)

(51) International Patent Classification: (84) Designated States (unless otherwise indicated, for every
C09D 5/18 (2006.01) C08G 59/50 (2006.01) kind of regional protection available) . ARIPO (BW, GH,
C08G 59/44 (2006.0 1) C09D 163/00 (2006.0 1) GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, ST, SZ, TZ,
UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, RU, TJ,
(21) International Application Number:
TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, DK,
PCT/US20 19/05623 3
EE, ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, LU, LV,
(22) International Filing Date: MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SI, SK, SM,
15 October 2019 (15. 10.2019) TR), OAPI (BF, BJ, CF, CG, Cl, CM, GA, GN, GQ, GW,
KM, ML, MR, NE, SN, TD, TG).
(25) Filing Language: English
(26) Publication Language: English Published:
— with international search report (Art. 21(3))
(71) Applicant: SWIMC, LLC [US/US]; 101 West Prospect
Avenue, Cleveland, Ohio 441 15 (US).
(72) Inventor: HILTON, Sharon L.; Tower Works - Kestor
Street, Bolton Lancashire BL2 2AL (GB).
(74) Agent: BARAONA, Robert C.; McDonald Hopkins LLC,
600 Superior Ave., E., Suite 2100, Cleveland, Ohio 441 14
(US).
(81) Designated States (unless otherwise indicated, for every
kind of national protection available) : AE, AG, AL, AM,
AO, AT, AU, AZ , BA, BB, BG, BH, BN, BR, BW, BY, BZ,
CA, CH, CL, CN, CO, CR, CU, CZ, DE, DJ, DK, DM, DO,
DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, HN,
HR, HU, ID, IL, IN, IR, IS, JO, JP, KE, KG, KH, KN, KP,
KR, KW, KZ, LA, LC, LK, LR, LS, LU, LY, MA, MD, ME,
MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, NZ,
OM, PA, PE, PG, PH, PL, PT, QA, RO, RS, RU, RW, SA,
SC, SD, SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN,
TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW.

(54) Title: INTUMESCENT COATING COMPOSITIONS EFFECTIVE AT LOW TEMPERATURES

(57) Abstract: An intumescent composition capable of withstanding temperature cycling as low as - 60° C without cracking is con¬
templated. The composition also exhibits enhanced durability due to its resistance to water absorption, its acceptable cure times, and
(when exposed to fire conditions) its well-adhered, foamed char layer.
 TITLE

INTUMESCENT COATING COMPOSITIONS EFFECTIVE AT LOW

TEMPERATURES

TECHNICAL FIELD

[0001] The present invention relates generally to intumescent compositions and, more

specifically, to intumescent coatings which can retain their structural integrity even when

repeatedly exposed to environmental temperatures approaching -60° C .

BACKGROUND

[0002] In the last fifty years, flame-retardant materials have become increasingly important,

particularly with respect to the manufacture of consumer goods, construction materials, and

other commonly used and/or mass-produced articles. Insofar as many flame-retardant

materials incorporate specialized chemical compounds, it is often useful to coat the flame-

retardant(s) onto a substrate rather constructing the article entirely from the flame-retardant

material itself.

[0003] Flame-retardants applied to a substrate function in any combination of ways to protect

the substrate. Some materials will endothermically degrade upon exposure to flames or high

temperature, thereby removing heat energy from the substrate. Additionally or alternatively,

flame-retardants can act as a thermal barrier to transfer heat energy away from the substrate.

As a final mechanism, some materials release compounds upon exposure to heat (e.g., inert or

non-combustible gases) so as to dilute the combustible reactants. Generally speaking, rather

than actively suppress flames, the purpose behind these mechanisms is to slow the rate of
temperature increase (i.e., the reaction rate contributing heat), thereby prolonging the amount

of time the substrate can withstand the fire/flame condition.

[0004] Intumescent coatings are a form of passive fire protection, usually applied as a thin

film, that swell many times their original thickness forming an insulation char. This acts as a

barrier between the fire and substrate (such as structural steel). Intumescent coatings are often

categorized according to the type of fire they are designed to provide protection against, for

example, cellulosic fueled or hydrocarbon fueled fires.

[0005] Intumescent coatings are particularly utilized for application on steel and other metal

structural components (e.g., beams, sheets, columns etc). For example, these coatings can be

employed on structural steel to prevent collapse and/or structural compromise of bulk-heads,

decks, and firewalls of buildings as a further protection for occupants during a fire event.

[0006] Conventional intumescent coatings may contain a resin system “pigmented” with

various intumescent ingredients that under the influence of heat, react together to produce an

insulating foam or “char.” Preferably, this char will have low thermal conductivity but a

volume that is many times that of the original coating, thereby greatly reducing the rate of

heating experienced by the substrate and extending the time before the steel loses its integrity

and the building/ structure collapses.

[0007] In particular, when conventional intumescent coatings are exposed to fire or excessive

heat, an acid forms and reacts with a char-forming agent (carbon source) to create char.

Simultaneously, a blowing agent degrades to produce a non-flammable gas, thereby driving

expansion of the char as a foam. The resulting thick, porous, highly-insulating,

nonflammable, solid foam protects the substrate it covers from incident heat. Thus, the

coating should produce a tough, hard, strong, and compact char foam which is robust enough

to resist the extreme erosive forces of the certain fires, while still maintaining sufficient

adhesion to the substrate (structural steel in this case).

[0008] Cellulosic fueled fires are typical of modem day commercial and infrastructure

projects in the Built Environment, usually for architectural applications internally and

externally exposed structural steelwork. The cellulosic standard fire test curve (BS 476-20

Cellulosic) reaches 500°C within about 3 minutes and rises to in excess of 1000°C (i.e.,

1832°F) over 90 minutes.

[0009] Hydrocarbon fueled fires are typical of oil and gas installations. The hydrocarbon

standard fire test curve (BS476-20 Hydrocarbon) reaches 500°C within 1 minute and rises to

in excess of 1000°C (i.e., 1832°F) in about 8 minutes.

[0010] Hydrocarbon fueled jet fires are highly erosive, extremely turbulent fires (ISO 22899-

1), and have an immediate heat rise to 1 100°C. Fires of this nature experience heat fluxes in

the order of 250Kw/m 2.

[0011] During any type of fire, the rate of heating depending on the specific dimensions of

the steel sections used in the structure. The rate of heating is dependent on the Hp/A value of

the section, Where Hp is the perimeter of the steel When viewed in cross-section, and A is

the cross-sectional area. A steel section with a large perimeter (Hp) will receive more heat

than one with a smaller perimeter. On the other hand, the greater the cross-sectional area (A),

the more heat the steel section can absorb. Thus, a large thin steel section having a high Hp/A

value will heat up more quickly than a small thick section having a lower Hp/A value.

[0012] Adhesion of unbumed coating composition is extremely important prior to a fire in

order to ensure the intumescent functions properly. Cracking brought about by cyclic climatic

exposure (i.e., via regular heating and cooling cycles, as will occur both on a day-to-day basis

and, in many regions, on a season-by-season basis, as well as more extreme or dramatic drops

brought on by unusual weather events) is problematic.

[0013] In view of the foregoing, there is a need for a curable intumescent composition which

is capable of adhering to a steel substrate without cracking in the unbumed state, even when

exposed to extreme changes in temperature and weather conditions. In addition, the coating
composition needs to be capable of intumescing to form a uniform carbonaceous char upon

exposure to heat or flame thereby protecting the underlying steel substrate from structural

damage which may be brought about by a fire.

[0014] At present, Jotachar JF750 from Jotun (Sandefjord, Norway) is one type of

commercially available intumescent epoxy coating. Chartek 7 by Akzo Nobel (Amsterdam,

the Netherlands) and Firetex M90/02 by Sherwin Williams (Cleveland, Ohio) are other

examples of intumescent coatings. Additional intumescent and/or flame-retardant products

may be sold under these or other tradenames by each of these respective entities or other

entities.

[0015] United States Patent Publication 2016/0145466 discloses intumescent coatings that

are suitable for protecting substrates against hydrocarbon fires, such as jet fires. The

compositions include thermosetting polymer(s), curing agent(s), phosphoric and/or sulphonic

acid, metal or metalloid ions, and an amine functional blowing agent. As such, the

intumescent coating can be used without a supporting mesh.

[0016] United States Patent Publication 2016/0152841 contemplates similar types of

intumescent coatings. Here, boric acid may be used in addition to the phosphoric/sulphonic

acid(s), and melamine and isocyanurate are also included. Metal or metalloid ions are not

required.

[0017] United States Patent Publication 2016/0145446 describes a further iteration in

comparison to the above referenced documents. In this instance, the intumescent comprises

thermosetting polymer(s), curing agent(s), phosphoric and/or sulphonic acid, metal or

metalloid ions, and urea-, dicynamide-, and/or melamine-based blowing agent(s).

[0018] United States Patent Publication 2016/0160059 provides an intumescent coating

based upon an organic polymer, a spumific, and an additive providing a combination of two

different sources of metal/metalloid ions. Hydroxy-functional polysiloxanes are claimed in

this particular use, and specific types of metal atoms are recited.
[0019] In still a further example, United States Patent Publication 2015/0159368 describes a

liquid intumescent coating with at least one ethylenically unsaturated monomeric polymer

resin. The resin is cured by free radical polymerization adhesively bound onto a

reinforcement structure, such as inorganic fabric.

[0020] In contrast, examples of coating compositions specifically engineered for cold-

weather conditions are also known. For example, United States Patent 5,070,119, European

Patent EP0477840B1, United States Patent Publication 2018/0079915 and International

Patent Publications W02010131037A1 and WO2018227458A1 all provide examples of such

materials. Silicone-based alternative coatings are also sold under the trade names

SILOTHERM from Elox-Prom (Moscow, Russia) and NULLFIRE from Tremco-Illbruck

Ltd. (London, England).

SUMMARY OF INVENTION

[0021] An intumescent coating composition is able to repeatedly withstand extremely low

temperatures (i.e., -60° C) without cracking while retaining sufficient durability (as

demonstrated by resistance to water absorption), acceptable cure times, shore D hardness, and

an expandable, well-adhered, foamed char layer. In one aspect, the coating composition

balances the flexibility of an epoxy resin and curing agent combination by incorporating an

internally flexibilised acetoacetoxy polyacetoacetate (AcAc ) terminal unit in a polymer, such

as an AcAc functional epoxy polyester block copolymer or an AcAc functional dimer fatty

acid / polyester block copolymer. In another embodiment, a synergistic balance of specific

epoxy resin binders and amine functional curing agents—with or without catalytic

accelerators —also achieves these goals. In further aspect, a resin system relies upon either of

these same principles/approaches.

[0022] The compositions and coatings produced by these compositions have particular utility

in providing intumescent protections. Thus, the cured coating should be at least 20 mm,
capable of curing at 23° C to a Shore D hardness of least 5.0 in less than 24 hours, at least 25

in less than 7 days, and at least 35 in less than 14 days. The water (deionized, natural, or salt

water) absorption for the cured coating is at least less than 10.00 wt.% and, more preferably,

less than 5.0 wt.% after 28 days of submersion and at least less than 3.00 wt.% and, more

preferably, less than 1.00 wt.% after 5 days of submersion (with all wt.% relative to the dry

weight of the coating before submersion). Further still, the cured coating can withstand

temperatures of - 55° C or less (even as low as - 67.5° C) without cracking, and this

durability applies for at least 5 and, more preferably, at least 12 complete temperature cycles

from its lowest point back up to ambient conditions. Test procedures and further quantitative

and qualitative details are provided in the description and examples below, all of which

specifically inform and augment aspects of this disclosure.

[0023] One aspect of the invention encompasses a flexible resin system appropriate for use

with epoxy intumescent coating compositions. This resin system may include any

combination of the following features (in addition to all of the other details disclosed within

this description):

• at least one epoxy resin and an acetoacetate polyacetatoacetate (AcAc ) functional

polymer combined with an amine functional curing agent to form a coating that cures

within 24 hours with a shore D hardness of at least 2.5 or that cures within 24 hours at

23° C with a shore D hardness of at least 5.0;

• a catalyst selected from: dipropylenetriamine, benzyldimethylamine, n,n-

dimethylpropylamine, bis(dimethylaminoethyl)ether, bis-n,n-

dimethylethanolaminether, 1,3-propanediamine, l,3-bis[3-

(dimethylamino)propyl]urea, N'-(3- (dimethylamino)propyl)-N,N-dimethyl, 1,4-

diazabicyclooctane (DABCO), 2-(2-(2-dimethylaminoethoxy)-ethylmethylamino)-

ethanol, l,8-diazabicyclo[5.4.0]undec-7-en (DBU), 1,3-propanediamine, N'-(3-

(dimethylamino)propyl)-N,N-dimethyl l,5-diazabicyclo[4.3.0]non-5-en, 1,1, 3, 3-

 tetramethylguanidine, N,N,N',N",N"-pentamethyldiethylentriamine,

triphenylphosphine, trioctylphosphine, nonylphenol, 2-ethyl-4-methylimidazole, 2,6-

dimethylpyridine, N,N-bis-(2-hydroxyethyl)-3-methylaniline,

dimethylphenylphosphine, methyldiphenylphosphine, triphenylphosphite,

N,N,N',N",N"-pentamethyl, dimethylaminopyridine,N-(3-dimethylaminopropyl)-N,N-

diisopropanolamine, styrenated phenols,Tris-(dimethylaminomethyl)phenol, and

amino-n-propyldiethanolamine N,N,N',N",N"-pentamethyl- dipropylenetriamine.

• wherein the AcAc functional polymer includes at least one terminal AcAc unit as

follows:

in which R2 is -CH 2- and R 3 is -CH 3;

• wherein the cured coating: (i) when equilibrated to -60° C, does not crack after a

manual bend test, and (ii) when immersed in water for at least 5 days, gains less than

7.5 or less than 5.0 wt.% (relative to a dry weight of the film prior to being

immersed);

• wherein the AcAc functional polymer is at least one selected from: an polyester

block copolymer, a dimer fatty acid/polyester block copolymer, and an adduct,

modification, or derivative thereof;

• wherein the at least one epoxy resin is selected from: bisphenol A diglycidyl ether

epoxide resin; bisphenol F diglycidyl ether epoxide resin; epoxidized polyurethane,

oxymethylene bisoxirane resin; epoxidized alkyl phenols, epoxidized polyglycol

diglycidyl ether, bis- and oxirane bisphenol A diglycidyl ether resins; epoxidized

dimer acid; oleic acid; linoleic acid; erucic acid; epoxidized trimer fatty acid;

ethoxylated or propoxylated methacrylate monomers; bisphenol A, F, and A/F epoxy,

epoxy phenolic, novolac resins; epoxy cresol novolac resin; epoxidized castor oil
 triglycidyl ether; epoxidized phenyleneoxy[I -(butoxym ethyl) ethylene, di -functional

glycidyl ether; C13, C15-alkyl glycidyl ether; poly tetramethylene ether glycol;

polypropylene glycol copolymers; and any combination of two or more thereof;

• wherein the amine functional curing agent is selected from: polyamine, polyamide,

polyamidoamine, polyamidoimidazoline, aliphatic amine, phenalkamine,

polyetheramine modified phenalkamine, dimer-diamine mixtures comprising C36

Dimeric diamine, C18 amine, and C54 Trimeric amine, cycloaliphatic polyamine,

polyetherpolyamine, alkyletheramine, polyethylenimine, fatty alcohol adducted

polyetheramine, polyetherurethanamine, polyether-urethanepolyamine,

polyurethaneamine, polyetheramine, polyetheramide, polypropyleneamide,

polypropyleneamine, polyamide made by reacting with dimer fatty acids,

phenalkamide, polyamidoimidazoline, polyetherpolyamides, polyaminoamide, any

combination of two or thereof, and adducts or modifications thereof;

• wherein the at least one epoxy resin is selected from: (a) a bisphenol A /

epichlorohydrin derived epoxy resin (b) a multifunctional resin containing both

epoxide groups and reactive unsaturation (c) an internally flexibilised bisphenol A /

epichlorohydrin derived epoxy resin (d) a polyacetoacetate epoxy polyester (e) dimer

fatty acid polyester block copolymer (f) polyurethane epoxy resin or (g) a cashew nut

based and Castor Oil triglycidyl ether epoxy resin or can be a combination thereof;

• wherein the epoxy resin or resins account for between 10.00 and 70.00 wt.% of a total

mass of the coating, the amine functional curing agent or agents account for between

5.00 and 60.00 wt.% of the total mass of the coating, and the AcAc functional

polymer accounts for between 0.50 and 30.00 wt.% of the total mass of the resin

system;

• wherein the AcAc functional polymer is provided as part of the epoxy resin so that the

epoxy resin includes the at least one terminal AcAc unit; and
 • wherein the acetoacetate polyacetoacetate functional polymer has any of the structural

features shown in Figures 1A through ID.

[0024] A separate aspect of the invention specifically contemplates intumescent coating

composition resistant to cracking at -60° C and water absorption. It includes any combination

of the following features (in addition to all of the other details disclosed within this

description):

• a first part comprising at least one epoxy resin, an acetoacetoxy polyacetoacetate

(AcAc ) functional polymer, and an optional liquid plasticizer;

• a second part comprising at least one amine functional curing agent including

polyamide having an H eq.wt. between 90 and 110, and an optional liquid plasticizer;

• an intumescent ingredient package including an acid source, a carbon source, and a

gas source;

• wherein the AcAc functional polymer includes a terminal AcAc unit as follows

in which R2 is -CH 2- and R 3 is -CH 3;

• wherein the intumescent ingredient package further comprises at least one of: a

nucleating agent, fibres, a plasticiser, rheology modifiers, wetting/dispersion

additives, and any combination thereof;

• wherein every chain in the AcAc functional polymer ends with the terminal AcAc

unit;

• wherein the AcAc functional polymer consists of at least 0.50 wt.% relative to a

combined mass of the composition and, more preferably, about 5.00 to about 25.00

wt.% relative to the combined mass of the composition;

 • wherein the at least one amine functional curing agent consist of at least 5.00 wt.%

relative to a combined mass of the composition and, more preferably, about 15.00 to

about 30.00 wt.% relative to the combined mass of the composition;

• wherein the at least one epoxy resin consists of at least 10.00 wt.% relative to a

combined mass of the composition and, more preferably, about 15.00 to about 25.00

wt.% relative to the combined mass of the composition;

• wherein the at least one epoxy resin is derived from bisphenol A;

• wherein the amine functional curing agent includes polytetramethylene ether glycol-

based polyether amines having an H eq wt between 500 and 770;

• wherein the acetoacetate polyacetoacetate functional polymer has any of the structural

features shown in Figures 1A through ID;

• wherein the AcAc functional polymer is integrated with the epoxy resin so that the

epoxy resin includes the at least one terminal AcAc unit; and

• wherein the cured coating has a thickness of at least 20 mm, at least 22 mm, or at least

24 mm.

DESCRIPTION OF THE DRAWINGS

[0025] Operation of the invention may be better understood by reference to the detailed

description taken in connection with the following illustrations. These appended drawings

form part of this specification, and any information on/in the drawings is both literally

encompassed (i.e., the actual stated values) and relatively encompassed (e.g., ratios for

respective dimensions of parts). In the same manner, the relative positioning and relationship

of the components as shown in these drawings, as well as their function, shape, dimensions,

and appearance, may all further inform certain aspects of the invention as if fully rewritten

herein. Unless otherwise stated, all dimensions in the drawings are with reference to inches,

and any printed information on/in the drawings form part of this written disclosure.
[0026] In the drawings and attachments, all of which are incorporated as part of this

disclosure:

[0027] Figures 1A through ID depict the chemical structure of various chemical structures

useful as acetoacetoxy polyacetoacetate (AcAc ) components in certain embodiments.

[0028] Figure 2A is a schematic representation of a stress-strain curve for brittle and ductile

work pieces, while Figure 2B schematically illustrates the difference in failure mode for each.

[0029] Figure 3 is a series of stress-strain curves for various resin system formulations

reported in Tables l a and l b below.

DETAILED DESCRIPTION

[0030] Specific reference is made to the appended claims, drawings, and description, all of

which disclose elements of the invention. While specific embodiments are identified, it will

be understood that elements from one described aspect may be combined with those from a

separately identified aspect. In the same manner, a person of ordinary skill will have the

requisite understanding of common processes, components, and methods, and this description

is intended to encompass and disclose such common aspects even if they are not expressly

identified herein.

[0031] As used herein, the words “example” and “exemplary” mean an instance, or

illustration. The words “example” or “exemplary” do not indicate a key or preferred aspect or

embodiment. The word “or” is intended to be inclusive rather an exclusive, unless context

suggests otherwise. As an example, the phrase “A employs B or C,” includes any inclusive

permutation (e.g., A employs B; A employs C; or A employs both B and C). As another

matter, the articles “a” and “an” are generally intended to mean “one or more” unless context

suggest otherwise.
[0032] Temperatures as low as -60°C are experienced in many parts of the world where there

is a requirement for hydrocarbon fire and/or jet fire protection. Temperature fluctuations are

also frequently experienced leading to cracking problems, among other things.

[0033] Prior art epoxy intumescent coatings designed for hydrocarbon fire and jet fire

applications (e.g., PITT-CHAR XP sold by PPG Industries, Inc. in Pittsburgh, Pennsylvania

and/or those described in International Patent Publication WO/2018/227458, as well as the

patent documents identified above), sometimes claim unique flexibility but this is generally at

‘ambient temperature’ and usually for thinner coatings (i.e., < 15 mm for less than 1.5 hours

of protection) than those needed to deliver jet fire protection (i.e., 20 to 28 mm for at least 2

hours of protection). In any case, no claim is made of crack resistance below -40°C. In

addition, no claim is made as to low water absorption. Indeed, many technologies in the art

have significant water absorption, which is detrimental to the coating.

[0034] Further, prior art technologies that claim offer low temperature usually experience

high water absorption. In turn, cure rates for water-absorbing coatings may become

unacceptably protracted, and other problems associated with water absorption in intumescent

coatings will be familiar to those in this field.

[0035] In particular, it was understood that, for flexibility at extremely low temperatures (i.e.,

less than -40°C and approaching -60°C), it was preferable to select a resin with comparatively

low glass transition (Tg), such as an epoxy resin binder with an amine functional curing

agent. However, these systems can also be slow to cure and may not be durable as-they can

tend to absorb high levels of water. It was understood that adding a catalyst may speed up the

cure speed but the coating could become more brittle and not able to withstand temperatures

below -30°C while also leading to increased water adsorption. Such amine catalysts as like

Tris-(dimethylaminomethyl)phenol, Benzyldimethylamine (BDMA), Amino-n-

propyldiethanolamine, Triethanolamine, N,N-dimethyldipropylenetriamine, Tris-

(dimethylaminomethyl)phenol, have increased effect on water adsorption and detrimental

effects on coating low temperature flexibility.

[0036] The inventors determined that many urethane epoxy resin binder and /or

polyetherurethanamine or polyetherurethane amine functional curing agents were sufficiently

flexible and did not crack at temperatures down to -60°C. However, the water adsorption for

these systems was unacceptably high and their cure speed slow—leading to a coating with a

tacky surface that was not suitable.

[0037] The present invention relies upon a unique balance between the both epoxy resin

binders, amine functional curing agents with or without catalyst. Such formulations are

directed to intumescent coatings designed for hydrocarbon fuelled and jet fire protection in

such cold weather environments (i.e., where -60°C is regularly or occasionally observed).

This invention addresses the issue of both low temperature flexibility and water uptake by

presenting a low water absorption version and a cure rate close to conventional materials

(when curing conditions are at ~23°C at 50°% humidity).

[0038] The compositions contemplated herein are typically epoxy/polyamide based systems

that form a robust and hard char when exposed to a hydrocarbon or jet fire. This hard char is

designed to withstand the extreme erosive forces of these fires. The coating can swell

typically up to 20 times its dry film thickness and insulates (protects) the steel from heat by

slowing the rate of heating.

[0039] To achieve the specified fire resistance period the intumescent coating can typically

be applied at up to 30mm dry film thickness. This presents challenges when the material is

exposed in situ to extreme low temperatures. When sub-zero temperatures reach around -

20°C to -40°C, traditional epoxy intumescent coatings will typically crack especially when

temperature variation from cold to warm is experienced cyclically.

[0040] The present invention overcomes this problem and allows for an epoxy based coating

formulation that when installed on steel at 20 mm and even up to 28 mm, without a

reinforcing mesh, can withstand temperatures down to -60°C without visually cracking.

Moreover it can withstand continuous temperature cycles from +20°C to -60°C without

visually cracking.

[0041] Still other characterizing features of the coatings produced by the compositions herein

relate to hardness, adhesion, and expansive char formation. These properties can be measured

by applicable standardized tests (such as various regimes published by ASTM International),

with shore D hardness being particularly pertinent. The test methods set forth in the

Examples below, including the qualitative and/or quantitative metrics for pass or fail, provide

means for characterizing and distinguishing various aspects of the invention.

[0042] The present invention is directed to epoxy intumescent coatings. Generally epoxy

based paints offer unrivalled corrosion protection and water resistance which is highly

desirable in heavy industrial and ocean and marine environments. In this present invention

the intumescent coating would be used for ‘on-shore’ or ‘off-shore’ applications.

[0043] Epoxy resin binders are obtained in a known manner, for example from the oxidation

of the corresponding olefins or from the reaction of epichlorohydrin with the corresponding

polyols, polyphenols or amines. Basic information on and examples for epoxide resins can be

inferred from the section “Epoxy resins” of the Encyclopedia of Polymer Sciences and

Technology, Vol. 9, Wiley-Interscience, 2004. Reaction products of polyhydroxy compounds

can be mentioned by way of example as suitable epoxide resins, in particular polyvalent

phenols or phenol-aldehyde condensates with epihalohydrins or the precursors thereof, in

particular: (a) reaction products of epichlorohydrin with bisphenol A; (b) reaction products of

epichlorohydrin with bisphenol F; (c) aromatic glycidyl amine resins ; phenyl eneoxy [I -

(butoxym ethyl) ethylene: (d) epoxy novolacs on phenol such as alkyl phenols or cresol basis;

(e) epoxide resins without aromatic structural units; as well as mixtures of two or more

epoxide resins of this type in any ratio and in any degrees of purity.
[0044] Here, the epoxy resin binder may be produced by any suitable method. The epoxy

resin binder may comprise one or more epoxy resins. Such ‘epoxy resins’ may include

(homo) polymers and copolymers derived from combinations of compounds comprising at

least one epoxide functionality such as glycidol with cyclic co-reactants, suitably aromatic

co-reactants comprising at least two hydroxyl groups such as Bisphenol A, alkyl phenolics.

As used herein, the terms “epoxy” and “epoxide” are used interchangeably. Examples of

suitable compounds comprising at least one epoxide functionality include, but are not limited

to one or more of the following: epichlorohydrin, fatty acids , glycidol , glycol amines or

mixtures thereof. Examples of suitable cyclic co-reactants, suitably aromatic co-reactants

include, but are not limited to one or more of the following: Bisphenol A; Bisphenol F;

Epoxidized Polyurethane, Epoxidized phenyl eneoxy [I -(butoxym ethyl )ethylene, poly

tetramethylene ether glycol, polyethylene oxide, polypropylene glycol copolymer. alkyl

phenolics, Novolac resins such as alkyl phenol novolac, phenolic novolac and cresol novolac

or mixtures thereof . As well as mixtures of two or more of epoxy resin binders of any type in

any ratio and in any degrees of purity.

[0045] Suitable epoxy resin binders (i.e., epoxy functional resin) can derived from or include

(a) polyglycidyl ethers derived from such polyhydric alcohols such as ethyleneglycol,

diethyleneglycol, triethyleneglycol, 1,2-propyleneglycol, 1,4-butyleneglycol, 1,5-pentanediol,

1,2,6-hexanetriol, glycerol, thrimethylolpropane, bisphenol-A (a condensation product of

acetone and phenol), bisphenol-F (a condensation product of phenol and formaldehyde),

hydrogenated bisphenol-A, or hydrogenated bisphenol-F, (b) polyglycidyl ethers of

polycarboxylic acids, formed by the reaction of an epoxy compound such as epichlorohydrin

with an aromatic or aliphatic polycarboxylic acid such as oxalic acid, succinic acid, glutaric

acid, terephthalic acid, 2,6-napthalene dicarboxylic acid, or dimerised linoleic acid, fatty

acids, adipic acid; oleic acid, linoleic acid, erucic acid and the like: decanedioic acid or

dimer, or Trimer fatty acids and a like with polyglycol diglycidyl ethers thereof (c) epoxy
resins containing oxyalkylene groups, (d) epoxidized phenyleneoxy[I -(butoxym ethyl )

ethylene, (e) Epoxidized olefmically unsaturated alicyclic materials such as epoxy alicyclic

ethers and esters, (f) Epoxy resins containing or reacted with either poly tetramethylene ether

glycol and /or polypropylene glycol including mixture thereof (g) Epoxy novolac resins,

which are prepared by reacting an epihalohydrin (e.g. epichlorohydrin) with the condensation

product of an aldehyde with a monohydric or polyhydric phenol (e.g. phenolformaldehyde

condensate), (h) Epoxidized Polyurethane or Polyetherurethane (i) Amine-terminated

polyether adducted. Epoxidized phenyleneoxy[I -(butoxym ethyl )ethylene, (j) any

combination of two or more of the foregoing in any appropriate ratio and in any degrees of

purity.

[0046] Polyepoxide liquid resins are particularly suitable as epoxy resin binders, they are

commonly termed “liquid epoxy resin”. These have a glass transition temperature which is

usually below 25° C., In this present invention the suitable compounds are the glycidylization

products of: dihydroxybenzene derivatives such as resorcinol, hydroquinone and

pyrocatechol; further bisphenols or polyphenols such as bis-(4-hydroxy-3-methylphenyl)-

methane, 2,2-bis-(4-hydroxy-3-methylyphenyl)-propane (bisphenol-C), bis-(3,5-dimethyl-4-

hydroxyphenyl)-methane, 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane, 2,2-bis-(4-

hydroxyphenyl)-butane (bisphenol-B), 3,3-bis-(4-hydroxyphenyl)-pentane, 3,4-bis-(4-

hydroxyphenyl)-hexane, 4,4- bis-(4-hydroxyphenyl)-heptane, 2,4-bis-(4-hydroxyphenyl)-2-

methylbutane, polyoxyethylene ,2,4-bis-(3, 5-dimethyl-4-hydroxyphenyl)-2-methylbutane,

l,l-bis-(4-hydroxyphenyl)-cyclohexane (bisphenol-Z), 1 l,l-bis-(4-hydroxyphenyl)-3,3,5-

trimethylcyclohexane (bisphenol-TMC), l,l-bis-(4-hydroxyphenyl)-l -phenyl-ethane, 1,4-

bis[2-(4-hydroxyphenyl)-2-propyl] -benzol) (bisphenol-P), l,3-bis-[2-(4-hydroxyphenyl)-2-

propyl] benzol) (bisphenol-M), 4,4'-dihydroxydiphenyl, 4,4'-dihydroxybenzophenon, bis-(2-

hydroxynaphth- 1-yl)-methane, bis-(4-hydroxynaphth-l -yl)-methane 1,5-dihydroxy-

naphthalin, tris-(4-hydroxyphenyl)-methane, l,l,2,2-tetrakis-(4-hydroxyphenyl)-ethane bis-

(4-hydroxyphenyl)- ether, polyglycidyl ether, bis-(4-hydroxyphenyl)sulfate; condensation

products of phenols with formaldehyde which are obtained under acidic conditions, such as

phenol novolacs or cresol novolacs, also called bisphenol F novolacs; aromatic amines, such

as aniline, toluidine, 4-aminophenol, 4,4'-methylendiphenyldiamine (MDA), 4,4'-

methylendiphenyldi-(N-methyl)-amine, 4,4'-[ 1,4-phenylene-bis-(l -methylethylidene)] -

bisaniline (bisaniline-P),[l,3-phenylene-bis-(l-methylethylidene)]-bisaniline (bisaniline-

M);as well as mixtures of two or more of any type in any ratio and in any degrees of purity.

[0047] The epoxy resin used in the practice of this invention may include one or more epoxy

resins employed in combination. In general, the epoxy resins can be derived from glycidated

resins, cycloaliphhatic resins, epoxidized oils, fatty acids, polyhydric alcohols and so forth.

The glycidated resins are frequently the reaction product of a glycidyl ether, such as

epichlorohydrin, and a bisphenol compound such as bisphenol A . C4-C28 alkyl glycidyl

ethers; C2-C28 alkyl-and alkenyl-glycidyl esters; C1-C28 alkyl-, mono- and poly-phenol

glycidyl ethers; polypropyleneglycol diglycidyl ether, C13, C15-alkyl glycidyl ether,

polypropylene glycol-triglycidyl ether, glycerol propoxylate triglycidyl ether, bis- and oxirane

Bisphenol A diglycidyl ether, di-functional glycidyl ether, polyglycidyl ethers of

pyrocatechol, resorcinol, hydroquinone, 4,4'-dihydroxydiphenyl methane (or bisphenol F),

4,4'-dihydroxy-3,3'-dimethyldiphenyl methane, 4,4'-dihydroxy diphenyl dimethyl methane (or

bisphenol A), 4,4'-dihydroxydiphenyl methyl methane, 4,4'-(l-methylethylidene) phenol

diglycidyl ether, 4,4'-dihydroxydiphenyl cyclohexane, 4,4'-dihydroxy-3,3'-dimethyldiphenyl

propane, 4,4'-dihydroxydiphenyl suflone, and tris (4-hydroxyphynyl)methane; polyglycidyl

ethers of the chlorination and bromination products of the above-mentioned diphenols;

polyglycidyl ethers of novolacs; polyglycidyl ethers of diphenols obtained by esterifying

ethers of diphenols obtained by esterifying salts of an aromatic hydrocarboxylic acid with a

dihaloalkane or dihalogen dialkyl ether; polyglycidyl ethers of polyphenols obtained by

condensing phenols and long-chain halogen paraffins containing at least two halogen atoms;
Ν ,Ν '-diglycidyl-aniline; N,N'-dimethyl-N,N'-diglycidyl-4,4'-diaminodiphenyl methane;

N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenyl methane; N,N'-diglycidyl-4-aminophenyl

glycidyl ether; N,N,N',N'-tetraglycidyl-l, 3-propylene bis-4-aminobenzoate, phenol novolac

epoxy resin binder; cresol novolac epoxy resin; and combinations thereof in any ratio.

[0048] More specifically, the epoxy resin binder may comprise commercially available

epoxy resin materials. In certain embodiments, the epoxide resin binder may comprise

Bisphenol diglycidyl ether epoxide resins, such as Bisphenol A diglycidyl ether and/or

Bisphenol F diglycidyl ether epoxide resins. In a further embodiment, the epoxide resin

binder may comprise one or more of the following: Bisphenol A diglycidyl ether epoxide

resin; Bisphenol F diglycidyl ether epoxide resin; epoxidized polyurethane, oxymethylene

bisoxirane based resin, epoxidized alkyl phenols, epoxidized polyglycol diglycidyl ether, b is

and oxirane Bisphenol A diglycidyl ether, epoxidized dimer acid such as but not limited to

oleic acid, linoleic acid, erucic acid and the like, epoxidized trimer fatty acid, acrylate and

alkyne monomers (unsaturated acrylate, carbon -carbon double or triple bonds) including

methacrylate monomers which can be ethoxylated or propoxylated. Bisphenol A or F and A/F

epoxy, epoxy phenolic, novolac resin, epoxy cresol novolac resin. Including but not limited

to epoxidized; castor oil triglycidyl ether, epoxidized phenyleneoxy[I -(butoxym ethyl)

ethylene, di-functional glycidyl ether, C13, C15-alkyl glycidyl ether , poly tetramethylene

ether glycol, polypropylene glycol copolymer, as well as mixtures of two or more of epoxide

resins of this type in any ratio and in any degrees of purity.

[0049] Preferably, the aforementioned epoxies include a bisphenol diglycidyl ether epoxide

resin along with an AcAc functional polymer comprising an internally flexibilised

acetoacetoxy polyacetoacetate (acetoacetyl- functional groups) functional epoxy polyester

block copolymer and/or an acetoacetate functional dimer fatty acid based polyol / polyester

block copolymer.
[0050] The acetoacetyl-functional polymers or copolymers may include one or more of the

acetoacetyl-functional groups. A generalized example of an acetoacetyl-functional group

structure is shown in Figure 1A , which has the formula C4H5O3, where R2 is a CH 2, R3 is a

methyl group, and ester group is provided pendant to the main chain. The acetoacetyl can

provided with the epoxy functional resin. While all of these components may be initially

combined, relatively limited pot times may necessitate the use of a two-part system and/or

with the AcAc- functional polymer used as a separate additive (relative to the epoxy resin(s)

and the amine curing agent) so as to maximize the ability to effectively coat substrates as

desired. The acetoacetyl-functional groups can be internal, terminal, branched or side chained

or mixtures of, although at least one branch of the polymer preferably terminates with

acetoacetyl-functionality. The acetoacetyl-functional group may be bonded to the polyester

functional block or directly to the polyol functional block as needed for a particular

application.

[0051] Derivative of these acetoacetate copolymers are also viable, including but not limited

to (a) polypropylene glycol based (e.g., co-reacted with polypropylene glycol), poly- diol

based (e.g., co-reacted with a polycarbonate diol, polypropylene glycol, polyether diol,

polyester diol, etc), (b) urethane modified (e.g., co-reacted with isocyanate) iterations thereof

(c) silicones, silanes , (meth) acrylates, acrylics, but not limited to . Such (Acetoacetate)

based epoxy resin binder(s) can be used on its own or mixed with any other epoxy resin

binders listed in this invention in any ratio or purity.

[0052] A generalized formula for the AcAc functional polymer is shown below and in

Figure 1A, where R2 is -CH 2- and R 3 is -CH 3. This structure is positioned on at least one

terminal end of a straight or branched chain, with that structure linked to the remaining

polymer chain by way of an ester linkage. In some embodiments, this ester linkage may be

part of the polymeric repeating unit. Broadly speaking throughout this disclosure, any

reference to AcAc functional polymers encompasses this structure on at least one end of the
polymer chain. In certain embodiments, the AcAc functional polymer may take the form of

an acetoacetate functional dimer fatty acid based polyol and/or polyester block copolymer, as

elsewhere herein. As used in this disclosure, AcAc polymers may be characterized as

terminating in either or both of these structures, provided such structure is appended to the

terminal end of at least one branch or chain of the polymer (thereby rendering the polymer an

AcAc functional polymer).

[0053] One particular type of AcAc functional polymer can be based on reactions with

polyols, and the structure below provides an example. Here, the structure is shown below and

in Figure IB, with n being a whole integer between 5 and 75 and, more preferably, at least 8

and no greater than 68. Note that an AcAc unit, as shown in Figure 1A, is positioned at a

terminal end of the chain.

[0054] More specific examples of other AcAc functional polymers are shown in Figures 1C

and ID . In these Figures, n is at least 3 and may be up to 1,000 (or whatever practical upper

limit is set by reaction conditions). Notably, Figure 1C is representative of a acetoacetate

functional dimer fatty acid based polyol/polyester block copolymer, while Figure ID is an

AcAc functional polymer initially formed from caprolactones. In each instance, the AcAc

unit (Figure 1A) terminates at least one, if not all, of the branches/chains. Notably, these

structures are exemplary as specific embodiments, and modifications and derivatives of these
structures can also be employed. For example, the length of the repeating chains, as well as

the non-AcAc block(s), can be altered.

[0055] The acetoacetate functional flexible block copolymer may include at least a

hydrophobic polyol block; functional endcaps provided by epoxy groups, acetoacetate

groups, or both. Preferably, the endcaps have a functionality greater than 1. In some

approaches, the polymer may also include optional functional extension groups such as

isocyanates or silicones for flexibility. To provide flexibility, the block copolymer may either

include select polyalkylene glycol diol blocks having a molecular weight to impart flexibility

or, if the hydrophobic polyol block includes epoxy and/or fatty acid derived polyol groups,

then the flexible copolymer may also include one or more lactone-derived flexibility blocks

each having the residue of at least 3 or more repeating lactone groups. The optional

functional groups may include hydroxyl and other groups that do not create unfavourable

reactions/conditions with the remaining constituents.

[0056] Use of the foregoing AcAc functional polymers, in combination with the epoxy

resin(s) and amine functional curing agents(s) disclosed herein, enable the creation of a

flexible coating formulation which is ideally suited for low temperature intumescent

applications, with AcAc functional polymer facilitating flexible portions of the epoxy

becoming integrated into the final, cured coating. Thus, by judiciously selecting appropriate

epoxy resin(s), amine curing agent(s), and intumescent components (acid source, blowing

agent, char former, plasticizer, etc.), a thick coating appropriate for intumescent protection

can be achieved. Further, owing to its flexibility and low water uptake, the coating can

withstand temperature cycling to extreme lows—well beyond current commercially available

products.

[0057] The epoxy resin binder suitable for this invention can be selected from (a) a bisphenol

A / epichlorohydrin derived epoxy resin of typical viscosity 100 - 2200 mPas (25°C) and

having a weight per epoxide of 165-250 g/Eq, (b) an internally flexibilised bisphenol A /
epichlorohydrin derived epoxy resin typical viscosity 500 - 1400m Pas but not limited to

(25°C) and having a weight per epoxide of 400-2500 g/Eq (c) a polyacetoacetate epoxy

polyester or dimer (or Trimer)fatty acid based polyol polyester block copolymer, (d)

polyurethane epoxy resin, (e) alkenyl phenol formaldehyde novolac resin, (f)

poly(tetramethylene oxide, (g) Polyglycol diglycidyl ether or castor oil triglycidyl ether

resin, epoxy resin binders which can be used in any combinations thereof, in any ratio and in

any degrees of purity.

[0058] Additional epoxy resin binder suitable for this invention can be selected from but not

limited to oxymethylene bisoxirane, epoxidized phenyleneoxyl -(butoxym ethyl )ethylene di-

functional glycidyl ether epoxy resin, Flexible epoxy resin -dimer acid based, acrylate

monomer , C l 3, Cl 5-alkyl glycidyl ether , Bisphenol F and A/F epoxy and

mixtures/derivatives thereof.

[0059] These epoxy resin binders preferably have number-average molecular weight (Mn)

from about 100 to 12000 Daltons (Da=g/mole) and, more preferably, from about 100 to 3500

Da. Their epoxy equivalent weight (EEW) should range from 75 to 6,000 and, more

preferably, 130-2500 g/eq. The glass transition temperature (Tg) of the epoxy resin binder

can be from about -80 to 80° C., with -60 to 40° C and -40 to 30° C being more preferred

ranges.

[0060] The epoxy resin binder component is combined with an amine functional curing

agent. These agents can be selected from but not limited to polyamines, polyamides,

polyamidoamines, aliphatic polyamines, polyamidoimidazolines, polyimidazolines,

polyamidoamines, dimerdiamine amines, polyetheramines, phenalkamines, phenalkamides,

dimer-diamines, (mixtures of C36 dimeric diamine, C18 amine, C54 or Trimeric amines),

fatty alcohol adducted polyamines, cycloaliphatic amines, polyamines, trimeric amines,

cycloaliphatic polyamines, polyetherpolyamines, alkyletheramines, polyethylenimines,

polyetheramines, polyetherurethanamines, polyether-urethanepolyamines,

polyurethaneamines, polyetherpolyamides, polypropyleneamides, polypropyleneamines,

polyoxypropylenediamine, polyetherpolyamine or polyaminoamides, polyetheramides,

polyetherpolyamides, polyaminoamines, or derived from polytetramethylene ether glycol,

polytetramethylene oxide, glycol, polypropylene glycol , propylene oxide, ethylene oxide,

dimer ( or trimer) fatty acid based amine functional curing agents or a mixture thereof. But

not limited to. This is inclusive of adducted above amine curing agents; as well as mixtures

of one or more of amine functional curing agents of this type in any ratio and in any degrees

of purity modifications combinations and derivatives thereof and mixtures thereof..

[0061] Further suitable amine functional curing agent for this invention can be, but not

limited to, derived from aliphatic and aromatic amines, cycloaliphatic amines, a Lewis base

or a Mannich base. For example, the aliphatic amine linear, branched, and cycloaliphatic

amines may be but not limited to alkylene diamines such as ethylene diamine, propylene

diamine, diamines are chosen from the group ethyl enediamine diethylenetriamine,

triethylenetetramine, tetraethyl enepentamine, m-xylylendiamine), isophorone diamine. 1,4-

diaminobutane, 1,3- or 1,4-cyclohexame diamine, 1,3-diaminopentane, 1,6-diaminohexane,

2,5-diamino-2,5-dimethylhexane, 2,2,4-trimethyl-l,6-diaminohexane, 1,1 1-diaminoundecane,

1,12-diaminododecane, dimer-diamines (such as but not limited to mixtures of C36 dimeric

diamine, C18 amine, C54 or trimeric amines), 1-amino-3, 3, 5-trimethyl-5-aminomethyl-

cyclohexane, 2,4- or 2,6-hexahydrotolxylene diamine, 2,4'- or 4,4'-diaminodicyclohexyl

methane, 3,3'-dialkyl-4,4'-diamino-dicyclohexyl methane isophoronediamine, triethylene

diamine, trimethythexamethylene diamine, piperazine-n-ethylamine, polyoxyalkylene,

diamines made from either or combinations of linear polyether glycol, alkyl phenols ,poly

(tetramethylene oxide) glycol, polybutylene glycol, ethylene oxide, propylene oxide and/or

polyether glycol. In any degrees of purity, modifications combinations and derivatives

thereof and mixtures thereof.

[0062] In other embodiments, the amine functional curing agent may be a

polyamidoimidazoline. Suitable polyamidoimidazolines but not limited to may be formed by

any suitable method. For example, such polyamidoimidazolines may include

(homo)polymers or copolymers derived from combinations of polyamines and dicarboxybc

acids. Examples of suitable polyamines include, but are not limited to one or more of the

following: ethylenediamine; diethylenetriamine; triethylenetetramine; tetraethylenepentamine

or mixtures thereof. Examples of suitable dicarboxybc acids include, but are not limited to:

dimerised or trimerised fatty acids; adipic acid oleic acid, bnoleic acid, erucic acid and the

like , In any degrees of purity modifications, combinations and derivatives thereof and

mixtures thereof mixtures thereof.

[0063] In still other embodiments, amine functional curing agents can be polyamines such as

diethylene triamine, triethylene tetramine, isophorone diamine, tetraethylene pentamine,

alkylene diamines ,dicyandiamide, polyamido-amine, polyamide resin, ketimine compounds,

m-xylene diamine, m-phenylene diamine, l,3-bis(aminomethyl)cyclohexane, bis(4-

aminocyclohexyl) methane, diethylene glycol-bis-1- propamine ,N-aminoethyl piperazine,

polyetheramine ,polyetherpolyamines Polyetherurethanamine, Polyetherurethane polyamine,

dimer diamine, 4,4'-diaminodiphenyl methane, 4,4'-diamino-3, 3'-diethyl-diphenyl methane,

and diaminodiphenyl sulfone, phenalkamine, mannich bases or derivatives thereof.

Commercial grade quality curing agents of any of these polyamines may be used. In any

degrees of purity modifications, combinations and derivatives thereof and mixtures thereof

mixtures thereof . Adducts of any of these polyamines can also be used.

[0064] In addition, adducts of any above amine functional curing agents can also be used.

The adduct of an amine functional curing agent is formed by partially reacting amine

functional curing agents with a suitable reactive compound, such as an epoxy resin. This

reaction will decrease the content of free amine in the curing agent, making it more useful at

low temperature and/or high humidity environment.

[0065] When polyamides are used as the amine functional curing agent it can make the

coating have a good balance between corrosion resistance and waterproof property. Further

polyamides can also make the coating have good flexibility, proper curing rate and other

advantageous factor.

[0066] The amine functional curing agent’s may be produced by any suitable method but are

not limited to one or more of the following: in any ratio and in any degrees of purity

combinations/mixtures thereof. Such amine curing agent’s may include (homo)polymers or

copolymers derived from combinations of polyamines, mannich bases , alkyl phenolic

compounds and dicarboxylic acids. Examples of suitable polyamines include, but are not

limited to one or more of the following: polyethylenimine: triethylenetetramine;

hexamethylenediamine; ethylenedi amine; diethylenetriamine; di ethylene glycol-bis-1-

propamine, tetraethylenepentamine, diethylene glycol-bisl -propamine, isophoronediamine or

mixtures thereof. Examples of suitable dicarboxylic acids (or anhydride or ester derivatives)

include, but are not limited to one or more of the following: dimerised fatty acids, adipic acid;

oleic acid, linoleic acid, erucic acid and the like: decanedioic acid or dimer, or Trimer fatty

acids, dimer of stearic acid; dimer of palmitic acid; dimer of lauric acid, adipic acid or type

and / or a like . Dicarboxylic acids form of cyclic anhydrides of dicarboxylic acids, examples

include maleic anhydride; sulfonic anhydride; phthalic anhydride or mixtures thereof.

Dicarboxylic acids can also be used in the form of the di-ester materials such as diethyl

malonate; dimethyl malonate or mixtures thereof. Suitably, the dicarboxylic acids are in the

form of. In any degrees of purity modifications combinations and derivatives thereof and

mixtures thereof mixtures thereof.

[0067] The amine functional curing agent has a number-average molecular weight (Mw)

from about 100 to 8000 Daltons (Da=g/mole) and, more preferably, from about 200 to 4000

Da. The amine functional curing agent’s preferably has an hydrogen equivalent weight (H

EqWT) in the range of 50 to 4,000 and, more preferably, 65-1100 g/eq. The glass transition
temperature (Tg) may be from about -50 to 50° C suitably from about -30 to 30° C., or even

from about -20 to 20° C .

[0068] The epoxy component of the resin system preferably constitutes from 10% to 70% by

weight of the total formulation. In turn, amine component preferably constitutes 5% to 60%

by weight of the total formulation. In coating compositions, additional components may be

added, with weight ratios of epoxy to amine components being adjusted accordingly based on

the disclosure for the resin system. Still other coating composition formulations are disclosed

in more detail below.

[0069] The coating composition of the invention, in one preferred embodiment, is typically

100% solids but may also have additional solvent added to aid application. It is a 2 pack,

ambient cure system with one part containing the epoxy resin binder component (Part A) and

the other component containing the amine functional curing agent (as described above)

functional component (Part B). The intumescent ingredients can be added to either or both

components. A catalyst can be included in the composition to aid the curing mechanism. The

coating cures to a dry film typically over several hours but this can vary dependent on the

choice of resins and catalyst type / level used.

[0070] The total resin components of the mixture of Part A and Part B ideally constitute from

15% to 80% by weight of the total coating composition. More preferably the total resin

components constitute from 25% to 60% by weight of the coating composition.

[0071] The amount of amine functional curing agent may vary depending on the amount of

epoxy resin binder to be cured. In general, the amount of amine functional curing agent

employed is so that the volumetric ratio of an amine side to an epoxy side is from about 30:70

to about 70:30, with a weight ratio of from about 1:15 to 15:1 being most typical. Typically,

the mole ratio of amine functional curing agent to the epoxy resin binder is in the range from

about 0.25 to about 2.5, and in one embodiment is about 1.5:1.

[0072] A catalyst may be used to aid/quicken curing of the epoxy resin binder with the amine

functional curing agent. Catalysts may be selected from compatible tertiary amines,

aminophenols, polyalcohols , phenols, phosphines and phosphonium salts. In preferred

embodiments, the catalyst is selected from one or more catalysts (accelerators) maybe used

to speed up the curing mechanism. The catalysts maybe dipropylenetriamine,

benzyldimethylamine, n,n-dimethylpropylamine, bis(dimethylaminoethyl)ether, bis-n,n-

dimethylethanolaminether, 1,3-propanediamine, l,3-bis[3-(dimethylamino)propyl]urea, N'-

(3- (dimethylamino)propyl)-N,N-dimethyl, 1,4-diazabicyclooctane (DABCO), 2-(2-(2-

dimethylaminoethoxy)-ethylmethylamino)-ethanol, l,8-diazabicyclo[5.4.0]undec-7-en

(DBU), 1,3-propanediamine, N'-(3- (dimethylamino)propyl)-N,N-dimethyl 1,5-

diazabicyclo[4.3.0]non-5-en, 1, 1,3,3-tetramethylguanidine, N,N,N',N",N"-

pentamethyldiethylentriamine, triphenylphosphine, trioctylphosphine, nonylphenol, 2-ethyl-

4-methylimidazole, 2,6-dimethylpyridine, N,N-bis-(2-hydroxyethyl)-3-methylaniline,

dimethylphenylphosphine, methyldiphenylphosphine, triphenylphosphite, N,N,N',N",N"-

pentamethyl, dimethylaminopyridine,N-(3-dimethylaminopropyl)-N,N- diisopropanolamine,

styrenated phenols,Tris-(dimethylaminomethyl)phenol, amino-n-propyldiethanolamine

N,N,N',N",N"-pentamethyl- dipropylenetriamine, are preferred.

[0073] The catalyst content is preferably in the range of 0.02 - 5% by weight of the coating

composition, more preferably in the range of 0.2 - 3% by weight of the coating composition.

[0074] When formulated as a comprehensive intumescent coating composition, a number of

varying additives and enhancements can be employed. First, intumescent compositions

according to the invention may contain an epoxy reactive diluent. Epoxy reactive diluents are

sometimes used to lower the viscosity of the composition or induce more flexibility into the

epoxy coating. Such epoxy reactive diluents may be formed from the reaction of a compound

comprising at least one aliphatic epoxide functionality such as diglycidyl ether with an

aliphatic alcohol or polyol. Examples of suitable compounds comprising at least one epoxide
functionality include, but are not limited to one or more of the following: monoglycidyl ether;

polytetramethylene oxide, castor oil triglycidyl ether diglycidyl ether; polypropyleneglycol

diglycidyl ether, triglycidyl ether, glycerol propoxylate triglycidyl ether and mixtures thereof.

Examples of suitable alcohols and polyols include, but are not limited to one or more of the

following: hexanediol; butanediol; glycerol; trimethylolpropane; trimethylolethane;

pentaerythritol; neopentyl glycol and mixtures thereof.

[0075] Additionally or alternatively, the composition may have a low viscosity acrylate or

methacrylate monomers (containing ethylenically unsaturated double bonds) and Allyl

monomers. These ethylenically unsaturated monomeric components can be monofunctional,

difunctional or trifunctional. Commercially available examples of acrylate or methacrylate

reactive monomers include, but are not limited to: 1,6-Hexanediol diacrylate,

Trimethylolpropane triacrylate, Tripropylene glycol diacrylate and propoxylated-glycerol-

triacrylate or mixture thereof but not limited to, in any ratio or purity.

[0076] Further components may be included that react together under the influence of heat

from a fire to form a protective insulating foam or char. These intumescent ingredients should

be of low solubility to ensure that the coating has an acceptable level of durability, and

maintains its integrity throughout the service life of the coating. Additionally, the intumescent

ingredients used should have a sufficiently small particle size, in order to obtain satisfactory

dispersion in the resin components, and thus allow application by spray application methods

giving high rates of transfer of the coating to the substrate.

[0077] The intumescent ingredients preferably consist of three components, an acid source,

a carbon source and a spumific or gas source. An inorganic “nucleating agent” may also be

present along with other, optional additives, all of which may be solid or liquid in nature and

added to the composition to aid char formation and/or to strengthen the char. The carbon

source may be the epoxy resin itself or an additional source such as pentaerythritol. While

this combination of preferred components has proven to produce reliable intumescent

compositions, compositions according to this invention need not possess each every item

identified in this paragraph. In fact, skilled persons may further adjust the additives and/or

provide additional components to further enhance the intumescent protection provided by the

inventive coatings contemplated herein. Collectively, any combination of these components

will be referred to as an intumescent ingredient package.

[0078] Under the influence of heat (between 100°C. and 200°C) the resin components and

the intumescent ingredients begin to melt and flow. As the temperature increases (>200°C.)

the acid source, usually by decomposition, produces copious amounts of acid which can react

with other constituents in the coating. If the acid source is ammonium polyphosphate,

polyphosphoric acids are released which can react with polyhydric alcohols such as

pentaerythritol (carbon source) or the epoxy resin to form polyphosphoric acid esters. The

decomposition of these esters leads to the formation of carbon compounds, which together

with a blowing agent such as melamine, or the ammonium polyphosphate itself, give rise to a

carbon foam or char.

[0079] Ideally, at least one acid source, either sulphonic or phosphoric acid, is provided.

The source of sulphonic or phosphoric can be one or more components(s) that are capable of

producing sulphonic or phosphoric acid upon exposure to heat. By exposure to heat, this

typically means exposure to temperatures of around 100-250° C and higher. Examples of

such sources include potassium, sodium, or ammonium phosphate or sulphate salts e.g.

potassium phosphate (such as potassium tripolyphosphate), para-toluene sulphonic acid,

ammonium polyphosphate (APP) , monoammonium phosphate, diammonium phosphate,

sodium phosphate, ammonium sulphate, potassium sulphate magnesium sulphate and sodium

sulphate. The preferred acid source is ammonium polyphosphate. The acid source preferably

constitutes from 12% to 80% by weight of the intumescent ingredients content of the coating

composition.
[0080] Ammonium polyphosphate can vary in molecular weight (chain length), the lower the

molecular weight, the higher the solubility. By having very high molecular weight and a cross

linked structure it is possible to have very low water solubility, though higher thermal

stability is observed.

[0081] Coating ammonium polyphosphate with silane, melamine or melamine formaldehyde

is beneficial in further reducing solubility and can also lead to higher loadings due to a

reduction in resin absorbing properties. The use of coated ammonium polyphosphate is

preferred, and ammonium polyphosphate coated with melamine formaldehyde is most

preferred.

[0082] The intumescent ingredient may also comprise at least one gas source capable of

releasing nitrogen or inert gas upon exposure to heat. The gas source preferably constitutes

from 0.5% to 50% by weight of the intumescent ingredients content of the coating

composition.

[0083] Common gas sources are amine-functional. Examples of which include ammonium

polyphosphate, azodicarbonamide, p-toluene sulfonylsemicarbazide, 4,4 oxybis (benzene

sulfonyl hydrazide), dinitrosopentamethylenetetramine, p-toluene hydrazide, 5-

phenyltetrazole, diazoaminobenzene, melamine or melamine derivatives, and urea or urea

derivatives.

[0084] Melamine derivatives are well known in the art but are not limited to are salts of

melamine, such as melamine cyanurate, melamine formaldehyde, methylolated melamine,

hexamethoxymethylmelamine, melamine monophosphate, di-melamine phosphate melamine

biphosphate, melamine polyphosphate, melamine pyrophosphate, dimelamine phosphate,

hydroxymethylated melamine, , melamine phosphate melamine monophosphorate, di

(melamine phosphorate) , hexmethoxymethyl melamine, melamine dihydric phosphorate,

melamine borate, hexamethoxymethyl melamine, melem (-2,5,8-triamino 1,3,4,6,7,9,9b-

Heptaazaphenalene) and melon (poly[8-amino-l,3,4,6,7,9,9b-Heptaazaphenalene-2,5-

diyl)imino and melam (l,3,5-triazine-2,4,6-triamine-n-(4,6-diamino-l,3,5-triazine-2-yl).

[0085] Urea derivatives are known in the art and can include N-alkylureas such as methyl

urea, Ν ,Ν '-dialkylureas such as dimethylurea, and Ν ,Ν ,Ν '-trialkylureas such as timethylurea,

guanylurea, guanylurea phosphate, formamide amineo urea, biurea, 1,3-diamino urea

guanylurea phosphate.

[0086] Still other gases sources include but are not limited to are tris-(hydroxyethyl)

isocyanurate (THEIC), Boric Acid, trichloroethyl phosphate (TCEP), trichloropropyl

phosphate (TCPP) or chlorinated paraffins. The resin itself may be a gas source as it

undergoes decomposition. The preferred gas source is melamine.

[0087] Although not an essential ingredient in intumescent reactions, inorganic “nucleating”

agents promote sites for the intumescent char to form, thereby improving the thermal

resistance properties and stability of the intumescent char during a fire. The intumescent

coating compositions of the present invention ideally contain at least one nucleating agent.

The nucleating agent preferably constitutes from 0% to 30% by weight of the intumescent

ingredients content of the coating composition.

[0088] .Examples of nucleating agents include titanium dioxide, zinc oxide, aluminium

oxide, silica, fumed silica silicates such as magnesium silicate, potassium silicate, sodium

silicate, calcium silicate, aluminium silicate, combinations of these five key silicates

particularly; calcium magnesium silicate (talc), and zeolites (interlocking tetrahedra of Si04

and A104, metal oxides such as cerium oxide, lanthanum oxide and zirconium oxide, mica

and bentonite clay. A preferred nucleating agent is titanium dioxide which also provides

opacity to the coating.

[0089] Further additives may be optionally included as part of the intumescent ingredients to

aid char formation and to strengthen the char and prevent char degradation especially in

jetfire scenarios. Such additives include solids such as zinc borate, zinc stannate, Zinc
hydroxystannate, glass flake, glass spheres, polymeric spheres,), pigment dispersants,

stabilisers, mould releasing agents, surface modifiers, flame retardants, antibacterial

agents, hydrophobing agents; antimoulds, low density fillers, endothermic fillers, char

promoters, radiation curing additives; fluxing aids, and levelling agents aluminium

trihydroxide, aluminium hydroxide antimony oxide, boron phosphate, fumed silica.

[0090] Fibres may optionally be added to the intumescent coating composition to strengthen

the char, such fibres can be but not limited to ceramic, mineral, carbon, glass/silica based.

Fibres can added to the coating composition during it's manufacture or be added to the

coating composition just before application.

[0091] Fibre examples are inorganic fibres include carbide fibres, such as silicon carbide

fibres, boron carbide fibres, niobium carbide fibres; nitride fibres, such as silicon nitride

fibres; boron containing fibres, such as boron fibres, boride fibres; silicon-containing fibres,

such as silicon fibres, aluminium silicate fibres alumosilicate fibres alumina-boron-sibca

fibres, , E-glass (non-alkabne alumoborosilicate) fibres, C-glass (non-alkaline or low-alkaline

soda lime-alumoborosilicate) fibres, organic polymer, A-glass (alkaline soda lime-silicate)

fibres, S-glass fibres, CEMFIL-glass fibres, ARG-glass fibres, mineral-glass fibres, non-

alkaline magnesia alumosilicate fibres, quartz fibres, silicic acid fibres, silica fibres, high-

silica fibres, alumina high-silica fibres, alumosilicate fibres, magnesia, soda silicate fibres,

polycarbosilane fibres, polytitanocarbosilane fibres, polysilazane fibres, hydridopolysilazane

fibres, tobermorite fibres, samarium silicate fibres, slagwool fibres, wollastonite fibres,

potassium aluminium silicate fibres. Metal fibres, such as iron fibres, aluminium fibres, steel

fibres, volcanic rock fibres, attapulgite fibres, iron fibres, zinc fibres; carbon fibres, such as

pure carbon fibres, graphite fibres, charcoal fibres. Rockwool fibres, such as pure rockwool

fibres and basalt rockwool fibres, processed mineral fibres from mineral wool, etc .These

fibres can coated or modified by any known process. Blends of fibres may be used.
[0092] In the intumescent coating composition of the present invention the preferred fibres

are mineral fibres such as rockwool. The amount of the reinforced fiber is typically up to 5 wt

% , based on the total weight of the intumescent coating composition, although the amount of

the reinforced fiber in the coating composition of the present invention may be any value less

than 5 wt.%.

[0093] Liquid plasticisers may optionally be added to the intumescent coating composition to

increase flexibility. Suitable plasticisers include, but are not limited to the following:

aromatic alcohols (i.e., benzyl alcohol and phosphate esters such as triaryl phosphate ester,

mono- tbutylphenyl) triphenyl phosphate ester, isopropylated triaryl phosphate ester or

combinations thereof. The plasticiser, when present, is typically present in amounts from 0 to

25 weight % based on the total solid weight of the intumescent coating composition.

[0094] In order to apply intumescent coatings at high film thickness in a single coat, the

rheology modifiers (rheological agents/thixotrope) may be used. Such thixotropic additive(s)

preferably constitute from 0.0% to 2% of the total coating composition. A more preferred

level is from 0.02% to 1%. Suitable rheology modifiers include organically modified

inorganic clays such as bentonite clays, hectorite clays or attapulgite clays, or castor oil and

fumed silica or micronized amide waxes or combinations thereof. The most preferred

thixotropic additives are micronized amide waxes and fumed silicas.

[0095] “High film thickness” will be understood in the context of the field of intumescent

coatings, and the term “film” is not intended to imply a maximum except as disclosed herein.

Maximum thicknesses realized by the compositions described herein depend on a

combination of factors, such as the intended level of protection delivered by the final coating,

the substrate, the composition itself and its ability to cure at the environmental conditions in

which it is used, and other factors. Non-limiting examples of the attainable and useful

maximum thicknesses include: no greater than 50 mm, no great than 40 mm, no greater than

35 mm, no greater than 30 mm, no greater than 28 mm, and no greater than 26 mm. Because
intumescent compositions are designed to deliver a minimal level of fire protection, persons

skilled in this field will appreciate that the minimum thickness of a coatings is more

significant than whatever maximum thickness might be realized, given the extant

circumstances (content of the composition, ambient conditions, etc.)·

[0096] To improve or facilitate dispersion of the intumescent ingredients and also to reduce

the overall viscosity of the intumescent coating, it may be necessary to incorporate wetting/

dispersion additives. Such additives are usually liquid in form and can be supplied either

containing a solvent or be solvent free. Where required preferably a solvent free wetting

agent is used, even more preferably a wetting agent with acid functionality is recommended

at levels between 0% - 2% by weight of the intumescent coating composition.

[0097] The total intumescent ingredients ideally constitute from 20% to 90% of the total

coating composition. More preferably the total intumescent ingredients constitute from 35%

to 80% of the total coating composition.

[0098] When the coating is formulated in two parts, the aforementioned organic and

inorganic additives are split between the Epoxy Resin Component (Part A) and the Amine

Resin Component (Part B) to give the most suitable handling viscosity.

[0099] These intumescent coating components are preferably blended into Part A and Part B

by the coating manufacturer using high speed dispersion equipment, whereby the solid

intumescent ingredients are wetted out and dispersed in the resin components. Optional

dispersion aids may be incorporated to facilitate this process.

[00100] Prior to application of the intumescent coating composition Part A and Part B

are combined in a ratio of typically between 1:4 and 4:1 (by weight) Part A to Part B, more

preferably 1:05 to 1:1.5. This can be carried out along with the application by a number of

processes:
 • High Speed dispersion on a mixer or using for example a plaster mixing paddle

and then trowel apply. The pot life will typically be around 1 - 2 hrs depending on

the temperature of the material and environmental conditions.

• Using a heated plural component airless spray unit for example Graco XM,

WIWA Duomix 333PFP. Part A and Part B are heated to a temperature typically

between 30 to 50° C and then mixed in the fluid line before spray application onto

the substrate. This temperature can vary depending on mixing machines used, film

build of the paint required.

[00101] Advantageously since the intumescent coating compositions of the present

invention are liquid, the coating composition is easy to apply by conventional methods such

as but are not limited to the following: brush, spray coating (airless or conventional spray),

roll coating, pouring, dipping, trowelling, casting and/or painting.

[00102] The intumescent coating compositions of the present invention may also be

formulated with small percentage of solvent or no solvent. The volatile organic content

(VOC) of the coating compositions of the present invention can be less than 250 g/L. The

VOC of the coating composition may be less than 100 g/L. or even less than 50 g/L.

[00103] The intumescent coating compositions of the invention may be applied to any

suitable substrate. Examples include but are not limited to steel and/or concrete construction

units such as beams; hollow beams; cellular beams; columns and hollow columns. This

application may be in a single layer or as part of a multi-layer system. In certain

embodiments, the intumescent may be applied on top of a primer or as the primer layer itself.

The intumescent may form a top coat layer. The intumescent may be applied to a substrate

once or multiple times.

[00104] These intumescent coating compositions may be cured by a heat curing

process. Preferably, the coating composition may be cured at a temperature from about 10 to
50° C . Also, the coating compositions are cured for a period of time from about 18 to 30

hours.

[00105] The foregoing examples provide additional details on various aspects

disclosed above. In comparing the resins embracing aspects of the invention (i.e., resins 1-5

and trials 11-55), individual values for certain ingredients/components in any two specific

resins provide the lower and upper ends of ranges for that ingredient/component. All of these

values should, therefore, be considered part of this disclosure of specific and preferred

embodiments.

EXAMPLE 1

[00106] A series of resin systems were formulated according to the information

provided in Table l a below. Unless otherwise noted, the conditions and procedures for

blending, applying, and curing of these compositions was substantially identical. Testing

methods are set forth below, with certain characteristics for these resin systems set forth in

Table lb.
 Table la: Resin system compositions and characteristics.

Table lb: Resin system characteristics.

[00107] Alphabetical designations (i.e., resins blends A and B) are representative of

conventional resin systems not expected to have sufficient characteristics as a low

temperature and low water adsorption vehicle, while numeric designations (resins 1-5) are

representative of certain aspects of the invention.

[00108] After 5 days immersion resin blends 1-5 all had very low water adsorption

less than 0.85% but in the majority of cases, less than 0.62%. Also, resins 1-5 passed the
“manual bend test”. Thus, these are key metrics in identifying appropriate resin systems for

use in the low temperature intumescent coating.

[00109] In contrast, resin blend B incorporated a highly flexible polyurethane epoxy

with some polyamide curing agent so as to pass the “manual bend test” down to -60°C.

However, this system failed the water adsorption test by an order of magnitude in comparison

to resins blends 1-5.

[00110] The inventors believe this is representative of a synergistic effect in balancing

the flexible components in the system, although the internally flexibilized, acetoacetoxy

polyacetoacetate (AcAc ) functional epoxy polyester block copolymer (which may include an

AcAc functional dimer fatty acid / polyester block copolymer) is believed to cold climate (no

cracking at < - 60° C, as well as the ability to repeatedly cycle down to that temperature

without cracking) and water resistance (< 5.0 wt.% increase upon submersion in water-based

solutions for a period of time), as well as a coating with sufficient hardness. The specific

examples in Tables I B and 2B further inform the precise characteristics and quantitative

measures for the inventive coating.

EXAMPLE 2

[00111] All of the epoxy/amine resin blends from Example 1 were formulated into

intumescent coating compositions and tested for low temperature flexibility down to -50°C

after 14days cure at 23°C. As above, water adsorption was also a significant consideration.

All compositions were formulated as two part compositions, as reported in Table 2a below.

Various characteristics were tested and reported in Table 2b, with the trial indicated as

“COM” being representative of a currently available commercial product.

 Table 2a. Paint Compositions.

TOTAL(g) 100 100 100 100 100 100

 Table 2b. Paint Characteristics.

* water was changed every 7 days, and the initial mould was allowed to setfor 14 days.

[00112] As with the resin systems in Example 1, both low temperature performance

(absolute and number of passing cycles) and water absorption were considered as key

metrics. Paint compositions that could not maintain the metrics set forth above were not

deemed to provide sufficient, sustained low temperature performance.

TESTING METHODS

[00113] The following test methods inform all aspects of this disclosure. Not only are

some of these items pertinent to the examples, but these methods also help to inform the

meaning of any relative or comparative terminology used herein. Also, these methods may

also be applied within the context of certain aspects of the invention, including those that may

be claimed below.

A . Manual bend test

[00114] A fast screening by way of the “manual bend test” was carried out down to -

60°C . The resin blends were made by mixing epoxy and amines resins together and then

pouring the mix in to a silicone moulds sized at 60 x 3 x 12 mm. The strips produced from

this mould were left to cure at 23°C 50% relative humidity for 14 days. After 14 days, all

strips were placed in the Thermotron environmental cabinet and pre-conditioned at 23°C. The
temperature of cabinet was reduced by 10°C per day to -15°C. The first test for bending was

carried out at -15°C each strip was bent with firm pressure to give 90° angle between both

fore fingers and thumbs (using thermal gloves) to test for any bending /movement pass /

failure criteria was as follows:

• Pass: flexed or was rigid (i.e., would not bend) and did not crack into 2 or break or

more pieces.

• Fail: strip cracked or broke into 2 or more pieces.

[00115] Assuming the first test passed, repeated tests were conducted at 5 °C intervals

down to -60°C. If the film snapped into 2 pieces at any stage, the test was recorded as a fail,

while progression to -60°C without failure was recorded as a pass.

[00116] The manual bend test results are reported in Table lb.

B . Shore D Hardness

[00117] For purposes of this disclosure, the Shore D hardness was measured using a

Elcometer 3120 Shore D Durometer, DIN 53 505 or ISO R 868 test methods. However, other

methods and instruments could be used to the extent only a comparative understanding of

hardness was required.

[00118] The Shore D hardness results are reported in Tables l b and 2b.

C. Water Absorption

[00119] Many combinations of flexible epoxy resins and curing agent are known to be

water sensitive, so all epoxy amine resins blends were tested for water adsorption. Generally

speaking, the less water absorbed by a resin system, the more durable it should be.

[00120] Here, resin blends were made by mixing epoxy and amines resins together and

then pouring the mix in to a cube shaped silicone moulds 4.5cm x 2cm x 2cm and left for 24

hours to cure. The cured resin cubes where removed from silicone mould and left to set for an

additional 7 days at 23°C 50% humidity (unless noted differently, as in Table 2b). Each

individual cube was weighted to 4 decimal places before being immersed in deionised water
(Wl), where they were left for 5 days (or time specified). After immersion each cube was

patted dry with an absorbent cloth before weighed again (W2). Then percentage water

absorption is then calculated as follows:

• Percentage Water absorption = (W1-W2/W1) x 100

[00121] The water absorption results are reported in Tables l b and 2b.

I). Thermal Stress-Strain Analysis

[00122] For the sake of context, Figure 2A is a generic representation of stress-strain

data. Curve B illustrates a generalized relationship between increasing stress and strain for

brittle pieces as compared to curve D for ductile pieces. The terminal point at each curve

represents the failure point (graphically illustrated in Figure 2B). The area under the curve is

representative of absorbed energy.

[00123] A goal in this analysis is to identify whether the example epoxy/amine cured

coatings are brittle or ductile at a specific temperature (e.g., -50°C as in Figure 2, although

lower temperatures could be used as a benchmark) using TA Instruments RSAG2 according

to ASTM D638 Type 5 . Dogbones were cut from resin and amine blend cured film

(composition of the present invention), conditioned in RSA 3 furnace at -50°C for 2 minutes

and tested at a Hencky strain rate of 0.01% per second to failure at -50°C.

[00124] Without intending to be bound by any theory, it is speculated that using more

flexible epoxy resins with ductile behaviour allows the energy from the contracting coating to

be absorbed within the system rather than the coating snapping in a brittle manner. Another

mechanism of energy absorption is also demonstrated by a number of the resin systems

withstanding more stress before breakage.

[00125] The stress verses strain results are reported in Figure 3 (although such analysis

of resin 5 was not performed/reported).

E . Thermal Elongation and Toughness

[00126] Elongation and toughness of the epoxy/amine film was tested according to

ASTM D638 Type 5 at -50 °C. The results are reported in Table l b (as elongation (mm/mm

10 2 strain at break) and toughness (Pa 10 +4 -area under stress-strain curve) are averaged over

6 separate samples from each resin type.

[00127] As above, resins blends 1-5 tend to have both higher elongation and toughness

than comparative control resin A at -50°C. Thus, resins 1-5 dissipate energy at a much lower

temperature with some showing greater ductile behaviour. While resin B appears to perform

as well as resins 1-5 in this regard, its lack of water resistance (as noted above) makes it

impractical for low temperature use, especially in on-site conditions where environmental

exposure to water (via humidity and/or precipitation) is likely.

F. Cold Climate Cracking and Cycle Tests

[00128] A target of 20 mm for dry film thickness is used in this test of intumescent

paint compositions. The coating was applied to a mild steel T-section (face =

300x200x12mm, length x width x depth), which had been blasted and primed with a blast

primer. Intumescent paint was hand applied to the primed piece to a final dry film thickness

of 20 mm. The coating left to fully cure for 2 weeks at 23° C at 50% relative humidity. The

dry film thickness measurements recorded across the whole T section. After 2 week each T-

section was placed in the Thermotron (Environmental chamber) at 20° C and allowed to

equilibrate for 24 hours.

[00129] After equilibration, the temperature of the Thermotron was reduced by 10° C

per day in 5°C intervals until -50° C is reached. The sections are studied at each interval. Any

visual cracking observed (even hairline) is deemed a failure at that temperature. The

temperature is then held at -50°C for 3 days, after which the temperature is then increased by

10°C per day at 5° C intervals until 20°C is reached.

[00130] After each cycle of +20° C to -50° C to +20° C ( 1 cycle) , the condition of the

surface of each of the coated T-section was visually checked. The number cycles completed
before any coating cracking and/or releasing from the substrate was observed and reported in

table 2b above. Testing was considered successful after at least five (5) cycles, although

additional, lower temperatures and/or more cycles may have been repeated and reported in

certain instances.

[00131] Separately, these coated work pieces were cycled down to the lowest possible

temperature until a failure was observed. Insofar as -60° C was the initial benchmark

envisioned, cycles proceeded by intervals of only 2.5° C after that benchmark was passed. As

above, any cracking constituted a failure, at which point the lowest previously attained

temperature was recorded and total number of cycles to maximum of 12.

G. Furnace Testins

[00132] As in cold climate cracking and cycle tests, the paint compositions from Table

2a were hand applied in duplicate onto primed steel panels (300 x 200 x 5 mm) at 5-6mm wet

thickness. 400 grams of paint was directly weighed and evenly spread onto each steel panel

across whole surface. All panels were left to cure for 14 days at 23° C at 50% humidity. After

14 days the dry film thickness (DFT) was recorded (measured using an Elcometer 355

Coating Thickness Gauge) across the panel and average taken. This average DFT was then

used to calculate a corrected Time To Failure (TTF) by weight on fire test. For this invention,

two thermocouples were attached to the back of each of the painted steel panels and mounted

vertically so as to allow multiple panels to be tested simultaneously in the same furnace.

[00133] The fire test panels were burnt using- Hydrocarbon BS 476, Parts 20 & 2 1

Hydrocarbon fire test curve. -

[00134] The average thermocouple reading was calculated throughout the test and the

TTF recorded as the time when the average thermocouple temperature reached 500° C . The

results are in Table 2b.

[00135] Table 3 below summarizes the general and preferred weight ranges for the

inventive intumescent coating compositions according to certain aspects of this disclosure.

Any whole integer falling within these ranges is disclosed and contemplated as part of this

disclosure. All weight ranges are with respect to the components for that formulation. In the

case of the resin system, intumescent or other additives could be included as separate

components carried within the system. Also, the intumescent composition could be

formulated as a one or two part coating system, with the information from Table 2A

informing the latter.

 Table 3. Preferred weight percentages for resin system and two-part intumescent coating
compositions.

[00136] Certain terms familiar to the coating industry have been used throughout this

disclosure, and these should be understood accordingly. By reinforcing mesh we mean a

metal, carbon or synthetic mesh or cloth that is incorporated into the coating during

application, although one advantage of this invention is that mesh is not required (i.e., the use

of mesh generally relates to prior art embodiments that are considered inferior). By visual to

the eye we mean even the smallest of highline cracks that can be seen by the eye.

[00137] Generally speaking, chemical components and related constituent items should

also be selected for workability, cost, and weight. Unless specifically noted, all tests and

measurements are conducted in ambient conditions and relying upon commercially available

instruments according to the manufacturer-recommended operating procedures and

conditions. Unless noted to the contrary (explicitly or within the context of a given

disclosure), all measurements are in grams and all percentages are based upon weight

percentages.

[00138] All coatings contemplated herein normally exceed 5 micrometers in thickness.

When applied to a substrate, the dry film thickness of the layer of intumescent coating is

typically between 1 mm (millimeters) and 40 mm. The dry film thickness may be measured

using an Elcometer Dry Film Thickness Gauge.

[00139] To be clear, the stated values herein are merely exemplary of preferred and/or

likely ranges. Any and every combination of values within the individually stated minimum

and maximum limit are encompassed (e.g., if 1 to 10 is disclosed, every combination of

whole integers within the minimum and maximum of those ranges are disclosed, with the

incremental value—single digits (1), tenths (0.1), hundredths (0.01), etc. —corresponding to

the lowest placeholder provided).

[00140] The inventive compositions herein are well suited for coating on steel

substrates, and particularly structural steel beams and other load-bearing components. To the

extent the intumescent agent is incorporated with epoxy or other thermosetting or

thermoplastic resins and curing agents, the inventive formulations can serve as a direct

replacement for previously known, structural coatings.

[00141] For the avoidance of doubt, the features provided in the above description can

be combined in any order. Any appended figures and specific examples described herein are

intended to illustrate the invention but are not to be construed as limiting in any manner the

scope thereof. In the same manner, although the present embodiments have been illustrated in

the accompanying drawings and described in the foregoing detailed description, it is to be

understood that the invention is not to be limited to just the embodiments disclosed, and

numerous rearrangements, modifications and substitutions are also contemplated. The

exemplary embodiment has been described with reference to the preferred embodiments, but

further modifications and alterations encompass the preceding detailed description. These

modifications and alterations also fall within the scope of the appended claims or the

equivalents thereof.
 CLAIMS

What is claimed is:

1. A flexible resin system for epoxy intumescent coating compositions comprising:

at least one epoxy resin and an acetoacetate polyacetatoacetate (AcAc ) functional

polymer combined with an amine functional curing agent to form a cured flexible resin

system that cures within 24 hours with a shore D hardness of at least 2.5;

wherein the AcAc functional polymer includes at least one terminal AcAc unit as

follows:

in which R is -CH 2- and R3 is -CH ; and

wherein the cured flexible resin system: (i) when equilibrated to -60° C, does not

crack after a manual bend test, and (ii) when immersed in water for at least 5 days, gains less

than 7.5 wt.% (relative to a dry weight of the coating prior to being immersed).

2 . The resin system according to claim 1 wherein the cured flexible resin system cures within

24 hours at 23° C with a shore D hardness of at least 5.0 and, when immersed in water for at

least 5 days, gains less than 5.0 wt.% (relative to a dry weight of the coating prior to being

immersed).

3 . The resin system according to claim 1 wherein the AcAc functional polymer is at least

one selected from: an polyester block copolymer, a dimer fatty acid/polyester block

copolymer, and an adduct, modification, or derivative thereof.

4 . The resin system according to claim 1 wherein the at least one epoxy resin is selected

from: bisphenol A diglycidyl ether epoxide resin; bisphenol F diglycidyl ether epoxide resin;

epoxidized polyurethane, oxymethylene bisoxirane resin; epoxidized alkyl phenols,

epoxidized polyglycol diglycidyl ether, bis- and oxirane bisphenol A diglycidyl ether resins;

epoxidized dimer acid; oleic acid; linoleic acid; erucic acid; epoxidized trimer fatty acid;
ethoxylated or propoxylated methacrylate monomers; bisphenol A, F, and A/F epoxy, epoxy

phenolic, novolac resins; epoxy cresol novolac resin; epoxidized castor oil triglycidyl ether;

epoxidized phenyl eneoxy [I -(butoxym ethyl) ethylene, di-functional glycidyl ether; C13,

Cl 5-alkyl glycidyl ether; poly tetramethylene ether glycol; polypropylene glycol copolymers;

and any combination of two or more thereof.

5. The resin system according to claim 1 wherein the amine functional curing agent is

selected from: polyamine, polyamide, polyamidoamine, aliphatic amine, phenalkamine,

polyetheramine modified phenalkamine, dimer-diamine mixtures comprising C36 Dimeric

diamine, C18 amine, and C54 Trimeric amine, cycloaliphatic polyamine,

polyetherpolyamine, alkyletheramine, polyethylenimine, fatty alcohol adducted

polyetheramine, polyetherurethanamine, polyether-urethanepolyamine, polyurethaneamine,

polyetheramine, polyetheramide, polypropyleneamide, polypropyleneamine, polyamide made

by reacting with dimer fatty acids, phenalkamide, polyamidoimidazoline,

polyetherpolyamides, polyaminoamide, any combination of two or thereof, and adducts or

modifications thereof

6. The resin system according to claim 5 further comprising a catalyst selected from:

dipropylenetriamine, benzyldimethylamine, η,η-dimethylpropyl amine,

bis(dimethylaminoethyl)ether, bis-n,n-dimethylethanolaminether, 1,3-propanediamine, 1,3-

bis[3-(dimethylamino)propyl]urea, N'-(3- (dimethylamino)propyl)-N,N-dimethyl, 1,4-

diazabicyclooctane (DABCO), 2-(2-(2-dimethylaminoethoxy)-ethylmethylamino)-ethanol,

l,8-diazabicyclo[5.4.0]undec-7-en (DBU), 1,3-propanediamine, N'-(3-

(dimethylamino)propyl)-N,N-dimethyl l,5-diazabicyclo[4.3.0]non-5-en, 1, 1,3,3-

tetramethylguanidine, N,N,N',N'',N"-pentamethyldiethylentriamine, triphenylphosphine,

trioctylphosphine, nonylphenol, 2-ethyl-4-methylimidazole, 2,6-dimethylpyridine, N,N-bis-

(2-hydroxyethyl)-3-methylaniline, dimethylphenylphosphine, methyldiphenylphosphine,

triphenylphosphite, N,N,N',N",N"-pentamethyl, dimethylaminopyridine,N-(3-

dimethylaminopropyl)-N,N- diisopropanolamine, styrenated phenols,Tris-

(dimethylaminomethyl)phenol, and amino-n-propyldiethanolamine N,N,N',N",N"-

pentamethyl- dipropylenetriamine.

7. The resin system of according to claim 1 wherein the at least one epoxy resin is selected

from: (a) a bisphenol A / epichlorohydrin derived epoxy resin (b) a multifunctional resin

containing both epoxide groups and reactive unsaturation (c) an internally flexibilised

bisphenol A / epichlorohydrin derived epoxy resin (d) a polyacetoacetate epoxy polyester (e)

dimer fatty acid polyester block copolymer (f) polyurethane epoxy resin or (g) a cashew nut

based and Castor Oil triglycidyl ether epoxy resin or can be a combination thereof.

8. The resin system according to claim 1 wherein the epoxy resin or resins account for

between 10.00 and 70.00 wt.% of a total mass of the coating, the amine functional curing

agent or agents account for between 5.00 and 60.00 wt.% of the total mass of the coating, and

the AcAc functional polymer accounts for between 0.50 and 30.00 wt.% of the total mass of

the resin system.

9 . The resin system according to claim 1 further comprising:

an intumescent ingredient package including at least one of: an acid source, a carbon

source, a gas source, and any combination thereof; and

an optional package including any one or combination of a nucleating agent, fibres, a

plasticiser, rheology modifiers, and wetting/dispersion additives.

10. The resin system according to claim 9 wherein the at least one epoxy resin is provided at

10.00 to 70.00 wt.%, the AcAc functional polymer is provided at 0.50 to 30.00 wt.%, the

amine functional coating agent is provided at 5.00 to 60.00 wt.%, and the intumescent

ingredient package and the optional package (if present) are cumulatively provided at least

5.00 wt.% up to a remainder of wt.% and wherein all wt.% are relative to the total mass of the

resin system.
11. The resin system according to claim 1 wherein the cured coating has a thickness of at

least 20 mm.

12. The resin system according to claim 1 wherein the AcAc functional polymer is provided

as part of the epoxy resin so that the epoxy resin includes the at least one terminal AcAc unit.

13. An intumescent coating composition resistant to cracking at -60° C and water absorption,

the composition comprising:

a first part comprising at least one epoxy resin, an acetoacetoxy polyacetoacetate

(AcAc ) functional polymer, and an optional liquid plasticizer;

a second part comprising at least one amine functional curing agent including

polyamide having an H eq.wt. between 90 and 110, and an optional liquid plasticizer;

an intumescent ingredient package including an acid source, an optional a carbon

source, and a gas source; and

wherein the AcAc functional polymer includes a terminal AcAc unit as follows

in which R2 is -CH 2- and R 3 is -CH 3.

14. The intumescent coating composition according to claim 13 wherein the intumescent

ingredient package further comprises at least one of: a nucleating agent, fibres, a plasticiser,

rheology modifiers, wetting/dispersion additives, and any combination thereof.

15. The intumescent coating composition according to claim 13 wherein every chain in the

AcAc functional polymer ends with the terminal AcAc unit.

16. The intumescent coating composition according to claim 13 wherein the AcAc

functional polymer consists of at least 0.50 wt.% relative to a combined mass of the

composition.
17. The intumescent coating composition according to claim 16 wherein the AcAc

functional polymer consists of about 5.00 to about 25.00 wt.% relative to the combined mass

of the composition.

18. The intumescent coating composition according to claim 13 wherein the at least one

amine functional curing agent consist of at least 5.00 wt.% relative to a combined mass of

the composition.

19. The intumescent coating composition according to claim 18 wherein the amine

functional curing agents consist of about 15.00 to about 30.00 wt.% relative to the combined

mass of the composition.

20. The intumescent coating composition according to claim 13 wherein the at least one

epoxy resin consists of at least 10.00 wt.% relative to a combined mass of the composition.

21. The intumescent coating composition according to claim 20 wherein the at least one

epoxy resin consists of about 15.00 to about 25.00 wt.% relative to the combined mass of the

composition.

22. The intumescent coating composition according to claim 13 wherein the at least one

epoxy resin is derived from bisphenol A .

23. The intumescent coating composition according to claim 13 wherein the amine

functional curing agent includes polytetramethylene ether glycol-based polyether amines

having an H eq wt between 500 and 770.

24. The intumescent coating composition according to claim 13 wherein the the AcAc

functional polymer has a structure selected from at least one of:

a)

wherein n is at least 3 .

25. The intumescent coating composition according to claim 13 wherein the the AcAc

functional polymer is
wherein n is any integer from 8 to 68.

26. The intumescent coating composition according to claim 13 wherein the AcAc functional

polymer is integrated with the epoxy resin so that the epoxy resin includes the at least one

terminal AcAc unit.

 INTERNATIONAL SEARCH REPORT
International application No

PCT/US20 19/056233
A . CLASSIFICATION OF SUBJECT MATTER
I NV . C09D5/ 18 C08G59/44 C08G59/50 C09D 163/00
ADD .

According to International Patent Classification (IPC) or to both national classification and IPC

B. FIELDS SEARCHED
Minimum documentation searched (classification system followed by classification symbols)
C09D C08G C09J C09G

Documentation searched other than minimum documentation to the extent that such documents are included in the fields searched

Electronic data base consulted during the international search (name of data base and, where practicable, search terms used)

EPO - I nterna l , WP I Data

 INTERNATIONAL SEARCH REPORT
International application No
Information on patent family members
PCT/US2019/056233
Patent document Publication Patent family Publication
cited in search report date member(s) date

US 5070119 A 03-12-1991 NONE

EP 2475731 A1 18-07-2012 CN 102575138 A 11-07-2012

EP 2475731 A1 18-07-2012
JP 5752126 B2 22-07-2015
JP 2013504653 A 07-02-2013
KR 20120080195 A 16-07-2012
US 2012141803 A1 07-06-2012
WO 2011031429 A1 17-03-2011