenolic novolac type binders (bisphenol A novolac, bisphenol S novolac) and cresol novolac type binder or any combinations thereof.
  • the epoxy-based binder is an aromatic epoxy-based binder.
  • the aromatic epoxy-based binder is derived from a combination of a compound comprising a least one epoxide functionality with an aromatic coreactant comprising at least two hydroxyl groups.
  • Preferred epoxy binders are bisphenol epoxy binders.
  • Preferred epoxy-based binders are bisphenol A and bisphenol F epoxy-based binders or bisphenol A/F epoxy binders.
  • the epoxy-based binder may be a modified epoxy-based binder.
  • the epoxy-based binder is modified with fatty acids, polypropylene oxide and/or polyethylene oxide.
  • the solids content in the epoxy-based binder is preferably more than 70 wt.%, preferably more than 80 wt.%, preferably more than 90, most preferred more than 99 wt.%.
  • the epoxy-based binder is solvent free.
  • Bisphenol A type epoxy-based binders Epikote 828 from Hexion, Araldite GY 250 from Huntsman Advanced Materials,
  • Bisphenol F epoxy based binders Epikote 862 from Hexion, YDF- 170 from Kukdo, GY285 from Huntsman, DE 354 from Dow, BFE-170 from CCP, or KF8100 from Kolon.
  • the epoxy-based binder may be either a liquid epoxy-based binder or a solid epoxy-based binder or a combination thereof. It should be understood that “liquid” and “solid” refers to the physical state of the epoxy-based binder at ambient temperature and pressure (25 °C and 1 atm). In one preferred embodiment the epoxy-based binder is a liquid epoxy-based binder.
  • the liquid epoxy-based binder may have an epoxy equivalent weight (EEW) value of 140 to 1000. It is particularly preferred if the EEW is less than 500 such as 156 to 300, especially 156 to 250.
  • EW epoxy equivalent weight
  • the viscosity of the liquid epoxy-based binder is preferably 1000 to 20 000 mPa, more preferred 1500 to 15 000 mPas.
  • the solid epoxy-based binder may have an equivalent epoxy weight (EEW) of 300 to 1000. It is most preferred however if the EEW of the solid epoxy-based binder is in the range of 350 to 750, such as 400 to 700, especially 500 to 670. The use of a solid bisphenol A type epoxy-based binder is most preferred.
  • EW equivalent epoxy weight
  • liquid epoxy-based binder is in excess relative to the solid epoxy-based binder.
  • the epoxy-based binder is preferably present in 5.0 to 60 wt.% by dry weight of the intumescent coating composition, such as 5.0 to 40 wt% by dry weight of the intumescent coating. More preferably the epoxy-based binder is present in an amount of 10 to 30 wt.% by dry weight, especially 12 to 28 wt% by dry weight, most especially 16 to 25 wt% by dry weight. If a blend of epoxy binders is used these percentages refer to the total epoxy binder content, i.e. adding the wt% of each one.
  • the epoxy-based binders include bisphenol A based binders, such as 4,4'-isopropylidenediphenol-epichlorohydrin resins, bisphenol F based binders and/or novolac based binders.
  • Bisphenol A epoxy- based binders will be known to those in the field and have the general structure below.
  • the epoxy-based binder comprises one or more bisphenol F epoxy-based binders.
  • the bisphenol F epoxy-based binder may have an EEW value of 100 to 350. However, it is particularly preferred if the EEW is 300 or less such as 100 to 300, especially 150 to 250. Preferably the bisphenol F epoxy-based binder is a liquid.
  • the Mw of the bisphenol F resin may be more than 170 g/mol.
  • a preferred bipshenol F (4',4'-methylenebisphenol) epoxy-based binder derives from the combination of bisphenol F and epichlorohydrin. The use of a difunctional epoxybased bisphenol F binders is especially preferred.
  • a combination of two or more bisphenol F binders might be used.
  • the viscosity of the bisphenol F binders are preferably 1000 to 10 000 mPas, more preferred 2000 to 5000 mPas.
  • the intumescent or non-intumescent coating composition comprises at least one curing agent.
  • the curing agent can be any curing agent commonly known as a curing agent for epoxybased binders. Ideally it is amine based. Most preferably, it is a polyamine comprising at least two amino groups. Especially preferably, the curing agent is based on benzylamine, i.e. the curing agent comprises a benzylamine motif:
  • the benzylamine in the curing agent may be optionally substituted either on the ring, the methylene linker or the N atom although one active hydrogen must remain.
  • Suitable substituents include Ci-4 alkyl groups, OH, O-Ci-4-alkyl, halogen, cyano, amine and alkyl amine groups (C1-4-N).
  • the curing agent must contain at least two "reactive” hydrogen atoms.
  • “Reactive” hydrogen atom refers to the hydrogen atom that is transferred from the nucleophile to the oxygen atom of the epoxide during the ring opening reaction.
  • the curing agent typically contains at least two curing reactive functional groups. Curing active amine groups cannot therefore be tertiary.
  • Suitable curing agents are thiol curing agents, polythiol curing agents, amine curing agents, polyamine curing agents, amine functional polyamide and/or aminofunctional polymer curing agents.
  • the curing agent may also alternatively comprise at least one aminofunctional polysiloxane.
  • polythiol curing agents examples include pentaerythriol tetramercapto propionate.
  • Example of a suitable commercially available polythiol curing agent is GABEPRO® GPM800 from Gabriel performance materials.
  • the intumescent or non-intumescent coating composition comprises an epoxy-based binder and at least one amine functional curing agent.
  • the curing agent typically contains at least two amine groups.
  • the amine groups may be primary or secondary.
  • Suitable curing agents comprising amines or amino functional polymers are selected from aliphatic amines and polyamines (e.g. cyclo-aliphatic amines and polyamines), amine functional polyamides, polyether amines, polyimidazoles, polyoxy alkylene amines (e.g. polyoxy alkylene diamines), alkylene amines (e.g. alkylene diamines), aralkyl amines, aromatic amines, Mannich bases (e.g. those sold commercially as "phenalkamines”), polyamines comprising benzylamine structures, amino functional silicones or silanes, and including epoxy adducts and derivatives thereof.
  • aliphatic amines and polyamines e.g. cyclo-aliphatic amines and polyamines
  • amine functional polyamides e.g. polyether amines, polyimidazoles
  • polyoxy alkylene amines e.g. polyoxy alkylene di
  • the amine functional curing agent comprises a cyclic structure which includes alicyclic amines and modified products of alicyclic amines, preferably polyamines.
  • cyclic includes alicyclic, aromatic and heterocyclic polyamines.
  • the amine functional curing agent is a polyamine curing agent comprising one or more benzylamine motifs
  • the benzylamine in the curing agent may be optionally substituted either on the ring, the methylene linker or the N atom although one active hydrogen must remain.
  • Suitable substituents include Ci-4 alkyl groups, OH, O-Ci-4-alkyl, halogen, cyano, amine and alkyl amine groups (C1-4-N).
  • the curing agent is a polyamine curing agent comprising one or more benzylamine motifs. More specifically, the curing agent comprises two or more repeating units, i.e. the curing agent is polymeric or oligomeric.
  • the curing agent is a polyamine polymer that comprises a benzylamine motif on at least one end of the polyamine polymer chain.
  • the polyamine polymer may comprise benzylamine motifs at both ends of the polymer chain.
  • Each repeating unit may also comprise a benzylamine motif.
  • the benzylamine group may be substituted or unsubstituted.
  • the curing agent comprises at least two benzylamine groups.
  • the curing agent comprises a benzylated polyalkylene polyamine structure as described in WO2017/147138.
  • the benzylated polyalkylene polyamine structure may be further reacted with, for example phenolic compounds and formaldehyde to generate Mannich bases or epoxy-functional compounds to make epoxy-adducts.
  • the amine functional curing agent comprises a fatty amine motif. It is especially preferred if the fatty amine is a primary amine. It may be a fatty monoamine, such as a fatty mono primary amine. In particular, the curing agent may comprise a mixture of fatty monoamines, such as a mixture of fatty mono primary amines.
  • fatty amine is defined as any amine attached to an aliphatic carbon chain having 8 or more carbon atoms.
  • the fatty amine comprises a carbon chain of at least 10 carbon atoms, preferably at least 12 carbon atoms, e.g. 8 to 30 carbon atoms, especially C 12-20, e.g. one or more amine functional groups, e.g. NH2, bound to an aliphatic carbon chain having 8 or more carbon atoms.
  • the carbon chain may comprise one or more unsaturated double bonds.
  • the carbon chain is preferably linear (i.e. branch free).
  • Suitable fatty amines are octyl amine, decyl amine, dodecyl amine, tetradecyl amine, hexadecyl amine, octadecyl amine, pentadecyl amine, oleyl amine, didecyl amine, dodecyl- 1,3 -diaminopropane, coco alkyl amine, tallow amine and soya amine.
  • Coco alkyl amine and tallow amine are particularly preferred.
  • the amine functional curing agent comprises coco alkyl amine (CAS no. 61788-46-3).
  • fatty amines derived from natural sources such as coco alkyl amine, tallow amine and soya amine might comprise a mixture of different fatty amines.
  • the fatty amine in the amine functional curing agent may be part of a polyalkylene polyamine structure and/or an amine adduct.
  • the amine functional curing agent may comprise a mixture of a fatty amine and a polyalkylene poly amine and/or an amine adduct.
  • adducts of the amine curing agent might also be used.
  • Such adducts can be prepared by reaction of the amine with suitably reactive compounds such as epoxy-binders, epoxy-functional reactive diluent, acrylates, maleates, fumarates, methacrylates or electrophilic vinyl compounds such as acrylonitrile.
  • Suitable commercially available amine functional curing agents are:
  • the curing agent is an aliphatic and/or cycloaliphatic polyamine such as the Ancamine curing agents from Evonik.
  • the curing agent is an amine functional polyamide curing agent.
  • the amine functional polyamide curing agent comprises one or more benzylamine structures.
  • the curing agent can be supplied neat or in a solvent, ideally the curing agent is solvent free.
  • One or more curing agents might be used in combination. In one preferred option two or more curing agents are used in combination.
  • One preferred combination of curing agents is the combination of a polyamine curing agent comprising a benzylamine structure and a curing agent comprising an amine functional polyamide comprising a benzylamine structure.
  • the curing agent should cure the epoxy-based binder at temperatures ranging from 0 to 50 °C. It is preferred if the epoxy-based binder system cures at ambient temperatures.
  • the equivalent weight of the curing agent in terms of the “active hydrogen equivalent weight”.
  • the number of "active hydrogen equivalents" in relation to the one or more curing agents is the sum of the contribution from each of the one or more curing agents.
  • the contribution from each of the one or more curing agents to the active hydrogen equivalents is defined as grams of the curing agent divided by the active hydrogen equivalent weight of the curing agent, where the active hydrogen equivalent weight of the curing agent is determined as: grams of the curing agent equivalent to 1 mol of active hydrogen.
  • For adducts with epoxy resins the contribution of the reactants before adduction is used for the determination of the number of "active hydrogen equivalents" in the complete epoxy-based binder system.
  • the “epoxy equivalents” is the sum of the contribution from each of the one or more epoxy-based binders and any other component that contains an epoxy such as a silane or a reactive diluent.
  • the contribution from each of the one or more epoxy-based binders to the epoxy equivalents is defined as grams of the epoxy-based binder divided by the epoxy equivalent weight of the epoxy-based binder, where the epoxy equivalent weight of the epoxy-based binder is determined as: grams of the epoxy resin equivalent to 1 mol of epoxy groups.
  • For adducts with epoxy-based binder the contribution of the reactants before adduction is used for the determination of the number of "epoxy equivalents" in the epoxy-based binder system.
  • the ratio between the hydrogen equivalents of the totality of the curing agents and the totality of epoxy equivalents in the epoxy-based binder system of the present invention is in the range of 50: 100 to 120: 100.
  • compositions have a ratio between the hydrogen equivalents of the curing agent and the epoxy equivalents of the epoxy resin in the range of 60: 100 to 120: 100 such as 80: 100 to 120: 100, e.g. 90: 100 to 110: 100.
  • the curing agent is shipped separately to the epoxy-based binder and is only mixed with the epoxy-based binder shortly before application.
  • the mixing ratio of the compositions comprising the epoxy-based binder and the curing agent is, of course, governed by the relative amounts of epoxy and active hydrogens present.
  • the mixing ratio in solids volume is 1 : 1 to 10: 1, first to second composition, preferably 1 : 1 to 5: 1, most preferred 1 : 1.
  • the curing agent composition and the epoxy-based binder composition are mixed shortly before application to the substrate.
  • the curing agent may be present in the intumescent or non-intumescent coating composition in the range of 5 to 25 wt%, such as 10 to 22 wt%.
  • the curing agent Whilst a curing accelerator may be used, in one preferred embodiment, the curing agent is employed without the use of a separate accelerator to accelerate the crosslinking process. Some known curing agents are however, combined with an accelerator such as a tertiary amine catalyst and that is also within the scope of the invention.
  • the coating composition for the layer in question may undergo a curing reaction.
  • the coating layer may therefore be cured.
  • the coating layer A may therefore comprise an intumescent coating composition or the coating layer A can be formed from the intumescent coating composition, e.g by curing. It is challenging to identify the exact chemical make up of such a cured layer and hence it is simpler to define the coating layer with reference to the coating composition that is cured so as to form it.
  • the invention provides a multilayer intumescent coating system comprising an intumescent coating layer A and a non- intumescent coating layer B directly thereon, wherein:
  • coating layer A is formed from an optionally cured intumescent coating composition comprising a) a binder; b) an acid generating agent; and c) an expansion agent; and
  • coating layer B is formed from an optionally cured non-intumescent coating composition comprising a) a binder; and b) fibres.
  • Coating layers A to C can therefore be seen as dry coating layers.
  • the intumescent or non-intumescent coating composition further comprises a reactive diluent.
  • the reactive diluent preferably comprises epoxy and/or (meth) acrylic functional groups.
  • the reactive diluent forms part of the binder system and reacts with other components of the binder system during the curing process.
  • the reactive diluent is an epoxy-functional reactive diluent.
  • the epoxy-functional reactive diluent may be either monofunctional or difunctional or more. Combinations of reactive diluents with different functionality may also be used.
  • the epoxy-functional reactive diluent is reaction products of epichlorohydrin and an oil obtained from the shells of cashew nuts, like for example Cardolite NC-513 from Cardolite.
  • the epoxy-functional reactive diluents are aliphatic or cycloaliphtic epoxy-functional reactive diluents.
  • the aliphatic epoxy-functional reactive diluents are preferably formed from the reaction of a compound comprising at least one aliphatic epoxide functionality with an aliphatic alcohol or polyol such as 1,6-hexanediol diglycidyl ether or 1 ,4-butanediol diglycidyl ether.
  • Aliphatic glycidyl ethers of chain length 8 to 14 are also preferred.
  • Aliphatic epoxy-functional reactive diluents may contribute to the flexibility of the coating film.
  • the epoxy-functional reactive diluent is an aliphatic epoxy- functional reactive diluent such as 1,6-hexanediol diglycidyl ether.
  • the epoxy-functional reactive diluent is a cycloaliphatic epoxy-functional reactive diluent such as cyclohexanedimethanol diglycidyl ether.
  • the epoxy-functional reactive diluent is based on diglycidyl ethers of polyethers such as polyethylene glycol or polypropylene glycol.
  • the epoxy-functional reactive diluent may also be based on triglycerides such as castor oil.
  • the epoxy- functional reactive diluent is a triglycidyl ether of castor oil.
  • the epoxy equivalent weight (EEW) of the epoxy-functional reactive diluent is preferably 50 to 500, more preferred 100 to 400, most preferred 100 to 300.
  • the epoxy- functional reactive diluent is different from the epoxy binder. It is preferred if the reactive diluent is of low molecular weight such as less than 500 g/mol. Preferably the viscosity of the epoxy-functional reactive diluent is ⁇ 100 cp, preferably ⁇ 50 cP, preferably ⁇ 35 cp. It is therefore a liquid at 23°C and atmospheric pressure.
  • the reactive diluent comprises (meth) acrylic functional groups.
  • the (meth)acrylic functional reactive diluent is preferably an aliphatic (meth)acrylate comprising at least two (meth)acrylate functional groups linked by an organic linker.
  • a multiester may be a diester, a triester or a tetraester.
  • the molecular weight of the (meth)acrylate functional reactive diluent is preferably less than 1000, such as less than 750, especially less than 500 g/mol.
  • the (meth)acrylic functional reactive diluent will be the (meth)acrylate ester of a polyol such as a diol, or triol or a sugar based polyol such as a sugar alcohol. It is not essential for all OH groups within a polyol to carry the (meth)acrylate ester group, however there should preferably be at least two ester functionalities in the (meth)acrylic ester.
  • Suitable polyols for functionalization include alkylene diols (e.g.
  • hexanediol hexanediol, pentanediol
  • saccharides e.g. mono or disaccharides
  • polyols especially sugar alcohols
  • (Meth)acrylic functional reactive diluents of particular interest are of formula wherein R is H or Me; n is 2-5; and
  • L represents the residue of a polyol such as the residue of hexandiol or the residue of a saccharide or sugar alcohol.
  • a polyol such as the residue of hexandiol or the residue of a saccharide or sugar alcohol.
  • at least two OH groups of the polyol carry the acrylate ester shown in the formula above.
  • L preferably contains only C, H and O atoms.
  • the molecular weight of L is preferably low, such as 1000 g/mol or less.
  • the "acrylate equivalents” is the sum of the contribution from each of the one or more (meth)acrylic functional reactive diluents.
  • the contribution from each of the one or more (meth)acrylic functional reactive diluents to the acrylate equivalents is defined as grams of the (meth)acrylic functional reactive diluent divided by the acrylate equivalent weight of the (meth)acrylic functional reactive diluent, where the acrylate equivalent weight of the (meth)acrylic functional reactive diluent is determined as: grams of the (meth)acrylic functional reactive diluent equivalent to 1 mol of acrylate group.
  • a particularly preferred (meth) acrylic reactive diluent is trimethylol propane triacrylate.
  • the viscosity of the (meth) acrylic functional reactive diluent is preferably less than 300 mPas, more preferably less than 200 mPas, most preferred less than 150 mPas.
  • a preferred (meth)acrylic functional reactive diluent have an acrylate equivalent weight (AEW) value of 50 - 200, more preferred 70 - 150, most preferred 80 - 125.
  • AEW acrylate equivalent weight
  • the above reactive diluents can be used singly or in combination of two or more diluents.
  • the reactive diluent is preferably present in an amount of 0.25 to 15 wt.% by dry weight of the coating composition, preferably 0.5 to 10 wt.% by dry weight, more preferred 0.5 to 7.0 wt.% by dry weight of the intumescent or non-intumescent coating composition, especially 1.0 to 6.0 wt% by dry weight, more especially 1.0 to 5.0 wt% by dry weight. If a blend of reactive diluents is used these percentages refer to the total content of reactive diluents, i.e. adding the wt% of each one.
  • the intumescent or non-intumescent coating composition further comprises at least one silane.
  • the silane is part of the binder system and reacts with other components of the binder system during curing.
  • the silane is a functional silane comprising functional groups that can react with the binder system such as amine, epoxy, acryl, methacryl, thiol and isocyanate groups.
  • Silanes of use in the invention are generally of low Mw such as less than 400 g/mol. Suitable silanes are of general formula (I) or (II)
  • each R is a hydrocarbylene group having 1 to 12 C atoms optionally containing an ether or amino linker
  • R 1 is a hydrocarbyl group having 1 to 12 C atoms; each X independently represents a halogen group or an alkoxy group.
  • the binder system of the intumescent or non- intumescent coating system comprises:
  • R 1 is a hydrocarbyl group having 1 to 12 C atoms; each X independently represents a halogen group or an alkoxy group.
  • Y is a functional group bound to R that can react with the epoxy-based binder and/or the curing agent
  • Y is a isocyanate, epoxy, amino, hydroxy, carboxy, thiol, acrylate, or methacrylate group, more preferred epoxy, amino, acrylate or methacrylate groups, most preferred epoxy or amino group. It is particularly preferred if Y is an epoxy group.
  • the Y group can bind to any part of the chain R. It will be appreciated that where Y represents an epoxy group then R will possess at least two carbon atoms to allow formation of the epoxide ring system.
  • Y is an amino group or epoxy group.
  • the amino groups are preferably NH2.
  • Y is an epoxy group.
  • the silane is provided separately from the epoxy-based binder together with the curing agent. In general, in the kit of the invention, the silane should not react with any ingredient of the component of the kit in which the silane is present.
  • Each X independently represents a halogen group or an alkoxy group. It is especially preferred if X is an alkoxy group such as a Cl -6 alkoxy group, especially methoxy or ethoxy group. It is also especially preferred if there are two or three alkoxy groups present. Thus z is ideally 2 or 3, especially 3.
  • Subscript y is preferably 2.
  • R 1 is preferably Cl -4 alkyl such as methyl.
  • R is a hydrocarbyl group having up to 12 carbon atoms.
  • hydrocarbyl is meant a group comprising C and H atoms only. It may comprise an alkylene chain or a combination of an alkylene chain and rings such as phenyl or cyclohexyl rings.
  • the term "optionally containing an ether or amino linker” implies that the carbon chain can be interrupted by a -O- or -NH- group in the chain, e.g. to form a silane such as [3-(2,3-Epoxypropoxy)propyl] trimethoxysilane:
  • R is preferably an unsubstituted (other than Y obviously), unbranched alkyl chain having 2 to 8 C atoms.
  • a preferred silane general formula is therefore of structure (III)
  • R' is a unsubstituted, unbranched alkyl chain having 2 to 8 C atoms optionally containing an ether or amino linker
  • Y' is an amino or epoxy functional group bound to the R' group
  • X' represents an alkoxy group
  • silanes examples are the many representatives of the products manufactured by Evonik Industries AG in Rheinfelden and marketed under the brand name of Dynasylan(R)D, the Silquest(R) silanes manufactured by Momentive, and the GENIOSIL(R) silanes manufactured by Wacker.
  • Specific examples include methacryloxypropyltrimethoxysilane (Dynasylan MEMO, Silquest A- 174NT), 3-mercaptopropyltri(m)ethoxysilane (Dynasylan MTMO or 3201 ; Silquest A- 189), 3-glycidoxypropyltrimethoxysilane (Dynasylan GLYMO, Silquest A- 187), 3-glycidoxypropyltriethoxysilane (Dynasylan GLYEO), tris(3 -trimethoxy silylpropyl) isocyanurate (Silquest Y- 11597), gammamercaptopropyltrimethoxysilane (Silquest A- 189), beta-(3,4- epoxycyclohexyl)ethyltrimethoxysilane (Silquest A- 186), gamma- isocyanatopropyltrimethoxysilane (Silquest
  • silanes of interest include 3 -Aminopropyltriethoxysilane, 3 - Aminopropyltrimethoxysilane, N-(Aminoethyl)-aminopropyltrimethoxysilane H2NCH2CH2NHCH2CH2CH 2Si(OCH3)3, 3-aminopropylmethyldiethoxysilane, 3-(2- aminoethylamino)propylmethyldimethoxysilane, (H2NCH2CH2NHCH2CH2CH2CH 2 SiCH3(OCH3)2), [3-(2,3- Epoxypropoxy)propyl]triethoxysilane (H2COCHCH2OCH2 CH2CH2Si(OCH2CH3)3, [3 -(2,3 -Epoxypropoxy)propyl]trimethoxy silane (H2COCHCH2OCH2CH2CH2 Si(OCH3)3 ) and epoxy functional silane oligomers such as
  • the amount of silane present in the intumescent or non-intumescent coating composition may be in an amount of 0.1 to 15 wt% by dry weight, preferably 0.25 to 15 wt.% by dry weight such as 0.5 to 10 wt.% by dry weight, more preferred 0.5 to 7.0 wt.% by dry weight of the coating composition, especially 1.0 to 6.0 wt% by dry weight, more especially 1.0 to 5.0 wt% by dry weight.
  • the silane is present in an amount of 1.5 to 4.5 wt% by dry weight of the intumescent coating composition. If a blend of silanes is used these percentages refer to the total silane content, i.e. adding the wt% of each one.
  • silane comprises functional groups that can react with the epoxy binder it should be kept separate from the epoxy binder in the kit used to form the intumescent coating composition.
  • the intumescent or non-intumescent coating composition may further comprise a hydrocarbon resin.
  • hydrocarbon resin is a term of the art and refers to a group of typically petroleum derived hydrophobic resins although some resins may also be sourced naturally.
  • Preferred hydrocarbon resins of the invention contain C and H atoms only but some may also contain O atoms, e.g. where the -O- content may be 0 to 10.0 wt% such as 0 to 5.0 wt% of the hydrocarbon resin.
  • the hydrocarbon resins have a low water solubility such as less than 5 g/L, more preferred 2 g/L, most preferred 1 g/L.
  • hydrocarbon resin such as solid or liquid pure aromatic and/or aliphatic C5 and C9 hydrocarbon resins, mixtures of C5/C9, aliphatic/aromatic feedstocks and modified type hydrocarbon resins with epoxy or hydroxyl
  • the C5 resins are generally oligomers or polymers formed from aliphatic monomers with five carbons.
  • the C9 resins are generally oligomers or polymers of nine-carbon aromatic monomers.
  • the hydrocarbon resin has a molecular weight less than 1000 g/mol and most preferably molecular weight less than 500 g/mol.
  • the hydrocarbon resin is a petroleum resin.
  • the petroleum resin is a polymer that may contain a hydroxyl group, which is formed using, as a main raw material, a fraction produced as a by-product in the petroleum refining, from petrochemical and carbon feedstocks.
  • Examples of the petroleum resins suitable in the present invention include an aromatic petroleum resin obtained by polymerizing a C9 fraction (e.g.
  • styrene derivatives such as alpha methylstyrene, o, /??, -cresol, indene, methyl indene, cumene, napthalene or vinyltoluene) obtained from a heavy oil that is produced as a by-product by naphtha cracking, an aliphatic petroleum resin obtained by polymerizing a C5 fraction such as 1,3 -pentadiene or isoprene, 2-methyl-2-butene, cyclopentadiene, dicyclopentadiene or cyclopentene.
  • Also employable in the invention are a copolymer-based petroleum resin obtained by copolymerizing the C9 fraction and the C5 fraction, an aliphatic petroleum resin wherein a part of a conjugated diene of the C5 fraction such as cyclopentadiene or 1,3 -pentadiene is cyclic-polymerized, a resin obtained by hydrogenating the aromatic petroleum resin, and an alicyclic petroleum resin obtained by polymerizing dicyclopentadiene.
  • a hydroxyl group-containing aromatic petroleum resin is particularly preferable.
  • a phenolic hydrocarbon resin is preferred.
  • Another possibly hydrocarbon resin is a xylene resin synthesized from 1,3- dimethylbenzene and formaldehyde.
  • xylene resins modified with phenols such as bifunctional phenol (e.g., phenol, para-t- butylphenol, p- Cumylphenol, o,p-Dicumylphenol).
  • a coumarone resin which is a copolymer containing a coumarne constituent unit, an indene constituent unit and/or a styrene constituent unit in its main chain.
  • the indene-coumarone resin may be modified with phenol at the end, and at least a part of aromatic rings in the coumarone resin may be hydrogenated.
  • Such coumarone resins include a liquid product having a number-average molecular weight Mn of 200 to 300 and a solid product having a number-average molecular weight Mn of 600 to 800, and any one of them may be used singly, or both of them may be used in combination.
  • the hydrocarbon resin is a xylene formaldehyde resin such as EPODIL LV5 from Evonik or a phenol modified hydrocarbon resin such as Novares LC15 from Rutgers.
  • the hydrocarbon resin is a liquid hydrocarbon resin.
  • the hydrocarbon resin is preferably non-reactive, i.e. it does not react with other components of the intumescent coating composition. It is therefore preferred if the hydrocarbon resin is free of any epoxy groups. These resins can help decrease the viscosity of the binder system resin and reduce surface tension for improved surface wetting. They also add hydrophobic character to the composition which often results in improved water tolerance. They may also improve the flexibility of the coating film. The skilled person is familiar with the concept of hydrocarbon resins.
  • hydrocarbon resin with an “O atom” content of 0 to 8.0 wt% such as 0 to 5.0 wt% or a xylene formaldehyde with a OH content ⁇ 3 wt%.
  • hydrocarbon resins based on hydrogenation of natural resins such as rosins, e.g. gum rosin, wood rosin and tall oil rosins.
  • Hydrocarbon resins based on esterification of rosin esters can also be employed.
  • Hydrocarbon resins based on cardanol can also be employed.
  • the hydrocarbon resin forms 0.1 to 15 wt% by dry weight of the coating composition, preferably 0.5 to 10% by dry weight, e.g. 0.5-8.0 wt% by dry weight, especially 0.75 to 5.0 wt% by dry weight, most especially 1.0 to 4.0 wt% by dry weight.
  • hydrocarbon resin is preferably unreactive it can form part of either component in the kit used to form the intumescent coating composition.
  • the hydrocarbon resin can also act as a carbon donor in an intumescent coating.
  • the intumescent or non-intumescent coating composition further comprises a curing accelerator.
  • the curing accelerator may be any known curing accelerator for epoxy-based coating systems such as tertiary amines, (meth)acrylic esters, imidazoles, organic acids, phenols and organic phosphines.
  • tertiary amines examples include triethanol amine, dialkylamino ethanol, triethylene diamine, l,4-diazabicyclo[2.2.2]octane, 1,8-diaza- bicyclo[5.4.0]undec-7-ene and 2,4,6-tris(dimethylaminomethyl)phenol.
  • One particularly preferred accelerator is 2,4,6-tris(dimethylaminomethyl)phenol such as Ancamine K54 from Evonik.
  • Examples of suitable imidazoles are 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methyl imidazole and 2-heptadecylimidazole.
  • Suitable organic acids are benzoic acid derivatives such as salicylic acid.
  • organic phosphines examples include tributyl phosphine, methyldiphenyl phosphine, triphenyl phosphine, diphenyl phosphine and phenyl phospine.
  • Suitable phenols are alkyl phenols such as nonylphenol.
  • the intumescent or non-intumescent coating composition may also comprise at least one flame retardant such as a phosphorus containing flame retardant.
  • Suitable flame retardants include phosphoric acid, phosphite, phosphonate and phosphoric acid esters.
  • triarylphosphate esters especially triphenyl phosphate esters are preferred. Where a flame retardant is used this must be different and hence separate from any other component of the intumescent or non-intumescent coating composition.
  • the flame retardant forms from 0.5 to 10 wt% by dry weight of the intumescent or non-intumescent coating composition, preferably 1 to 10% by dry weight, e.g. , especially 1 to 8.0 wt% by dry weight.
  • the non-intumescent coating composition comprises fibres. In some embodiments the intumescent coating composition also comprises fibres. In some embodiments the intumescent coating composition does not comprise fibres.
  • the fibres are inorganic fibres or organic fibres.
  • Typical inorganic fibres include: carbide fibres, such as boron carbide fibres, silicon carbide fibres, niobium carbide fibres, etc.; nitride fibres, such as silicon nitride fibres; boron containing fibres, such as boron fibres, boride fibres; silicon containing fibres, such as silicon fibres, alumina-boron silica fibres, E-glass (non-base aluminum borates) fibres, C-glass (non-base or low base sodalime- aluminumborosilicate) fibres, A-glass (base -sodalime-silicate) fibres, S-glass fibres, inorganic glass fibres, quartz fibres, etc.
  • the glass fibres may include E-glass fibres, C-glass fibres, A-glass fibres, S-glass fibres, etc.
  • Useful inorganic fibres also include ceramic fibres and basalt fibres. Kevlar (para-aramid fibres) may also be used.
  • a preferred organic fibre is carbon fibres.
  • suitable fibres include mineral fibres.
  • the mineral fibres comprise aluminium oxide, calcium oxide, iron oxide, magnesium oxide and/or silica.
  • the fibres are mineral fibres.
  • the fibres form at least 0.25 wt% of the non-intumescent coating composition, preferably at least 1.0 wt%, preferably at least 5.0 wt%.
  • the fibres form 0.25 to 25 wt% of the non-intumescent coating composition, preferably 1.0 to 20 wt%.
  • the fibres form 0.5 to 40 dry wt% of the non- intumescent coating composition, preferably 2.0 to 30 dry wt%. It therefore follows that the fibres may be present in the non-intumescent coating layer B in the range of 0.5 to 40 dry wt%, such as 2.0 to 30 dry wt%.
  • the average length of the fibres is from 50 to 6000 pm, preferably from 100 to 3000 pm, especially 125 to 3000 pm.
  • fibers of different average length are used.
  • a first fibre population of length X might be combined with a second fibre population of differing length Y.
  • Using fibers of different average length helps to create the network of fibers needed to stabilize the char of the intumescent composition.
  • the difference in average length between the fibre populations may be at least 200 pm.
  • a first fibre population of 200 pm might be combined with a second fibre population of 500 pm.
  • a fibre population is a plurality of fibres of essentially the same length.
  • three or more fiber populations of different average length is used.
  • substantially all the fibres have an average length of 50 to 3000 pm. Fibers which have an average length less than 50 pm are not sufficiently long to provide the mesh effect that is the target here.
  • the melting point of the fibres is above 800 °C, preferably above 1000 °C, especially above 1200 °C.
  • the intumescent coating composition comprises a carbon donor compound.
  • the carbon donor compound can comprise an organic polyhydroxy compound (i.e. an organic polyol) and/or expandable graphite.
  • the carbon donor compound can comprise pentaerythritol, dipentaerythritol, tripentaerythritol, a polysaccharide (e.g., starch, cellulose, glycogen, and the like), a disaccharide sugar (e.g., sucrose, lactose, maltose, and the like), a monosaccharide sugar (glucose, fructose, galactose, and the like), glycerol, or expandable graphite, or a combination of any thereof.
  • the carbon donor is preferably pentaerythritol or dipentaerythritol.
  • the intumescent coating composition can comprise 0.0 to 20 wt% of the carbon donor compound, such as 3.0 to 20 wt% by dry weight, preferably 5.0 to 16 wt%, especially 7.0 to 14 wt% of the carbon donor compound based on the total weight of the intumescent coating composition.
  • the intumescent coating composition can comprise 0 to 30 dry wt% of a carbon donor compound, such as 8.0 to 20 dry wt%. It therefore follows that intumescent layer A may comprise 0 to 30 dry wt% of a carbon donor compound, such as 8.0 to 20 dry wt%. Acid Generating compound
  • the intumescent coating composition comprises an acid-generating compound.
  • the acid-generating compound can comprise a source of phosphoric or sulfonic acid that is capable of producing the phosphoric or sulfonic acid upon exposure to heat, particularly at temperatures greater than 200° C.
  • sources include sodium phosphate, potassium phosphate (e.g. potassium tripolyphosphate), ammonium phosphate (e.g. ammonium polyphosphate (APP), monoammonium phosphate, diammonium phosphate), sodium sulfate, potassium sulfate, ammonium sulfate, magnesium sulfate, or para-toluene sulfonic acid, or a combination of any thereof.
  • the acid-generating compound comprises a phosphoric acid ester of a polyhydroxy compound, or an ammonium phosphate (e.g., APP), or an amine phosphate (e.g., melamine phosphate), or a combination of any thereof.
  • an ammonium phosphate e.g., APP
  • an amine phosphate e.g., melamine phosphate
  • a particularly useful acid-generating compound is ammonium polyphosphate because APP yields phosphoric acid at temperatures generally below the decomposition temperatures of the carbon donor compounds described above. Thus, APP produces phosphoric acid that is readily available to participate in the charring reactions.
  • APP compounds are polymeric phosphates, having P-O-P linkages, which may be represented by the formula:
  • APP compounds in the intumescent coating compositions of the present invention include those having values of n>1000.
  • the acid-generating compound can also comprise boric acid or a source of boric acid that is capable of producing boric acid upon exposure to heat, particularly at temperatures greater than 200° C.
  • the source of boric acid can comprise, for example, borate salts such as ammonium pentaborate, zinc borate, sodium borate, lithium borate, aluminum borate, magnesium borate, borosilicate compounds, and combinations of any thereof.
  • the intumescent coating composition can comprise 10 to 50 wt% of an acidgenerating agent, preferably 12 to 40 wt%, more especially 15 to 30 wt% based on the total weight of the intumescent coating composition.
  • the intumescent coating composition can comprise 11 to 60 dry wt% of an acid-generating agent, preferably 15 to 40 dry wt%, more especially 20 to 40 dry wt% based on the total dry weight of the intumescent coating composition.
  • the intumescent coating layer A comprise 11 to 60 dry wt% of an acid-generating agent, preferably 15 to 40 dry wt%, more especially 20 to 40 dry wt% based on the total dry weight of the intumescent coating composition.
  • the intumescent coating composition comprises an expandable intumescent material (also known as a blowing agent or expansion agent).
  • the blowing agent will produce non-flammable gases, generally nitrogen, when exposed to fire or heat. The produced gases will expand the char derived from the carbon source, forming a foam-like protective layer.
  • Suitable examples of commercially available blowing agents include but are not limited to nitrogen-containing compounds such as glycine, melamine, melamine salts, melamine derivatives, urea, urea derivatives, dicyandiamide, guanidine, and isocyanurate derivatives, especially melamine.
  • Melamine derivatives include for example melamine formaldehyde, methylolated melamine, hexamethoxymethylmelamine, melamine monophosphate, di-melamine phosphate, melamine biphosphate, melamine polyphosphate, melamine pyrophosphate, melamine cyanurate, melamine borate, melam (N2-(4,6-diamino- l,3,5-triazin-2-yl)-l,3,5-triazine-2,4,6-triamine), melem (2,5,8-triamino- l,3,4,6,7,9,9b-heptaazaphenalene), and melon (poly[8-amino-l,3,4,6,7,9,9b- heptaazaphenalene-2, 5 -diyl)imino) .
  • Urea derivatives include, for example, N-alkylureas such as methyl urea; N,N'-dialkylureas such as dimethylurea; and N,N,N'-trialkylureas such as timethylurea; guanylurea; guanylurea phosphate; formamide amino urea; guanylurea phosphate; 1,3-diamino urea; biurea; and the like.
  • Isocyanurate derivatives of interest include tris-(2-hydroxyethyl)isocyanurate (THEIC).
  • Boron-containing compounds useful as blowing agents in the present invention include, but are not limited to, boric acid, and borates, such as ammonium pentaborate, zinc borate, sodium borate, lithium borate, aluminum borate, magnesium borate, and borosilicate.
  • the blowing agent may also comprise monomeric or polymeric compounds such as meso-lactide, polylactide, a poly sulfone, a polycarbonate, a polyester, a 1,1- di-activated vinyl compound, or an addition polymer of a 1,1-di-activated vinyl compound, or a combination of any thereof.
  • a physical blowing agent such as expandable graphite and/or gas incorporating expandable microspheres may also be used.
  • the intumescent coating composition can comprise 0.5 to 10 wt% of an expansion agent, preferably 1.0 to 8.0 wt%, more preferably 1.0 to 5.0 wt% based on the total weight of the intumescent coating composition.
  • the intumescent coating composition can comprise 1.5 to 15 dry wt% of an expansion agent, preferably 2.0 to 12 dry wt%, more preferably 2.0 to 10 dry wt% based on the total dry weight of the intumescent coating composition.
  • the intumescent coating layer A can comprise 1.5 to 15 dry wt% of an expansion agent, preferably 2.0 to 12 dry wt%, more preferably 2.0 to 10 dry wt% based on the total dry weight of the intumescent coating composition.
  • the intumescent and non-intumescent coating compositions may comprise other pigments and fillers in addition to the fibres described above.
  • Suitable fillers include titanium dioxide, zinc oxide, aluminium oxide, carbonates, borates, silica, silicates, heavy metal oxides such as cerium oxide, lanthanum oxide and zirconium oxide, kaolin, wollastonite, diatomaceous earth, bentonite clay, polymeric and inorganic microspheres such as uncoated or coated hollow and solid glass beads, uncoated or coated hollow and solid ceramic beads, porous and compact beads of polymeric materials.
  • Flaky fillers such as mica, glass flakes and micronized iron oxide (MiO) may also be used.
  • Preferred filler are titanium dioxide, kaolin and wollastonite.
  • the fillers preferably constitutes from 5% to 40% by weight of the intumescent or non-intumescent coating composition.
  • the fillers preferably constitutes from 10% to 50% dry weight of the intumescent or non-intumescent coating composition.
  • Examples of the colour pigments include titanium white, red iron oxide, yellow iron oxide, black iron oxide, carbon black and organic colour pigments.
  • the intumescent and non-intumescent coating compositions may also comprise various other additives. Suitable additives will depend on the binder used and whether the coating composition is solvent-borne, water-borne or solvent free.
  • additives examples include, rheology modifiers, surfactants, antifoaming agents, pH adjusting agents, dispersing agents, biocides, wetting agents, coalescing agents and anticorrosive agents.
  • Suitable rheology modifiers may be polyamide wax, polyethylene wax, polysaccharide rheology modifiers, associative rheology modifiers, clays, cellulosic rheology modifiers, fumed silica or a mixture thereof.
  • surfactants may also be used. This is especially relevant for the water-borne coating compositions.
  • a number of different surfactants may be suitable.
  • the surfactant may be non-ionic, anionic, cationic or amphoteric.
  • the coating compositions of the present invention may comprise an antifoaming agent.
  • Antifoaming agents are sometimes also referred to as foam control agents or defoamers.
  • foam control agents or defoamers A wide range of antifoaming agents are commercially available, and may be used in the coating compositions of the invention.
  • suitable antifoaming agents include organic siloxanes, polyethers, polyether-modified silicones, mineral oils and combinations thereof.
  • the coating compositions of the invention may comprise a pH adjusting agent such as ammonia, 2- aminopropanol, sodium hydroxide (NaOH), sodium carbonate (ISfeCCE) and sodium bicarbonate (NaHCCh).
  • a pH adjusting agent such as ammonia, 2- aminopropanol, sodium hydroxide (NaOH), sodium carbonate (ISfeCCE) and sodium bicarbonate (NaHCCh).
  • Coalescing agents may optionally be included if the coating compositions are waterborne.
  • the applied wet product is inhomogeneous, as opposed to a solventbome composition which will be homogenous when applied.
  • the polymeric binder droplets or particles must coalesce. Coalescing agents aid this process in the water phase.
  • coalescing agents examples include ester alcohol, benzyl alcohol, propylene glycol monomethyl ether (PM), propylene glycol propyl ether (PnP), dipropylene glycol n-butyl ether (DPnB), propylene glycol phenyl ether (PPh), tripropylene glycol n-butyl ether (TPnB), ethylene glycol propyl ether (EP), ethylene glycol butyl ether (EB), diacetone alcohol (DAA) and dipropylene glycol methyl ether (DPM).
  • PM propylene glycol monomethyl ether
  • PnP propylene glycol propyl ether
  • DPA propylene glycol phenyl ether
  • DPM diacetone alcohol
  • Suitable dispersing agents include conventional anionic, cationic, non-ionic and amphoteric dispersing agents as well as combinations thereof.
  • additives may be included to aid char formation and to strengthen the char and prevent char degradation.
  • Such additives include solids such as zinc borate, zinc stannate, zinc hydroxystannate, glass flake, glass spheres, polymeric spheres, fibres (ceramic, mineral, glass/silica based), aluminium hydroxide oxide, boron phosphate, fumed silica.
  • anticorrosive components may be metal oxides, metal carbonates, talc, feldspar and so on to act as anti-corrosive materials.
  • Specific anticorrosive functional pigments include zinc phosphate, zinc oxide, zinc dust, aluminium flakes, lead oxide.
  • Auxiliary corrosion inhibitors for example a molybdate, phosphate, tungstate or vanadate, ultrafine titanium dioxide, and/or zinc oxide and/or a filler such as silica, calcined clay, alumina silicate, talc, barytes or mica.
  • the total amount of the above-mentioned various additive components depend upon the use and cannot be determined indiscriminately, but they are frequently contained in the total amount of 0.1 to 65% by weight in the intumescent or non-intumescent coating composition, such as 0.5 to 50 wt%, preferably 0.5 to 30 wt%.
  • the total amount of various additive components may range from 0.5 to 75% by weight in the intumescent or non-intumescent coating composition, such as 2 to 60 by dry wt%.
  • the coating compositions of the present invention preferably contains low amounts of organic solvent.
  • organic solvent is not restricted, and publicly known solvents having boiling points of wide range are employable.
  • solvents include xylene, toluene, MIBK, methoxypropanol, MEK, butyl acetate, benzyl alcohol, octyl phenol, resorcinol, n-butanol, isobutanol and isopropanol.
  • the above solvents can be used singly or in combination of two or more kinds.
  • the coating compositions are waterborne polar organic solvent may be present such as acetone, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, 2-methoxyethanol, 2-ethoxyethanol, 2- butoxyethanol, l-methoxy-2-propanol, l-ethoxy-2-propanol, diacetone alcohol, dioxane, ethylene glycol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol monomethyl ether (Dowanol DPM), ethylene glycol monopropyl ether, and ethylene glycol monohexyl ether.
  • polar organic solvent such as acetone, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, 2-methoxyethanol, 2-ethoxyethanol, 2- butoxyethanol, l
  • the substrate has a primer layer therein onto which the intumescent coating layer A is applied.
  • the primer layer is conventional and is typically formed from an epoxy resin but other options may be used.
  • the primer layer preferably comprises at least 20 wt% epoxy resin, preferably at least 25 wt% epoxy resin.
  • primer layers are coatings based on epoxy, modified epoxy (such as modified with polyvinyl butyral), polyurethane, acrylic, vinyl and chlorinated rubber.
  • the primer layer is an epoxy-based primer or a zinc- rich epoxy-based primer.
  • the primer layer is a polysiloxane sol primer such as described in US2014/0106176.
  • the polysilane sol may be a component formed by the condensation reaction of at least one silane to form a highly branched polysilane sol which contains a plurality of free silanol functionalities.
  • the polysilane sol may be derived from at least one alkoxy silane precursor that has been subjected to hydrolysis to form the corresponding silanol. It will be appreciated that in many alkoxysilanes there are multiple alkoxy groups (typically up to three such groups) and hence there are multiple hydrolysis products possible depending on the hydrolysis procedure. Fully hydrolysed and partially hydrolysed products can be formed. This hydrolysis reaction results in the formation of alcohol.
  • hydrolysed silanes/partially hydrolysed silanes can then be condensed together as is well known to form complex oligomers/polymers. Due to the various different monomers present when a hydrolysis reaction is effected, a complex polysilane sol forms which cannot be easily characterised by a general formula.
  • the dry film thickness of the primer is ideally in the range of 15 to 500 pm.
  • a top coat layer may be applied over the intumescent coating system.
  • a top coat is general present for aesthetics but also helps protect the underlying layers from the weather and sun damage.
  • the top coat layer is obtained by the application of a top coat composition onto the non-intumescent coating layer B or optional intumescent coating layer C which is optionally cured or partially cured before application of the top coat composition.
  • the top-coat composition may be solvent borne or waterborne.
  • the top coat is preferably non-intumescent, e.g. it should be free of an acid generating compound and/or expansion agent, for example.
  • the top coat is preferably free of fibres.
  • the top coat composition has a volume solids content of at least 35%, such as at least 50%, e.g. 50 to 60% volume solids.
  • the top coat composition may comprise an (meth)acrylic-based binder, polyurethane-based binder, alkyd based binder, vinyl-based binder or a silicone- based binder.
  • the use of an (meth)acrylic based binder, silicone-based binder and a polyurethane-based binder is preferred.
  • the top coat composition may comprise at least 30 dry wt% of the binder polymer such as at least 40 dry wt.% of the binder.
  • the top coat composition may also contain standard additives such as pigments and fillers, thickening agents, dispersants and biocides.
  • Suitable pigments and fillers include titanium dioxide, zinc oxide, aluminium oxide, barium sulphate, carbonates, borates, silica, silicates, heavy metal oxides such as cerium oxide, lanthanum oxide and zirconium oxide, mica, diatomaceous earth and bentonite clay.
  • a preferred filler is barium sulphate.
  • the fillers preferably constitute from 1% to 25% by dry weight of the top coat composition.
  • the intumescent and non-intumescent coating compositions may be prepared by any suitable technique that is commonly used within the field of paint production.
  • the various constituents may be mixed together using a high speed disperser, a ball mill, a pearl mill, a three-roll mill, an inline mixer etc.
  • the intumescent or non-intumescent coating composition may be supplied as a one component coating composition that is ready to use or a kit of parts, especially when an epoxy binder is used.
  • part (A) comprises the epoxy resin and part (B) the curing agent.
  • Non-reactive components such as the hydrocarbon resin, additives such as fillers and pigments, fibres and the intumescent components can be supplied in either part (A) or (B).
  • the skilled person will be able to design an appropriate kit to supply the components for transport.
  • the relative amounts of each component within any part of the kit will be determined by the final wt% values in the intumescent coating composition and the relative mixing ratios.
  • the intumescent and non-intumescent coating compositions to be used herein can either be applied directly from the one component coating composition or are conveniently prepared by mixing the components if supplied as a kit of parts.
  • the first composition (A) and the curing agent component (B) can be mixed by adding the curing agent to the first composition and stirring well until the mixture is homogeneous.
  • the mixture is immediately ready for application, e.g. by spray application or manually, but may also be given an induction time prior to application.
  • the intumescent and non-intumescent coating compositions can be applied to a substrate (in particular a steel structure) by spray using well-known, specialised, 2 component airless spray pumps, 1 component airless spray pumps or manually, using, for example, a trowel or brush.
  • a substrate in particular a steel structure
  • pre heating of the product up to 60 °C and pressures such as 3 to 6 bars may be required.
  • the coating compositions forming the intumescent coating layer A and the non-intumescent coating layer B may be applied in several layers in order to buildup layer thickness.
  • each layer is cured (dried) before a further layer is applied.
  • application of further layers can be carried out on a wet (or uncured) underlayer. This speeds up the application process.
  • coating layer B is a liquid it can be sprayed on top of coating layer A with no stoppage in the process.
  • Intumescent layer A may be wet or dry when non- intumescent layer B is applied on top.
  • An advantage of the coating system described herein is that the non- intumescent coating layer B is much easier to apply than using a mesh as described earlier.
  • the intumescent coating composition A comprises: (i) 10 to 50 dry wt% of at least one binder;
  • the invention provides a non- intumescent coating composition B comprising:
  • the invention provides a multilayer intumescent coating system comprising an intumescent coating layer A and a non- intumescent coating layer B, wherein: coating layer A comprises
  • coating layer B comprises
  • the invention provides a multilayer intumescent coating system comprising an intumescent coating layer A, a non- intumescent coating layer B and an intumescent coating layer C, wherein: coating layer A comprises
  • coating layer B comprises
  • coating layer C comprises
  • compositions were mixed on a high-speed dissolver in the indicated parts by weight.
  • the non-intumescent coating composition 1 was produced by the following process. A mill base was produced with water, additives and fillers. The mill base was stirred at high speed. Next the binder and the fibres were added and dispersed at low speed until no lumps were observed.
  • non-intumescent coating composition 2 the binder was added first, then any pigments and fillers were added and mixed at a high speed until no lumps could be seen.
  • the total amount of each component in the coating composition after mixing is listed in Tables 3 and 4 below.
  • Components of the intumescent coating composition 3 were mixed on a high-speed dissolver in the indicated parts by weight. The resins were added first and blended at low speed. Then the intumescent pigments and fillers were added and mixed at a high speed until no lumps could be seen. Component (A) and (B) were prepared separately.
  • examples 1-3 and comparative example 1 and 2 the coating systems were tested on circular hollow sections (0.5 m tall, diameter 219 mm, wall thickness 8 mm) according to BS476-part 20:1987.
  • example 4 and comparative examples 3 - 5 the coating systems were tested on H columns (0.5m tall, 254 flange dept, 254 web debt and 73 kg/m) according to BS476-part 20 appendix D.
  • Adhesion testing was performed by applying three layer coating systems comprising Intumescent coating 3 as first layer, Intumescent coating 4 or Non- intumescent coating composition 2 as second layer and Intumescent coating 3 as the third layer to sandblasted steel panels (Sa 2 ⁇ 2) with dimensions 150 mm x 75 mm x 6 mm.
  • the first layer was applied to a dry film thickness of 3 mm and cured 1 day at 25 °C
  • the second layer was applied to a dry film thickness of 0.3 mm and cured 2 days at 25 °C
  • the third layer was applied to a dry film thickness of 3 mm and cured 2 days at 25 °C.
  • Intumescent coating 1 Commercially available water-based, vinyl acetate based binder with 60 mins fire protection.
  • Intumescent coating 2 Commercially available water-based, vinyl acetate based binder with 120 mins fire protection.
  • Intumescent coating 3 solvent free, epoxy-based binder, see Table 2.
  • Non-intumescent composition 1 See Table 3.
  • Non-intumescent composition 2 See Table 4.
  • Table 1 List of components
  • AHEW Amine Hydrogen Equivalent Weight
  • Non-intumescent coating composition 2 1 1 Component A and B were prepared separately and mixed shortly before application
  • Table 7 Test results Comparative example 1 and Examples 1-3 are directly comparable as the same intumescent coating is used and the overall DFT of the coating system is comparable.
  • Comparative example 1 opens up and collapses after 60 mins.
  • Examples 1-3 show that the presence of a non-intumescent layer increases the time to failure at both 500 °C and 520 °C.
  • Examples 2 and 3 shows a 27% improvement in TTF at 500 °C and
  • Example 1 shows a 52% improvement in TTF at 500 °C.
  • An advantage of the present invention is that the char is prevented from splitting in the first place and therefore failure due to char failure is significantly reduced.
  • Examples 1-3 demonstrate that the use of a non-intumescent coating comprising fibres can increase the efficiency of an intumescent coating.
  • Example 1 has the lowest DFT for the non-intumescent layer and overall thickness but has the best performance in the fire tests. This suggests that there is an optimum DFT of the layer.
  • Comparative example 2 comprises intumescent coating 2 that is designed to have a longer TTF than intumescent coating 1. Despite this, Examples 1-3 all have significantly improved TTF relative to intumescent coating 2.
  • Example 1 provides a 31.9% improvement in TTF at 500 °C when compared to Comparative Example 2, while Examples 2 and 3 provide a 10.1% improvement in TTF at 500 °C.
  • Example 4 show that the non-intumescent coating composition 2 prevents cracking of the char and provided a 32% improvement in performance compared to the coating system without the non-intumescent coating layer (comparative example 3) for an epoxy-based intumescent coating system.
  • comparative example 4 and 5 show that the non-intumescent coating composition 2 of the invention gives as good performance as the traditional mesh in epoxy-based intumescent coating systems.
  • the present invention increases the efficiency of existing or new intumescent coating products without the need to optimise or redevelop the intumescent composition itself.
  • An additional advantage of the present invention is that, unlike a traditional mesh, a non-intumescent coating can be used in a low DFT system without affecting aesthetics.

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Abstract

L'invention concerne un système de revêtement intumescent multicouche comprenant une couche de revêtement intumescente A et une couche de revêtement non intumescente B directement sur celle-ci, dans lequel : (i) la couche de revêtement A comprend une composition de revêtement intumescente comprenant a) un liant ou est formée à partir de celle-ci ; et (ii) la couche de revêtement B comprend une composition de revêtement non intumescente comprenant a) un liant ou est formée à partir de celle-ci ; et b) des fibres.
PCT/EP2023/085361 2022-12-12 2023-12-12 Revêtements WO2024126494A1 (fr)

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US5989706A (en) 1998-09-30 1999-11-23 Battelle Memorial Institute Thermally-protective intumescent coating system and method
WO2005000975A1 (fr) 2003-06-24 2005-01-06 W. & J. Leigh & Co., Compositions de revetement intumescentes
US20110274863A1 (en) 2010-05-04 2011-11-10 Airbus Operations Gmbh Thermal insulating tape with fire protecting system and its use in aircraft construction
US20140106176A1 (en) 2011-03-25 2014-04-17 Evonik Degussa Gmbh Aqueous corrosion protection formulation based on silanes
US20160168393A1 (en) 2014-12-12 2016-06-16 United States Mineral Products Company Intumescent Coating
WO2017147138A1 (fr) 2016-02-22 2017-08-31 Evonik Degussa Gmbh Agents durcisseurs de type base de mannich benzylés, compositions et procédés
WO2021180488A1 (fr) 2020-03-11 2021-09-16 Röhm Gmbh Système de résine amélioré pour revêtements intumescents
WO2022117878A1 (fr) 2020-12-04 2022-06-09 Jotun A/S Revêtements

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5989706A (en) 1998-09-30 1999-11-23 Battelle Memorial Institute Thermally-protective intumescent coating system and method
WO2005000975A1 (fr) 2003-06-24 2005-01-06 W. & J. Leigh & Co., Compositions de revetement intumescentes
US20110274863A1 (en) 2010-05-04 2011-11-10 Airbus Operations Gmbh Thermal insulating tape with fire protecting system and its use in aircraft construction
US20140106176A1 (en) 2011-03-25 2014-04-17 Evonik Degussa Gmbh Aqueous corrosion protection formulation based on silanes
US20160168393A1 (en) 2014-12-12 2016-06-16 United States Mineral Products Company Intumescent Coating
WO2017147138A1 (fr) 2016-02-22 2017-08-31 Evonik Degussa Gmbh Agents durcisseurs de type base de mannich benzylés, compositions et procédés
WO2021180488A1 (fr) 2020-03-11 2021-09-16 Röhm Gmbh Système de résine amélioré pour revêtements intumescents
WO2022117878A1 (fr) 2020-12-04 2022-06-09 Jotun A/S Revêtements

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