WO2014080000A1 - An intumescent coating composition - Google Patents

An intumescent coating composition Download PDF

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Publication number
WO2014080000A1
WO2014080000A1 PCT/EP2013/074543 EP2013074543W WO2014080000A1 WO 2014080000 A1 WO2014080000 A1 WO 2014080000A1 EP 2013074543 W EP2013074543 W EP 2013074543W WO 2014080000 A1 WO2014080000 A1 WO 2014080000A1
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WO
WIPO (PCT)
Prior art keywords
coating composition
phosphoric acid
intumescent
intumescent coating
coating according
Prior art date
Application number
PCT/EP2013/074543
Other languages
French (fr)
Inventor
Ronnie PESKENS
Original Assignee
Ppg Coatings Europe B.V.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ppg Coatings Europe B.V. filed Critical Ppg Coatings Europe B.V.
Priority to EP13795739.5A priority Critical patent/EP2922923A1/en
Priority to CN201380068956.9A priority patent/CN104884542B/en
Priority to US14/647,007 priority patent/US10072163B2/en
Publication of WO2014080000A1 publication Critical patent/WO2014080000A1/en
Priority to HK15110620.0A priority patent/HK1210489A1/en

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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
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • C09D5/185—Intumescent paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/06—Organic materials
    • C09K21/10—Organic materials containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/14—Macromolecular materials

Definitions

  • the present invention relates to an intumescent coating composition, and a coating and coated substrates derived therefrom, in particular, an intumescent coating with improved fire performance.
  • Intumescent coatings are fire retard ant coatings which produce gases upon heating. The coating decomposes to form a char which is then expanded into foam by the release of gases. The trapped gases within the foam form the char into an insulating layer of carbon which protects the underlying substrate. Intumescent coatings are applied to surfaces which require improved fire resistance. They are commonly used in the construction industry to give improved fire resistance to building materials by reducing the rate of heating and hence prolonging the time for the building materials to reach critical failure temperature.
  • An intumescent coating may be water or solvent based or solvent free, and includes a polymeric binder for the intumescent components.
  • intumescent coatings have, in addition to the binder, a source of phosphoric acid, an expansion agent or blowing agent and a carbon source.
  • the carbon source is typically a solid carbon source such as pentaerythritoi (PER) or a derivative thereof, it is understood that the solid carbon source such as pentaerythritoi will be dehydrated as well as form esters with the phosphor of the polyphosphoric acid source (usually ammonium polyphosphate (APP)) prior to decomposition into a foaming carbonaceous char.
  • PER pentaerythritoi
  • APP ammonium polyphosphate
  • the low molecular weight esters that are formed from the reaction between polyphosphoric acid and glycerine have low temperatures of decomposition, possibly enhancing the fire retardant time by faster char formation.
  • the use of glycerine is problematic and does not necessarily result in enhanced fire retardant properties.
  • an intumescent coating composition comprising:-
  • an expansion agent preferably one which decomposes at temperatures > 200 °C;
  • one or more pigments preferably one or more pigments;
  • a liquid carrier for the polymeric binder wherein the liquid carrier may be water or an organic solvent and when the liquid carrier is water the binder and liquid carrier are in the form of an aqueous polymeric dispersion; and wherein the ratio of combined components (b), (c), (e) and (f) : (a) is at least 4:1 w w.
  • the ratio of combined components (b), (c), (e) and (f): (a) is between 4:1 and 8:1 w/w in the composition, more preferably, between 4:1 and 5:1 w w.
  • the ratio of (b): (c) is at least 3:1 w/w.
  • the ratio of (e) : (c) is at least 3:2 w/w.
  • the ratio of (f) : (c) is at least 2:1 w w.
  • the level of components (b), (e) and (f) relative to component (d) is also important and it is found best results are achieved when the ratio of (b) : (d) is preferably at least 6:1 w/w; the ratio of (e) : (d) is typically, at least 3:2 w w; and the ratio of (f) : (d) is typically, at least 2:1 w/w.
  • the concentration of components (b), (e) and (f) in the coating composition is in the range 45-75% w/w solids, more preferably, 50-70% w/w solids.
  • an intumescent coating composition comprising:-
  • an expansion agent preferably one which decomposes at temperatures > 200 °C;
  • liquid carrier for the polymeric binder wherein the liquid carrier may be water or an organic solvent and when the liquid carrier is water the binder and liquid carrier are in the form of an aqueous polymeric dispersion;
  • concentration of components (b), (e) and (f) in the coating composition is in the range 55-75% w w solids.
  • the solid carbon donor (c) may be present in the coating composition in the range 0-80 % w/w total carbon donor i.e. total liquid (d) and solid carbon donor (c), more preferably, 15-50%w w, most preferably, 20-50%, especially, 30-40% w w.
  • the liquid carbon donor may be present in the composition in the range 90-20% w w total carbon donor (c) & (d), more preferably, 85-50% w/w, most preferably, 70-60% w/w.
  • the concentration of components (b), (c) (e) and (f) in the composition is in the range 50-80% w/w solids, more preferably, 50-70% w/w solids, most preferably, 60-70% w/w solids.
  • liquid in liquid carbon donor is meant that the carbon donor is a liquid at 25°C and atmospheric pressure.
  • the liquid carbon donor is glycerine.
  • a dry coating composition coated onto a surface comprising:-
  • an expansion agent preferably one which decomposes at temperatures > 200 °C;
  • ratio of combined components (b), (c), (e) and (f) is at least 4:1 w/w
  • a coated metal substrate wherein the coating comprising:-
  • an expansion agent preferably one which decomposes at temperatures > 200 °C;
  • one or more pigments preferably one or more pigments;
  • the polymeric binders of the present invention are generally film forming binders known to those skilled in the art of intumescent coatings. Although, the compositions of the present invention may be used to coat any substrate they are generally to be applied to metal substrates such as steelwork either directly or indirectly via primer and/or intermediate layers. Generally, after curing the water dispersed polymeric binder is no longer soluble in water.
  • the polymeric binder may be a (co)polymer derived from (co)monomers including vinyl acetate, vinyl acetate-ethylene, or vinyl acetate-VeoVa.
  • polystyrene acrylic-styrene, acrylic-vinyl toluene, styrene-butadiene, vinyl toluene-butadiene, styrene-acrylonitrile, vinyl toluene-acrylonitrile, diisocyanate-polyol, vinyl alcohol, vinyl acetate, vinyl butyral, urea-formaldehyde, melamine-formaldehyde, alkyl phenol-formaldehyde, vinyl chloride-vinylidene chloride, or is derived from epoxy resins and amino-functional curing agents, or is derived from a dicarboxylic acid and a polyol and fatty acid modifiers.
  • acrylic monomer herein is meant any suitable alkyl(alk)acrylate or (alk)acrylic acid such as methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, methacrylic acid or acrylic acid, n-butyl acrylate, iso-butyl acrylate, t-butyl acrylate, n- butyl methacrylate, iso-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, laury!
  • methacrylate lauryl acrylate, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate; hydroxy!-functional acrylates such as 2-hydroxyethyl methacrylate, hydroxypropylethyl methacrylate, 2-hydroxyethy I acrylate, or hydroxy propyl acrylate; and mixtures thereof.
  • the liquid carrier may be water or an organic solvent.
  • the binder is generally in an aqueous polymeric dispersion, although solvent based systems are also envisaged.
  • the solvent based systems may comprise sole solvent or solvent blends.
  • a suitable solvent is xylene.
  • a suitable solvent blend is toluene/methyiketone blend.
  • the binder is present at 5-40% w/w solids, more preferably, 10-35% w/w solids, most preferably, 10-20% w w solids.
  • Suitable solid carbon donors may be selected from organic polyhydroxy compounds. Suitable compounds may be selected from pentaerythritol, dipentaerythritol, tripentaerythritoi, starch, sugars.
  • the solid carbon donor is pentaerythritol.
  • the expansion agent is typically effective to form a foam by emission of an inert gas. Suitable expansion agents are those which decompose/are activated above 200 °C, for example in the range 280 to 390 °C. Suitable expansion agents are generally nitrogen containing compounds such as melamine, meiamine salts, melamine derivatives, urea, dicyandiamide and guanidine. Preferably, the expansion agent is melamine.
  • the acid catalyst is one that thermal decomposes upon exposure to extreme heat such as that found in a fire, for example above 200°C. It will be appreciated that the phosphoric acid formed under such conditions from component (b) is then available to react with the liquid carbon donor of component (d) which is suitably one that forms a phosphoric acid ester upon contact therewith at such temperatures.
  • the solid carbon donor (c) is also effective to react with the phosphoric acid to form a phosphoric acid ester upon contact therewith at such temperatures.
  • Suitable acid catalysts (b) include phosphoric acid esters of polyhydroxy compounds (partiai phosphate esters) and aminophophates such as ammonium phosphate or amine phosphates.
  • Particularly preferred phosphates are the aminophosphates ammonium polyphosphate (APP) and melamine phosphate.
  • the acid catalyst (b) is APP.
  • the catalyst typically forms polyphosphoric acids on thermal decomposition and these are preferred but it is also possible in some embodiments for a monophosphoric acid to be formed.
  • Suitable pigments for the composition are those know to the skilled person in the intumescent coatings art such as Ti0 2 and carbon black, preferably Ti0 2 is used.
  • Suitable additives may include: - plasticisers, de-foamers, cellulose thix agents, acrylic thix agents, biocides etc.
  • the present inventors have found that the compositions of the invention provide several unexpected advantages:- the length of fire protection is improved; the speed of intumescent action increases as the temperature of char formation is lowered; the liquid carbon donor encapsulates the pigments in the present coating such that the char formed consists of small homogenous air chambers making the char denser and more effective at insulating the substrate; the char layer formed by the present invention has greater integrity and flexibility reducing the level of cracking observed; the increase in solids levels that the use of a liquid carbon donor allows by reducing viscosity means a lower volume of solvent is required hence providing increased solids and reducing drying times; the liquid carbon donor acts as a plasticizer within the present coating and prevents an increase in viscosity or gelling of the coating that is typically observed when intumescent coatings are stored, thereby increasing the shelf life of the present coating up to 12 months;
  • liquid carbon donor and high pigment volume concentration act together to decrease the drying time of the coating by up to 50% compared with coatings comprising only liquid carbon donors.
  • Comparative Example 2 Standard formulation with PER replaced by glyceri
  • Acrylic copolymer emulsion (rheology additive) 0,92 Titanium Dioxide 10,08
  • Acrylic copolymer emulsion (rheology additive) 0,60
  • Synthetic glycerine was used to prepare the modified coating by exchanging the OH content of PER with GLY.
  • the substrate in each case was an A/V 140, SA 2 1 ⁇ 2 grit blasted steel T-bar of 11 kg.
  • the coating was applied by first applying a zinc phosphate epoxy primer using a conventional air spray and then applying the intumescent paint also using a conventional spray.
  • the coated substrates were cured for one week at room temperature and one further week at 40 ' C after application of the intumescent coat.
  • the fire test was carried out up to 620°C steel temperature according to EN 13381 -4.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)

Abstract

An intumescent coating composition and a coated metal substrate are described. The composition comprises:(a) a polymeric binder; (b) an acid catalyst effective to form a poiyphosphoric acid on thermal decomposition; (c) a solid carbon donor; (d) a liquid carbon donor in the form of one or more polyhydric alcohols effective to form a phosphoric acid ester on contact with phosphoric acid; (e) an expansion agent; (f) one or more pigments; (g) optionally, one or more other additives; (h) a liquid carrier for the polymeric binder The ratio of combined components (b), (c), (e) and (f): (a) is at least 4:1 w/w. A coating composition wherein the concentration of components (b), (e) and (f) is in the range 55-75% w/w solids is further described.

Description

An Intumescent Coating Composition
The present invention relates to an intumescent coating composition, and a coating and coated substrates derived therefrom, in particular, an intumescent coating with improved fire performance.
Intumescent coatings are fire retard ant coatings which produce gases upon heating. The coating decomposes to form a char which is then expanded into foam by the release of gases. The trapped gases within the foam form the char into an insulating layer of carbon which protects the underlying substrate. Intumescent coatings are applied to surfaces which require improved fire resistance. They are commonly used in the construction industry to give improved fire resistance to building materials by reducing the rate of heating and hence prolonging the time for the building materials to reach critical failure temperature.
An intumescent coating may be water or solvent based or solvent free, and includes a polymeric binder for the intumescent components. Generally, intumescent coatings have, in addition to the binder, a source of phosphoric acid, an expansion agent or blowing agent and a carbon source.
The carbon source is typically a solid carbon source such as pentaerythritoi (PER) or a derivative thereof, it is understood that the solid carbon source such as pentaerythritoi will be dehydrated as well as form esters with the phosphor of the polyphosphoric acid source (usually ammonium polyphosphate (APP)) prior to decomposition into a foaming carbonaceous char. Horacek et al. (Journal of AppliedPo!ymer Science.Vol. 113, 1745-1756 (2009)) have found that glycerine (GLY) may be used as a liquid carbon source in addition to pentaerythritoi in intumescent coatings. The low molecular weight esters that are formed from the reaction between polyphosphoric acid and glycerine have low temperatures of decomposition, possibly enhancing the fire retardant time by faster char formation. However, the use of glycerine is problematic and does not necessarily result in enhanced fire retardant properties.
Surprisingly, it has now been discovered that the fire retardant properties of intumescent coatings can be enhanced by use of both a liquid carbon donor and by restoring the pigment volume concentration (PVC) to that in the region of an equivalent solid carbon donor system.
According to a first aspect of the present invention there is provided an intumescent coating composition comprising:-
(a) a polymeric binder;
(b) an acid catalyst effective to form a phosphoric acid, preferably, a polyphosphoric acid on thermal decomposition;
(c) a solid carbon donor;
(d) a liquid carbon donor in the form of one or more polyhydric alcohols effective to form a phosphoric acid ester on contact with phosphoric acid wherein the phosphoric acid ester has a lower temperature of decomposition than the equivalent pentaerythritol phosphoric acid ester;
(e) an expansion agent, preferably one which decomposes at temperatures > 200 °C; (f) one or more pigments;
(g) optionally, one or more other additives;
(h) a liquid carrier for the polymeric binder wherein the liquid carrier may be water or an organic solvent and when the liquid carrier is water the binder and liquid carrier are in the form of an aqueous polymeric dispersion; and wherein the ratio of combined components (b), (c), (e) and (f) : (a) is at least 4:1 w w.
Preferably, the ratio of combined components (b), (c), (e) and (f): (a) is between 4:1 and 8:1 w/w in the composition, more preferably, between 4:1 and 5:1 w w.
Preferably, the ratio of (b): (c) is at least 3:1 w/w.
Preferably, the ratio of (e) : (c) is at least 3:2 w/w. Preferably, the ratio of (f) : (c) is at least 2:1 w w.
The level of components (b), (e) and (f) relative to component (d) is also important and it is found best results are achieved when the ratio of (b) : (d) is preferably at least 6:1 w/w; the ratio of (e) : (d) is typically, at least 3:2 w w; and the ratio of (f) : (d) is typically, at least 2:1 w/w. Preferably, the concentration of components (b), (e) and (f) in the coating composition is in the range 45-75% w/w solids, more preferably, 50-70% w/w solids. By maintaining the non- carbon donor solids, components (b), (e) and (f), at high levels in a liquid carbon donor containing composition, the pigment volume concentration is maintained to the level of an equivalent solid carbon donor composition and a surprising improvement in fire resistance is observed. For the avoidance of doubt liquid carbon donor is included as a solid for this purpose because it is present in the dry coating. Accordingly, according to a further aspect of the invention there is provided an intumescent coating composition comprising:-
(a) a polymeric binder;
(b) an acid catalyst effective to form a phosphoric acid, preferably, a polyphosphoric acid on thermal decomposition;
(c) a solid carbon donor;
(d) a liquid carbon donor in the form of one or more polyhydric alcohois effective to form a phosphoric acid ester on contact with phosphoric acid wherein the phosphoric acid ester has a lower temperature of decomposition than the equivalent pentaerythritol phosphoric acid ester;
(e) an expansion agent, preferably one which decomposes at temperatures > 200 °C;
(f) one or more pigments;
(g) optionally, one or more other additives;
(h) a liquid carrier for the polymeric binder wherein the liquid carrier may be water or an organic solvent and when the liquid carrier is water the binder and liquid carrier are in the form of an aqueous polymeric dispersion; and
wherein the concentration of components (b), (e) and (f) in the coating composition is in the range 55-75% w w solids.
Preferably, according to any aspect of the invention, the solid carbon donor (c) may be present in the coating composition in the range 0-80 % w/w total carbon donor i.e. total liquid (d) and solid carbon donor (c), more preferably, 15-50%w w, most preferably, 20-50%, especially, 30-40% w w. Accordingly, the liquid carbon donor may be present in the composition in the range 90-20% w w total carbon donor (c) & (d), more preferably, 85-50% w/w, most preferably, 70-60% w/w. Preferably, the concentration of components (b), (c) (e) and (f) in the composition is in the range 50-80% w/w solids, more preferably, 50-70% w/w solids, most preferably, 60-70% w/w solids. By liquid in liquid carbon donor is meant that the carbon donor is a liquid at 25°C and atmospheric pressure.
Preferably, the liquid carbon donor is glycerine. According to a further aspect of the present invention there is provided a dry coating composition coated onto a surface comprising:-
(a) a polymeric binder derived from either an aqueous polymeric dispersion of the binder or an organic solvent based solution of the binder;
(b) an acid catalyst effective to form a phosphoric acid, preferably, a polyphosphoric acid on thermal decomposition;
(c) a solid carbon donor ;
(d) a liquid carbon donor in the form of one or more polyhydric alcohols effective to form a phosphoric acid ester on contact with phosphoric acid wherein the phosphoric acid ester has a lower temperature of decomposition than the equivalent pentaerythritol phosphoric acid ester;
(e) an expansion agent, preferably one which decomposes at temperatures > 200 °C;
(f) one or more pigments; and
(g) optionally, one or more other additives;
wherein the ratio of combined components (b), (c), (e) and (f) : (a) is at least 4:1 w/w
According to a further aspect of the present invention there is provided a coated metal substrate wherein the coating comprising:-
(a) a polymeric binder;
(b) an acid catalyst effective to form a phosphoric acid, preferably, a polyphosphoric acid on thermal decomposition;
(c) a solid carbon donor ;
(d) a liquid carbon donor in the form of one or more poiyhydric alcohols effective to form a phosphoric acid ester on contact with phosphoric acid wherein the phosphoric acid ester has a lower temperature of decomposition than the equivalent pentaerythritol phosphoric acid ester;
(e) an expansion agent, preferably one which decomposes at temperatures > 200 °C; (f) one or more pigments; and
(g) optionally, one or more other additives;
wherein the ratio of combined components (b), (c), (e) and (f) : (a) is at least 4:1 w w The polymeric binders of the present invention are generally film forming binders known to those skilled in the art of intumescent coatings. Although, the compositions of the present invention may be used to coat any substrate they are generally to be applied to metal substrates such as steelwork either directly or indirectly via primer and/or intermediate layers. Generally, after curing the water dispersed polymeric binder is no longer soluble in water. The polymeric binder may be a (co)polymer derived from (co)monomers including vinyl acetate, vinyl acetate-ethylene, or vinyl acetate-VeoVa. Other possible (co)monomers may be selected from acrylic-styrene, acrylic-vinyl toluene, styrene-butadiene, vinyl toluene-butadiene, styrene-acrylonitrile, vinyl toluene-acrylonitrile, diisocyanate-polyol, vinyl alcohol, vinyl acetate, vinyl butyral, urea-formaldehyde, melamine-formaldehyde, alkyl phenol-formaldehyde, vinyl chloride-vinylidene chloride, or is derived from epoxy resins and amino-functional curing agents, or is derived from a dicarboxylic acid and a polyol and fatty acid modifiers. By acrylic monomer herein is meant any suitable alkyl(alk)acrylate or (alk)acrylic acid such as methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, methacrylic acid or acrylic acid, n-butyl acrylate, iso-butyl acrylate, t-butyl acrylate, n- butyl methacrylate, iso-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, laury! methacrylate, lauryl acrylate, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate; hydroxy!-functional acrylates such as 2-hydroxyethyl methacrylate, hydroxypropylethyl methacrylate, 2-hydroxyethy I acrylate, or hydroxy propyl acrylate; and mixtures thereof.
As referred to above, the liquid carrier may be water or an organic solvent. The binder is generally in an aqueous polymeric dispersion, although solvent based systems are also envisaged. The solvent based systems may comprise sole solvent or solvent blends. A suitable solvent is xylene. A suitable solvent blend is toluene/methyiketone blend. Preferably, the binder is present at 5-40% w/w solids, more preferably, 10-35% w/w solids, most preferably, 10-20% w w solids. Suitable solid carbon donors may be selected from organic polyhydroxy compounds. Suitable compounds may be selected from pentaerythritol, dipentaerythritol, tripentaerythritoi, starch, sugars. Preferably, the solid carbon donor is pentaerythritol. The expansion agent is typically effective to form a foam by emission of an inert gas. Suitable expansion agents are those which decompose/are activated above 200 °C, for example in the range 280 to 390 °C. Suitable expansion agents are generally nitrogen containing compounds such as melamine, meiamine salts, melamine derivatives, urea, dicyandiamide and guanidine. Preferably, the expansion agent is melamine.
Suitably, the acid catalyst is one that thermal decomposes upon exposure to extreme heat such as that found in a fire, for example above 200°C. It will be appreciated that the phosphoric acid formed under such conditions from component (b) is then available to react with the liquid carbon donor of component (d) which is suitably one that forms a phosphoric acid ester upon contact therewith at such temperatures. Suitably, the solid carbon donor (c) is also effective to react with the phosphoric acid to form a phosphoric acid ester upon contact therewith at such temperatures. Suitable acid catalysts (b) include phosphoric acid esters of polyhydroxy compounds (partiai phosphate esters) and aminophophates such as ammonium phosphate or amine phosphates. Particularly preferred phosphates are the aminophosphates ammonium polyphosphate (APP) and melamine phosphate. However, the skilled person will be aware of many variations of the nitrogen containing acidic phosphorous compounds which are used in the art of intumescent coatings. Preferably, the acid catalyst (b) is APP. The catalyst typically forms polyphosphoric acids on thermal decomposition and these are preferred but it is also possible in some embodiments for a monophosphoric acid to be formed. Suitable pigments for the composition are those know to the skilled person in the intumescent coatings art such as Ti02 and carbon black, preferably Ti02 is used.
Suitable additives may include: - plasticisers, de-foamers, cellulose thix agents, acrylic thix agents, biocides etc.
Advantageously, the present inventors have found that the compositions of the invention provide several unexpected advantages:- the length of fire protection is improved; the speed of intumescent action increases as the temperature of char formation is lowered; the liquid carbon donor encapsulates the pigments in the present coating such that the char formed consists of small homogenous air chambers making the char denser and more effective at insulating the substrate; the char layer formed by the present invention has greater integrity and flexibility reducing the level of cracking observed; the increase in solids levels that the use of a liquid carbon donor allows by reducing viscosity means a lower volume of solvent is required hence providing increased solids and reducing drying times; the liquid carbon donor acts as a plasticizer within the present coating and prevents an increase in viscosity or gelling of the coating that is typically observed when intumescent coatings are stored, thereby increasing the shelf life of the present coating up to 12 months;
It is also observed that the liquid carbon donor and high pigment volume concentration act together to decrease the drying time of the coating by up to 50% compared with coatings comprising only liquid carbon donors.
The invention will now be described by way of example only with reference to the accompanying figures and examples in which:- Figure 1 is a fire curve for an example of the invention and two comparative examples.
Examples
An intumescent coating (Comparative example 1) was studied with glycerine added as a carbon source (Comparative example 2). Fire performance did not significantly improve with the addition of glycerine as replacement for pentaerythntol (PER). However, with the restoration of the original solids content of the formulation (Example 1) significant improvements in fire performance were observed. Comparative Example 1 : Standard formulation
Figure imgf000009_0001
APPffiOa/MEL solids «· 47
Comparative Example 2: Standard formulation with PER replaced by glyceri;
content)
Raw Material Weight
percentage (%)
Vinyl acetate VeoVal 0 copolymer dispersion 21 ,78
(50% solids by weight)
Water 18,66
Cellulose thickener 0,26
Sodium salt of carboxylate polyelectrolyte 0,21
Defoamer 0,20
Biocide 0,07
Coalescent 1 ,81
Acrylic copolymer emulsion (rheology additive) 0,92 Titanium Dioxide 10,08
Glycerine 8,40
Ammonium Polyphosphate 28,21
Melamine 9,40
APPmOz/MEL solids * 48 Example 1
Raw Material Weight
percentage (%)
Vinyl acetate VeoValO copolymer dispersion 14,10
(50% solids by weight)
Water 12,08
Cellulose thickener 0,17
Sodium salt of carboxylate polyelectrolyte 0,13
Defoamer 0,13
Biocide 0,05
Coalescent 1 ,17
Acrylic copolymer emulsion (rheology additive) 0,60
Glycerine 5,68
Titanium Dioxide 13,29
Pentaerythritol 3,01
Ammonium Polyphosphate 37,20
Melamine 12,40
APP Ti02/MEL solids * 63
EXPERIMENTAL
Synthetic glycerine was used to prepare the modified coating by exchanging the OH content of PER with GLY. The substrate in each case was an A/V 140, SA 2 ½ grit blasted steel T-bar of 11 kg. The coating was applied by first applying a zinc phosphate epoxy primer using a conventional air spray and then applying the intumescent paint also using a conventional spray. The coated substrates were cured for one week at room temperature and one further week at 40'C after application of the intumescent coat.
The fire test was carried out up to 620°C steel temperature according to EN 13381 -4.
As can be seen from comparative examples 1 and 2 when compared with example 1 , when PVC was brought back to standard level by filling out with the original pigment mix, the fire performance drastically improved by 0-30%. This is shown in figure 1 where it can be seen that the temperature of the substrate is lower for a longer period for the examples of the invention.
Attention is directed to all papers and documents which are filed concurrently with or previous to this specification in connection with this application and which are open to public inspection with this specification, and the contents of all such papers and documents are incorporated herein by reference.
All of the features disclosed in this specification (including any accompanying claims, abstract and drawings), and/or all of the steps of any method or process so disclosed, may be combined in any combination, except combinations where at least some of such features and/or steps are mutually exclusive.
Each feature disclosed in this specification (including any accompanying claims, abstract and drawings) may be replaced by alternative features serving the same, equivalent or similar purpose, unless expressly stated otherwise. Thus, unless expressly stated otherwise, each feature disclosed is one example only of a generic series of equivalent or similar features.
The invention is not restricted to the details of the foregoing embodiment(s). The invention extends to any novel one, or any novel combination, of the features disclosed in this specification (including any accompanying claims, abstract and drawings), or to any novel one, or any novel combination, of the steps of any method or process so disclosed.

Claims

1. An intumescent coating composition comprising:- (a) a polymeric binder;
(b) an acid catalyst effective to form a phosphoric acid, preferably, a polyphosphoric acid on thermal decomposition;
(c) a solid carbon donor;
(d) a liquid carbon donor in the form of one or more polyhydric alcohols effective to form a phosphoric acid ester on contact with phosphoric acid wherein the phosphoric acid ester has a lower temperature of decomposition than the equivalent pentaerythritol phosphoric acid ester;
(e) an expansion agent, preferably one which decomposes at temperatures >
200 °C;
(f) one or more pigments;
(g) optionally, one or more other additives;
(h) a liquid carrier for the polymeric binder wherein the liquid carrier may be water or an organic solvent and when the liquid carrier is water the binder and liquid carrier are in the form of an aqueous polymeric dispersion; and wherein the ratio of combined components (b), (c), (e) and (f) : (a) is at least 4:1 w/w.
2. An intumescent coating composition comprising:- (a) a polymeric binder;
(b) an acid catalyst effective to form a phosphoric acid, preferably, a polyphosphoric acid on thermal decomposition;
(c) a solid carbon donor;
(d) a liquid carbon donor in the form of one or more polyhydric alcohols effective to form a phosphoric acid ester on contact with phosphoric acid wherein the phosphoric acid ester has a lower temperature of decomposition than the equivalent pentaerythritol phosphoric acid ester;
(e) an expansion agent, preferably one which decomposes at temperatures >
200 °C;
(f) one or more pigments;
(g) optionally, one or more other additives; (h) a liquid carrier for the polymeric binder wherein the liquid carrier may be water or an organic solvent and when the liquid carrier is water the binder and liquid carrier are in the form of an aqueous polymeric dispersion; and
wherein the concentration of components (b), (e) and (f) in the coating composition is in the range 55-75% w/w solids.
3. A dry coating composition coated onto a surface comprising:- (a) a polymeric binder derived from either an aqueous polymeric dispersion of the binder or an organic solvent based solution of the binder;
(b) an acid catalyst effective to form a phosphoric acid, preferably, a polyphosphoric acid on thermal decomposition;
(c) a solid carbon donor ;
(d)a liquid carbon donor in the form of one or more polyhydric alcohols effective to form a phosphoric acid ester on contact with phosphoric acid wherein the phosphoric acid ester has a lower temperature of decomposition than the equivalent pentaerythritol phosphoric acid ester;
(e) an expansion agent, preferably one which decomposes at temperatures > 200 °C;
(f) one or more pigments; and
(g) optionally, one or more other additives;
wherein the ratio of combined components (b), (c), (e) and (f) : (a) is at least 4:1 w w.
4. A coated metal substrate wherein the coating comprises:-
(a) a polymeric binder;
(b) an acid catalyst effective to form a phosphoric acid, preferably, a polyphosphoric acid on thermal decomposition; (c) a solid carbon donor;
(d) a liquid carbon donor in the form of one or more polyhydric alcohols effective to form a phosphoric acid ester on contact with phosphoric acid wherein the phosphoric acid ester has a lower temperature of decomposition than the equivalent pentaerythritol phosphoric acid ester;
(e) an expansion agent, preferably one which decomposes at temperatures >
200 °C; (f) one or more pigments;
(g) optionally, one or more other additives; wherein the ratio of combined components (b), (c), (e) and (f) : (a) is at least 4:1 w/w.
5. An intumescent coating composition or coating according to any preceding claim, wherein the ratio of combined components (b), (c), (e) and (f): (a) is between 4:1 and 8:1 w/w.
6. An intumescent coating composition or coating according to any preceding claim, wherein the ratio of (b): (c) is at least 3:1 w w.
7 An intumescent coating composition or coating according to any preceding claim, wherein the ratio of (e) : (c) is at least 3:2 w/w,
8. An intumescent coating composition or coating according to any preceding claim, wherein the ratio of (f) : (c) is at least 2:1 w/w.
9. An intumescent coating composition or coating according to any preceding claim, wherein the ratio of (b) : (d) is at least 6:1 w w.
10. An intumescent coating composition or coating according to any preceding claim, wherein the ratio of (e) : (d) is at least 3:2 w w.
11. An intumescent coating composition or coating according to any preceding claim, wherein the ratio of (f) : (d) is at least 2:1 w w.
12. An intumescent coating composition or coating according to any preceding claim, wherein the solid carbon donor (c) is present in the coating composition in the range 10 - 80% w/w total carbon donor.
13. An intumescent coating composition or coating according to any of claims 1 to 12, wherein the liquid carbon donor (d) is present in the coating composition in the range 90 to 20% w w total carbon donor (c) and (d).
14, An intumescent coating composition or coating according to any preceding claim, wherein the concentration of components (b), (c) (e) and (f) is in the range 50 - 80% w/w solids.
15. An intumescent coating composition or coating according to any preceding claim, wherein the liquid carbon donor is glycerine.
16. An intumescent coating composition or coating according to any preceding claim, wherein the polymeric binder is vinyl acetate based.
17. An intumescent coating composition or coating according to claim 16, wherein the polymeric binder is selected from a vinyl acetate-ethylene copolymer or a vinyl acetate-VeoVa copolymer.
18. An intumescent coating composition or coating according to any of claims 1 to 15, wherein the polymeric binder is a (co)polymer derived from the (co)monomers consisting of:- vinyl acetate-ethylene, vinyl acetate-VeoVa, acryiic-styrene, acrylic-vinyl toluene, styrene-butadiene, vinyl toluene-butadiene, styrene-acrylonitrile, vinyl toluene-acrylonitrile, diisocyanate-polyolvinyl alcohol, vinyl acetate, vinyl butyral, urea-formaidehyde, melamine-formaidehyde, a Iky I phenol-formaldehyde, vinyl chloride-vinylidene chloride, or is derived from epoxy resins and amino-functional curing agents, or is derived from a dicarboxylic acid and a polyol and fatty acid modifiers.
19. A coated metal substrate according to claim 4, wherein the polymeric binder is derived from either an aqueous polymeric dispersion of the binder or an organic solvent based solution of the binder.
20. An intumescent coating composition or coating according to any of claims 1-19, wherein the liquid carrier comprises xylene or a toluene-methylketone blend.
21 . An intumescent coating composition or coating according to any preceding claim, wherein the binder is present at 5 - 40% w/w solids.
22. An intumescent coating composition or coating according to any preceding claim, wherein the solid carbon donor is an organic polyhydroxy compound.
23. An intumescent coating composition or coating according to claim 22, wherein the solid carbon donor is selected from pentaerythritol, dipentaerythritol, tripentaerythritol, starch or sugars.
24. An intumescent coating composition or coating according to claim 23, wherein the solid carbon donor is pentaerythritol.
25. An intumescent coating composition or coating according to any preceding claim, wherein the expansion agent decomposes/is activated in the range 280 to 390°C.
26. An intumescent coating composition or coating according to any preceding claim, wherein the expansion agent is a nitrogen containing compound.
27. An intumescent coating composition or coating according to claim 26, wherein the expansion agent is selected from melamine, melamine salts, melamine derivatives, urea, dicyandiamide and guanidine.
28. An intumescent coating composition or coating according to claim 27, wherein the expansion agent is melamine.
29. An intumescent coating composition or coating according to any preceding claim, wherein the acid catalyst (b) is selected from phosphoric esters of polyhydroxy compounds, ammonium phosphates or amine phosphates.
30. An intumescent coating composition or coating according to claim 29, wherein the acid catalyst (b) is APP.
31. An intumescent coating composition or coating according to any preceding claim, wherein the pigment is selected from Ti02 or carbon black.
32. An intumescent coating composition or coating according to any preceding claim, wherein the additives include one or more of the additives selected from plasticisers, de-foamers, cellulose thickening agents, acrylic thickening agents and biocides.
33. A method of fire protecting a substrate, comprising applying an intumescent coating composition according to any of claims 1 , 2, 5 to 18 or 20 to 32 to the substrate.
34. The use of an intumescent coating composition according to any of claims 1-3, 5 to 18 or 20 to 33 to fire protect a substrate, especially a metal substrate.
PCT/EP2013/074543 2012-11-23 2013-11-25 An intumescent coating composition WO2014080000A1 (en)

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US14/647,007 US10072163B2 (en) 2012-11-23 2013-11-25 Intumescent coating composition
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CN104194512A (en) * 2014-08-27 2014-12-10 苏州诚晟信息技术有限公司 Anticorrosive paint and preparation method thereof
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HK1210489A1 (en) 2016-04-22
EP2922923A1 (en) 2015-09-30

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