Intumescent coating composition

Abstract

The present application relates to an intumescent coating composition comprising: (A) a resin component comprising (a) a compound having at least two alpha, beta-unsaturated carbonyl groups, (b) an organic amine-based compound having at least two N-H bonds, and (B) a compound that provides an expansion gas upon thermal decomposition; wherein the stoichiometric ratio of the N-H groups in the compounds (a) and (b) to the alkenyl groups in the alpha, beta-unsaturated carbonyl groups (-C = C-) is in the range of 0.6 to 1.9. The intumescent coating composition according to the present application enables very short drying time while maintaining good expansion rate, mechanical properties and processability.

Description

Field of the Invention

[0001] The present application relates to a novel intumescent coating composition, a method for coating a substrate with the composition and a substrate obtained thereby. Background Art

[0002] Intumescent coatings are used on many structures to delay the effects of fire. These structures include profiles, cold rolled steel, concrete, wood, aluminum, mixed metals, plastic substrates and batteries, etc. Intumescent coatings usually contain some form of resin binder, such as a high temperature polymer, such as an epoxy resin, and a suitable cross-linking agent.

[0003] However, there is still a need to develop intumescent coatings based on new resin components for fire retardant intumescent coating compositions, and the intumescent coating compositions are required to have faster drying, better mechanical and fire retardant properties. SUMMARY OF THE INVENTION

[0005] These and other objects can be achieved by an intumescent coating composition comprising:

[0006] (A) comprising the following resin components:

[0007] (a) a compound having at least two α,β-unsaturated carbonyl groups, and

[0008] (b) an organic amine compound having at least two NH bonds; and

[0009] (B) a compound that provides an expansion gas upon thermal decomposition;

[0010] The stoichiometric ratio of the NH group to the alkenyl group (-C=C-) in the α,β-unsaturated carbonyl group in the compounds (a) and (b) is in the range of 0.6 to 1.9.

[0011] The present application further relates to a method of coating a substrate, the method comprising applying the intumescent coating composition according to the present application to the substrate.

[0012] Furthermore, the present application also relates to a substrate at least partially coated with a coating deposited from the intumescent coating composition according to the present application.

[0013] Finally, the present application also comprises the use of the composition according to the present application comprising components (A) and (B) as an intumescent coating composition applied to substrates, such as steel substrates, for flame retardancy and fire protection.

[0014] It has been found that the intumescent coating composition according to the present application is able to achieve very short drying time while maintaining good expansion rate, mechanical properties and processability. In particular, compared with common intumescent coatings based on epoxy resins or acrylic resins, the intumescent coating composition according to the present application has a faster drying time, higher expansion, improved flexibility and crack resistance. DETAILED DESCRIPTION OF THE INVENTION

[0016] The intumescent coating composition according to the present application comprises:

[0017] (A) comprising the following resin components:

[0018] (a) a compound having at least two α,β-unsaturated carbonyl groups,

[0019] (b) an organic amine compound having at least two NH bonds; and

[0020] (B) a compound that provides an expansion gas upon thermal decomposition;

[0021] The stoichiometric ratio of the compounds (a) and (b) based on the group -NH- to the alkenyl group (-C=C-) in the α,β-unsaturated carbonyl group is in the range of 0.6 to 1.9.

[0022] The intumescent coating composition according to the present application may be based on the resin component (A), which means that the binder of the coating may be substantially composed of the resin component (A), such as at least 90 wt%, at least 95 wt%, at least 98 wt% or at least 99 wt% or all of the resin component (A), based on the total weight of the binder of the coating. It is known to those skilled in the art that the binder in the coating generally refers to the non-volatile part of the coating used for film formation.

[0023] As used herein, the term "essentially composed of..." means that, based on the total weight of the relevant composition, part or component, the relevant component or composition contains more than 50% (weight percentage), such as at least 60% (weight percentage), at least 70% (weight percentage), or at least 80%, 90%, 95%, 97% or 99% (weight percentage), or even 100% (weight percentage) of the said ingredient or component, respectively, unless otherwise specified.

[0024] The resin component (A) according to the present application is formed by reacting a mixture comprising (a) a compound having at least two α,β-unsaturated carbonyl groups and (b) an organic amine compound having at least two NH bonds, and in some cases optionally (c) a catalyst and other possible additives such as promoters. The reaction between compounds (a) and (b) belongs to the "azaMichael addition" reaction type, through which a film-forming resin or film-forming polymer is formed. It has been found that the stoichiometric ratio of the group -NH- to the alkenyl group (-C=C-) is suitable in the range of 0.6 to 1.9. If the ratio is lower or higher, it may affect the expansion and damage the mechanical and curing properties.

[0025] In the field of chemistry, an α,β-unsaturated carbonyl compound is an unsaturated carbonyl compound in which a double bond (usually a carbon-carbon double bond or an olefinic group) forms a conjugated system with a carbonyl group, including, for example, an α,β-unsaturated aldehyde or ketone or ester. In the embodiment of the present application, the "compound having at least two α,β-unsaturated carbonyl groups" is a compound having at least two, three, four or more α,β-unsaturated carbonyl groups, for example, it can be represented as having two, three, four or more (meth)acryloyl groups ("CH 2 =CH-C(O)-" or "CH 2 =C(CH 3 )-C(O)-”).

[0026] For example, the α,β-unsaturated carbonyl compound according to the present application may be a compound having multiple (meth)acrylate groups as shown in the following structural formula (I):

[0027]

[0028] in

[0029] R is a main chain of an n-valent organic group, which optionally contains one or more moieties selected from ether groups (—O—), ester groups (—C(O)—O—), carbamate groups (—NH—C(O)—O—), or combinations thereof;

[0030] R' represents H or methyl; and

[0031] n represents an integer of 2 or more, such as 3, 4 or 5, and is preferably in the range of 2-10 or 2-6.

[0032] Generally speaking, the ether groups (—O—), ester groups (—C(O)—O—), carbamate groups (—NH—C(O)—O—) or combinations thereof are not included in the main chain in a manner that is connected to each other and is not directly connected to an α,β-unsaturated carbonyl group or a (meth)acrylate group.

[0033] In an exemplary embodiment, the α,β-unsaturated carbonyl compound according to the present invention may have the structure of the following formula (I-1):

[0034]

[0035] in

[0036] R' represents H or methyl,

[0037] R 1 It represents a main chain of a divalent organic group, which optionally contains one or more moieties selected from ether group (—O—), ester group (—C(O)—O—), carbamate group (—NH—C(O)—O—), or a combination thereof.

[0038] In some embodiments, the backbone of the organic group comprises a hydrocarbon group, wherein one or more -CH 2 The - group may be replaced by one or more moieties selected from an ether group (-O-), an ester group (-C(O)-O-), a carbamate group (-NH-C(O)-O-), or a combination thereof.

[0039] Therefore, here, the main chain of the organic group may include, for example, a hydrocarbon chain, including linear, branched or cyclic substituted or unsubstituted aliphatic, alicyclic and aromatic groups or combinations thereof, and may also be a polyurethane main chain, a polyester main chain or a polyether main chain. In the case of a polyurethane main chain, a polyester main chain or a polyether main chain, one or more carbamate groups, ester groups or ether groups may be preferably connected to an α,β-unsaturated carbonyl group or a (meth)acrylate group via an alkylene group (e.g., a linear, branched or cyclic C1-C18, such as a C2-C10 or C2-C8 alkylene group).

[0040] In an advantageous embodiment, the groups R and R 1 represents an n-valent or divalent hydrocarbon group, preferably a linear, branched or cyclic, substituted or unsubstituted aliphatic, alicyclic and aromatic group or a combination thereof, which optionally contains one or more parts selected from ether group (-O-), ester group (-C(O)-O-), carbamate group (-NH-C(O)-O-) or a combination thereof.

[0041] In another embodiment, the groups R and R 1 They represent an n-valent or divalent, linear, branched or cyclic aliphatic group such as an alkyl group, which is optionally substituted or unsubstituted with one or more hydroxyl groups or alkoxy groups, a linear, branched or cyclic aliphatic group such as an alkyl group having one or more ether oxygen atoms, or a combination thereof.

[0042] In some embodiments, the groups R and R 1They respectively represent an n-valent or divalent organic group, such as a C1-C18 group, a C2-C12, C2-C8, C3-C6 straight-chain, branched or cyclic aliphatic group such as an alkyl group, which is optionally substituted by one or more hydroxyl or alkoxy groups or optionally has one or more ether oxygen atoms.

[0043] In other embodiments, the groups R and R 1 Respectively represent an n-valent or divalent group selected from an n-valent or divalent linear, branched or cyclic alkyl group, an aryl group such as a phenyl group or a combination thereof, which is optionally substituted by one or more hydroxyl or alkoxy groups or optionally has one or more ether oxygen atoms.

[0044] In other embodiments, the groups R and R 1 Respectively represent n-valent or divalent polyurethane, polyester or polyether main chains.

[0045] In an advantageous embodiment, the groups R and R 1 The polyether backbone preferably comprises one or more moieties selected from ethyleneoxy, propyleneoxy, butyleneoxy or a combination thereof.

[0046] Accordingly, according to a favorable embodiment of the present invention, the compound having at least two α,β-unsaturated carbonyl groups may include linear, branched or cyclic alkyl esters of (meth)acrylic acid optionally having ether oxygen, epoxy (meth)acrylates optionally having ether oxygen, polyether (meth)acrylates, polyester (meth)acrylates and polyurethane (meth)acrylates, provided that they have at least two (meth)acrylic acid residues.

[0047] As used herein, the term "hydrocarbyl" refers to a group consisting of C, H, which may be substituted or unsubstituted, including aliphatic, alicyclic and aromatic groups and combinations thereof, which may have at least one or two carbon atoms, for example, 1 to 50 carbon atoms, such as 2 to 35, 3 to 28 or 4-18 carbon atoms, and may be straight-chain, branched and cyclic. Aliphatic groups may include alkyl, alkenyl or alkynyl, especially, for example, those with 1 to 18 carbon atoms, such as 2 to 12 or 3 to 8 carbon atoms, preferably alkyl, which may be branched or straight-chain. Alicyclic groups may include cyclic alkyl, alkenyl or alkynyl, especially, for example, those with 3 to 18 carbon atoms, such as 3 to 12 or 4 to 6 or 8 carbon atoms, preferably alkyl. The hydrocarbon radical, in particular an aliphatic or alicyclic radical, may be unsubstituted or substituted by one or more functional groups, such as hydroxyl, alkoxy (alkyl-O-), amino, halogen such as F or Cl or Br or aromatic groups such as phenyl. As for alkenyl and alkynyl, they may contain one or more -C=C- or -C≡C- groups, provided that these unsaturated groups are not directly connected to each other. Aromatic groups, also known as aryl groups, may, for example, have at least 5 or 6, for example 6 to 20 or 6 to 12 carbon atoms, and may optionally be substituted by one or more functional groups, such as epoxy, hydroxyl, alkoxy, amino, halogen such as F, Cl or Br or aliphatic groups such as alkyl such as methyl or ethyl, thus including, for example, phenyl, benzyl, naphthyl, ethylphenyl or biphenyl, etc.

[0048] It is obvious to those skilled in the art that these hydrocarbon groups can form monovalent or polyvalent hydrocarbon groups such as alkyl, n-valent alkyl, alkylene, alkenylene or arylene such as phenylene by losing one or more H atoms.

[0049] As examples of suitable alkyl or cycloalkyl groups there may be mentioned, for example, methane, ethane, propane, cyclopropane, butane, cyclobutane, pentane, cyclopentane, hexane, cyclohexane, heptane, octane, nonane, decane and dodecane groups and the like.

[0050] Accordingly, the "hydrocarbon main chain" described in the present application can be composed of the above-mentioned hydrocarbon groups, including, for example, alkyl, alkenyl, alkynyl, aryl, aryl(cyclo)alkylphenyl, (cyclo)alkylaryl and (cyclo)alkylaryl(cyclo)alkyl, etc.

[0051] "Epoxy (meth) acrylate" as described in the present application refers to those obtainable by reacting an epoxy resin or epoxy compound with (meth) acrylic acid in the presence of an optional catalyst. The product obtained by the reaction may not have an epoxy group. Here, the applicable epoxy resin or epoxy compound may include a compound or polymer derived from a compound containing at least one epoxide functionality (such as glycidol with a cyclic co-reactant, suitably an aromatic co-reactant containing at least two hydroxyl groups (such as bisphenol A)). As used herein, the terms "epoxy" and "epoxide" are used interchangeably. Examples of suitable compounds containing at least one epoxy functionality include, but are not limited to, one or more of the following: glycidol; epoxy soybean oil; epichlorohydrin; glycidylamine or a mixture thereof. Examples of suitable cyclic co-reactants and suitable aromatic co-reactants include, but are not limited to, one or more of the following: bisphenol A; bisphenol F; novolac resins, such as linear phenolic resins and cresol novolac resins or mixtures thereof.

[0052] The epoxy resin may comprise a commercially available epoxy resin material. In certain embodiments, the epoxy resin may comprise a bisphenol diglycidyl ether epoxy resin, such as bisphenol A diglycidyl ether and / or bisphenol F diglycidyl ether epoxy resin. In another embodiment, the epoxy resin may comprise an epoxy novolac resin and / or an epoxy cresol novolac resin. In yet another embodiment, the epoxy resin may comprise one or more of the following: bisphenol A diglycidyl ether epoxy resin; epoxidized soybean oil; bisphenol F diglycidyl ether epoxy resin; epoxy novolac resin; epoxy cresol novolac resin or a mixture thereof.

[0053] In this context, "polyurethane" as a possible main chain basis in the definition of groups R and R1 may include all polymers prepared by the so-called diisocyanate polyaddition process, which is usually obtained by reacting polyisocyanates and polyols. The α,β-unsaturated carbonyl compounds based on the main chain of the polyurethane group according to the invention are known in the prior art or can be prepared according to methods known in the prior art. For example, polyols and polyisocyanates can first be reacted to obtain a polyurethane prepolymer with an isocyanate group at the end, and then modified with an acrylate containing terminal hydroxyl groups.

[0054] Suitable polyols for preparing the polyurethane polymers may be polyether polyols, and also polyester polyols such as the polycondensation products of diols or triols with lactones or dicarboxylic acids or their esters or anhydrides, and also polycarbonate polyols, block copolymer polyols having blocks of at least two different polyether, polyester or polycarbonate units, polyacrylate and polymethacrylate polyols, polyhydroxy-functional fats and oils, in particular natural fats and oils, and polyhydrocarbon polyols, such as polyhydroxy-functional polyolefins.

[0055] In addition to the abovementioned polyols, it is also possible to use small amounts of low molecular weight or monomeric divalent or polyvalent alcohols, such as 1,2-ethanediol, 1,2-propylene glycol, neopentyl glycol, dibromoneopentyl glycol, diethylene glycol, triethylene glycol, the isomeric dipropylene glycols and tripropylene glycols, the isomeric butanediols, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, undecanediol, 1,3- and 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, dimeric fatty alcohols, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, glycerol, pentaerythritol, sugar alcohols such as xylitol, sorbitol or mannitol, sugars such as sucrose, further polyols, low molecular weight alkoxylation products of the abovementioned divalent or polyvalent alcohols, and mixtures of the abovementioned alcohols.

[0056] Preferred polyols are polyether polyols (especially polyoxyalkylene polyols), polyester polyols and polycarbonate polyols.

[0057] Polyoxyalkylene polyols are polymerization products of ethylene oxide, 1,2-propylene oxide, 1,2- or 2,3-butylene oxide, oxetanes, tetrahydrofuran or mixtures thereof, optionally polymerized using starter molecules having two or more active hydrogen atoms, such as water, ammonia or compounds having several OH- or NH-groups, such as 1,2-ethanediol, 1,2- and 1,3-propylene glycol, neopentyl glycol, diethylene glycol, triethylene glycol, the isomeric dipropylene glycols and tripropylene glycols, the isomeric butanediols, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, undecanediol, 1,3- and 1,4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, glycerol, aniline, and mixtures of the aforementioned compounds.

[0058] In an advantageous embodiment, the polyether polyol or polyoxyalkylene polyol is a polymerization product of ethylene oxide and / or propylene oxide.

[0059] Also advantageous are polyoxypropylene polyols and so-called ethylene oxide-terminated polyoxypropylene polyols. The latter are specific polyoxypropylene-polyoxyethylene polyols which are obtainable by postethoxylation of pure polyoxypropylene polyols and which therefore have primary hydroxyl groups.

[0060] In a further advantageous embodiment, the polyol is a polycarbonate polyol, in particular a polycondensation product of a dialkyl carbonate, a diaryl carbonate or phosgene with a diol or triol.

[0061] Suitable polyisocyanates for obtaining polyurethane polymers are as follows:

[0062] - aliphatic polyisocyanates, in particular 1,4-tetramethylene diisocyanate, 2-methylpentamethylene-1,5-diisocyanate, 1,6-hexane diisocyanate (HDI), 2,2,4- and 2,4,4-trimethyl-1,6-hexane diisocyanate (TMDI), 1,10-decane diisocyanate, 1,12-dodecane diisocyanate, lysine or lysine ester diisocyanates, cyclohexane-1,3- and -1,4-diisocyanate, 1-methyl-2,4- and -2,6-diisocyanatocyclohexane and any mixtures of these isomers (HTDI or H6TDI), 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (isophorone diisocyanate or IPDI), perhydro-2,4'- and -4,4'-diphenylmethane diisocyanate (HMDI or H12MDI), 1,4-diisocyanato-2,2,6-trimethylcyclohexane (TMCDI), 1,3- and 1,4-bis(isocyanatomethyl)cyclohexane, m- and p-xylylene diisocyanate (m- and p-XDI), m- and p-tetramethyl-1,3 and -1,4-xylylene diisocyanate (m- and p-TMXDI), bis(1-isocyanato-1-methylethyl)naphthalene, dimer or trimer fatty acid isocyanates such as 3,6-bis-(9-isocyanatononyl)-4,5-di-(1-heptenyl)cyclohexene (dimer diisocyanate), and α,α,α',α',α",α"-hexamethyl-1,3,5-trimethylbenzene triisocyanate. Preferably, it is HDI, TMDI, IPDI and H12MDI.

[0063] Aromatic polyisocyanates, in particular 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate and / or 2,2'-diphenylmethane diisocyanate and any mixtures of these isomers (MDI), 2,4- and / or 2,6-toluene diisocyanate and any mixtures of these isomers (TDI), 1,3- and 1,4-phenylene diisocyanate, 2,3,5,6-tetramethyl-1,4-diisocyanatobenzene, naphthalene-1,5-diisocyanate (NDI), 3,3'-dimethyl-4,4'-diisocyanatobiphenyl (TODI), dianisidine diisocyanate (DADI), 1,3,5-tris(isocyanatomethyl)benzene, tris(4-isocyanatophenyl)methane and tris(4-isocyanatophenyl)phosphorothioate. Preferred are MDI and TDI.

[0064] As a preferred embodiment, the α,β-unsaturated carbonyl compound having a polyurethane main chain may be aliphatic polyurethane acrylate.

[0065] As the groups R and R 1The "polyester" as a possible backbone basis in the definition may be derived from the polycondensation reaction of polycarboxylic acids with polyols (e.g. aromatic, aliphatic or alicyclic polyacids or alcohols, such as those mentioned above). In this case, the α,β-unsaturated carbonyl compound according to the invention may have a polyester backbone and at least two (meth)acrylate groups at the ends.

[0066] Such polyester acrylates can be prepared in a variety of ways, for example, by esterifying low molecular weight polyester diol with (meth) acrylic acid. In addition, they can also be prepared by, for example, one-step esterification of (meth) acrylic acid, dibasic acid and diol; or, first condensation of dibasic acid and diol to obtain polyester diol and then esterification with (meth) acrylic acid; or, dibasic acid and ethylene oxide are added and then esterified with acrylic acid, etc.

[0067] The α,β-unsaturated carbonyl compound based on the "polyether" main chain can be structurally regarded as a polyether polyol in which at least two hydroxyl groups are blocked by (meth)acrylate groups. Examples of the polyether polyol include those described above in the context of polyurethane synthesis.

[0068] The α,β-unsaturated carbonyl compound according to the present application can be synthesized by a skilled person according to chemical practice or can be commercially obtained, for example, from the market.

[0069] According to the present application, examples of the compound having at least two α,β-unsaturated carbonyl groups include ethylene glycol di(meth)acrylate, glycerol tri(meth)acrylate, butanediol di(meth)acrylate, pentanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, hexanediol di(meth)acrylate, heptanediol di(meth)acrylate, octanediol di(meth)acrylate, nonanediol di(meth)acrylate, decanediol di(meth)acrylate, dodecanediol di(meth)acrylate, cyclohexanedimethanol diacrylate, propoxylated neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate. Acrylate, di(trimethylolpropane) tetra(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propoxylated glycerol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, bisphenol A-di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, trihydroxypropyl methacrylate. In addition, polyester multi(meth)acrylates such as polyester hexa(meth)acrylate, polyurethane multi(meth)acrylates such as polyurethane di(meth)acrylate, epoxy soybean oil multi(meth)acrylate, etc. are also included.

[0070] Preferred examples of compounds having at least two α,β-unsaturated carbonyl groups according to the present application include hexanediol di(meth)acrylate (such as 1,6-hexanediol diacrylate, available from Allnex), trimethylolpropane triacrylate, di(trimethylolpropane) tetraacrylate (both available from Allnex), polyester hexaacrylate (for example, available from Arkema Group), aliphatic polyurethane acrylate (for example, available from Allnex) and epoxidized soybean oil tetraacrylate (for example, available from Allnex).

[0071] In the present application, an organic amine compound having at least two H groups (ie, NH) connected to N may also be referred to as a "polyamine compound", which can undergo a condensation reaction with a compound having at least two α, β-unsaturated carbonyl groups to obtain a resin component.

[0072] The organic amine compound according to the present application includes polyamide, polyetheramine, phenolic amine and multifunctional amine monomer or a combination thereof, which has at least two NH groups. Preferably, it may have at least 3, 4, 5, 6, 7 or 10 NH groups. The NH group may include one or more primary amine groups (-NH 2 ) or secondary amine group (-NH-).

[0073] Suitable polyamides may be prepared by any suitable method. Such polyamides may include homopolymers or copolymers derived from a combination of a polyamine and a dicarboxylic acid. Examples of suitable polyamines include, but are not limited to, one or more of the following: hexamethylenediamine; ethylenediamine; diethylenetriamine; triethylenetetramine; tetraethylenepentamine; 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: adipic acid; sebacic acid or mixtures thereof. Dicarboxylic acids may also be used in the form of cyclic anhydrides of the dicarboxylic acids, examples of which include maleic anhydride; sulfonic anhydride; phthalic anhydride or mixtures thereof. Dicarboxylic acids may also be used in the form of diester materials, such as diethyl malonate; dimethyl malonate or mixtures thereof.

[0074] Suitably, the dicarboxylic acid is in the form of a dimer fatty acid. Examples of suitable dimer fatty acids include, but are not limited to, one or more of the following: a dimer of stearic acid; a dimer of palmitic acid; a dimer of lauric acid or a combination / mixture thereof.

[0075] In certain embodiments, the polyamide may be a polyamide imidazoline. Suitable polyamide imidazolines may be prepared by any suitable method. For example, such polyamide imidazolines may include homopolymers or copolymers derived from a combination of a polyamine and a dicarboxylic acid. 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 dicarboxylic acids include, but are not limited to: dimer fatty acids; adipic acid and combinations thereof.

[0076] The polyamide may include commercially available polyamide materials. In certain embodiments, examples of suitable commercially available polyamide materials include, but are not limited to, one or more of the following: Versamid 115, 125, 140, and 150 commercially available from BASF; Aradur 115 and 125 commercially available from Huntsman; Aradur 140 (polyamide imidazoline) commercially available from Huntsman; Aradur 955, 9130, 9140, and 3376 commercially available from Huntsman; and Domide G-650 obtained from Kukdo Chemical.

[0077] Suitably, the polyamide material comprises polyamide imidazoline. Suitably, the polyamide material comprises Versamid 125, Versamid 140, Versamid 150 and / or Aradur 140. Most suitably, Versamid 140 and / or Aradur 140.

[0078] The polyamide may have any suitable weight average molecular weight (Mw).In certain embodiments, the polyamide may have a Mw of about 100 to 5000 Daltons (Da=g / mol) (suitably about 100 to 2000 Da, or even about 100 to 1000 Da).

[0079] The polyamide may have any suitable number average molecular weight (Mn). In certain embodiments, the polyamide may have an Mn of about 100 to 3000 Daltons (Da = g / mol) (suitably about 100 to 2000 Da, or even about 100 to 1000 Da).

[0080] In the present application, weight average molecular weight can be measured by any suitable method. Those skilled in the art are familiar with the technology of measuring weight average molecular weight. Suitably, Mw values ​​and ranges given herein can be determined by gel permeation chromatography using polystyrene standards according to ASTM D6579-11 ("Standard Practice for Molecular Weight Averages and Molecular Weight Distribution of Hydrocarbon, Rosin and Terpene Resins by Size Exclusion Chromatography". UV detector: 254nm, solvent: non-stable THF, residence time marker: toluene, sample concentration: 2mg / ml).

[0081] It will be apparent to those skilled in the art that the method used to measure weight average molecular weight can also be used to measure number average molecular weight.

[0082] The polyamide may have any suitable glass transition temperature (Tg).In certain embodiments, the polyamide may have a Tg of about -50 to 50°C (suitably about -30 to 30°C, or even about -20 to 20°C).

[0083] The Tg of a compound such as a polyamide may be measured in the present application by any suitable method. Those skilled in the art are familiar with methods for measuring Tg. Suitably, Tg is measured according to ASTM D6604-00 (2013) ("Standard Practice for Glass Transition Temperatures of Hydrocarbon Resins by Differential Scanning Calorimetry". Heat flux differential scanning calorimetry (DSC), sample pan: aluminum, reference: blank, calibration: indium and mercury, sample weight: 10 mg, heating rate: 20 ° C / min).

[0084] The organic amine compounds used to form the resin component of the present application may also include suitable polyetheramines. Suitable polyetheramines can be prepared by any suitable method. Suitably, the polyetheramines include suitable compounds based on a polyether backbone containing epoxide functionality, the epoxide functionality including but not limited to one or more of the following: propylene oxide (PO), ethylene oxide (EO) or a mixture thereof. Suitably, the polyether backbone is selected from polypropylene glycol and / or polyethylene glycol. The terminal hydroxyl groups of the polyether backbone are suitably aminated to form the corresponding polyetheramine.

[0085] The polyetheramine may include commercially available polyetheramine materials. In certain embodiments, examples of commercially available polyetheramine materials include, but are not limited to, one or more of the following: Jeffamine series commercially available from Huntsman, such as Jeffamine T-403.

[0086] The polyetheramine may have any suitable weight average molecular weight (Mw). In certain embodiments, the polyetheramine of the curing agent may have a Mw of about 200 to 7000 Daltons (Da=g / mol) (suitably about 200 to 2500 Da, or even about 200 to 500 Da).

[0087] The polyetheramine may have any suitable number average molecular weight (Mn). In certain embodiments, the polyetheramine may have an Mn of about 200 to 5000 Daltons (Da=g / mol) (suitably about 200 to 2500 Da, or even about 200 to 500 Da).

[0088] The polyetheramine may have any suitable glass transition temperature (Tg).In certain embodiments, the polyetheramine may have a Tg of about -50 to 50°C (suitably about -40 to 30°C, or even about -40 to 20°C).

[0089] Phenolic amines are also suitable organic amine compounds.

[0090] Phenolic amines generally refer to reaction products formed by Mannich condensation reaction of phenol, aldehyde and polyamine. It is generally used as a curing agent. The phenolic amine compound obtained by Mannich reaction may contain phenolic hydroxyl group and one or more primary amine groups (-NH 2 ) and secondary amine groups (-NH-).

[0091] Phenols used to synthesize phenalkamines include, for example, phenol, cardanol, etc. Aldehydes used to synthesize phenalkamines may be formaldehyde or paraformaldehyde, etc. Amines used to synthesize phenalkamines, particularly polyamines include aliphatic amines such as ethylenediamine, hexamethylenediamine, diethylenetriamine, etc., polyetheramines, aromatic amines, alicyclic amines, etc.

[0092] The phenalkamine suitable for the present invention is commercially available or can be synthesized by a skilled person using the knowledge known in the art, such as Cardolite NC541.

[0093] In addition, the amine compound may also include any other suitable multifunctional amine monomers. Suitably, the multifunctional amine monomers include monoamine or polyamine monomers.

[0094] Specifically, a monoamine refers to an amine having one primary amine group (-NH 2 The primary amino group is connected to a hydrocarbon group (such as an aliphatic, alicyclic, aromatic or a combination thereof) or a heteroaryl group.

[0095] In particular, in the case where the multifunctional amine monomer is a polyamine, two or more amino groups (such as primary and secondary amino groups) are connected by a divalent or more valent hydrocarbon group (such as aliphatic, alicyclic, aromatic or a combination thereof) or a heteroaryl group. In this article, the heteroaryl group is well known to technicians and comes from heteroaromatic hydrocarbons or heterocyclic compounds. They have a cyclic structure, and the ring atoms have other hetero elements such as O, S, N, etc. in addition to carbon atoms.

[0096] Suitable examples of multifunctional amine monomers include monoamines or polyamines based on aliphatic, cycloaliphatic, aromatic or heteroaromatic or combinations thereof, such as ethylamine, propylamine, butylamine, cyclohexylamine, aniline, o-, m-, p-toluidine or ethylaniline, isophoronediamine; m-xylylenediamine; diethylenetriamine (DETA); triethylenetetramine (TETA); tetraethylenepentamine (TEPA); N,N'-bis(3-aminopropyl)-1,3-propylenediamine; bis(3-aminopropyl)amine; N,N'-bis(2-aminoethyl)-1,3-propylenediamine; 1,2-bis(3-aminopropylamino)ethane; piperazine; 1,4-bis(3-aminopropyl)piperazine; polyethyleneimine; tris(2-aminoethyl)amine; N,N,N',N'-tetrakis(3-aminopropyl)-1,4-butanediamine; and combinations thereof.

[0097] In an advantageous embodiment of the present invention, the organic amine compound comprises phenalkamine. This may further lead to a shortened drying time.

[0098] In the intumescent coating composition of the present application, the content of the compound having at least α,β-unsaturated carbonyl group as component (a) may be in the range of 4-60 wt%, such as 5-40 wt% or 30 wt%, such as 6-25 or 7-15 wt%, based on the total weight of the coating composition. The content of the organic amine compound having at least two NH bonds as component (b) may be in the range of 3-50 wt%, such as 4-40 wt% or 25 wt%, such as 5-20 or 7-18 wt%, based on the total weight of the coating composition.

[0099] It is important for the realization of the intumescent coating of the present invention that the stoichiometric ratio of the compounds (a) and (b) in the resin component of the present application, calculated as NH groups to alkenyl groups (-C=C-) in the α,β-unsaturated carbonyl group, is in the range of 0.6 to 1.9, for example 0.7 to 1.8, 0.8 to 1.7 or 0.9 to 1.6. It has been found that if this stoichiometric ratio range is exceeded, i.e. too low or higher stoichiometric ratio is adopted, it may lead to lower expansion rate and poorer mechanical properties of the coating composition, especially hardness such as Shore D hardness. A person skilled in the art of chemistry knows how to calculate the stoichiometric ratio of the reactants in the reaction. Here, the stoichiometric ratio in the reaction of the compounds (a) and (b) is calculated based on the molar content of the groups -NH- and alkenyl groups (-C=C-) contained in each. For example, in the case of primary amino groups, 2 NH groups are counted.

[0100] In the intumescent coating composition according to the present invention, a catalyst may be used as needed to promote the aza-Michael addition reaction of the compounds (a) and (b) in the resin component. Suitable catalysts for the reaction include organic base catalysts such as 1,5-diazabicyclo[4.3.0]-5-nonene (DBN), 1,1,3,3-tetramethylguanidine (TMG), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), triethylenediamine (DABCO) and tertiary amine catalysts, etc.; and organic tin catalysts such as dibutyltin dilaurate, and titanate catalysts such as tetrabutyl titanate, etc.

[0101] In embodiments according to the present invention, the catalyst, if used, may be used in an amount of 0.1-5 wt%, such as 0.2-3 wt% or 0.3-2.2 wt%, based on the total weight of the intumescent coating composition.

[0102] The intumescent coating composition according to the present application requires, in addition to the resin component (A), a compound that provides an intumescent gas upon thermal decomposition as component (B).

[0103] When exposed to a high temperature flame, the intumescent gas serves to foam and expand the fireproof intumescent composition. As a result of this expansion, the char formed is a thick, porous material that serves to insulate and protect the underlying substrate. The source of intumescent gas that can be used in the intumescent coating composition of the present application is a nitrogen-containing material. Examples of suitable nitrogen-containing materials include melamine, salts of phosphoric acid, guanidine, hydroxymethylated melamine, hexamethoxymethylmelamine, urea, dimethylurea, melamine pyrophosphate, dicyandiamide, guanyl urea phosphate and glycine. Suitably, melamine is used. Other conventional sources of intumescent gas may also be used, such as those that release carbon dioxide. Examples are alkaline earth metals, such as calcium carbonate or magnesium carbonate. Compounds that release water vapor when decomposed when heated, such as calcium hydroxide, magnesium dihydroxide or aluminum trihydroxide, may also be used. Other examples of such compounds are boric acid and boric acid derivatives.

[0104] In the intumescent coating composition of the present application, a suitable amount of component (B) may be in the range of 0.1 to 25 wt%, suitably in the range of 1 to 10 wt%, wherein the weight percentages are based on the total solid weight of the composition.

[0105] The intumescent coating composition of the present application may contain optional additives (C) selected from phosphorus sources, boron sources, zinc sources, acid sources, carbon sources, inorganic fillers, mineral fibers, such as CHOPVANTAGE from PPG, Coatforce or Roxul fibers from Lapinus, rheological additives, organic solvents, pigments, foam stabilizers, flame spread control agents, etc. and combinations thereof. These ingredients are optional and may be added in varying amounts.

[0106] The source of phosphorus may be selected from a variety of materials, such as phosphoric acid, monoammonium and diammonium phosphate, tris(2-chloroethyl) phosphate, phosphorus-containing amides such as phosphoryl amide and melamine pyrophosphate. Suitably, the source of phosphorus is of the formula (NH 4 ) n+2 P n O 3n+1 The ammonium polyphosphate represented by wherein n is an integer of at least 2, suitably n is an integer of at least 50. The present application may comprise phosphorus in an amount of 0 to 20 wt %, suitably 0.5 to 10 wt %, based on the total solid weight of the coating composition. It is believed that phosphorus acts as a char promoter in the intumescent composition.

[0107] The optional source of zinc can be selected from a variety of materials. It is believed that zinc materials contribute to the formation of a small pore structure in the char. The small pores of the char provide better thermal insulation of the substrate and are able to better retain the integrity of the char and adhere to the substrate, even in the absence of external reinforcement materials. Therefore, cracking of the char and its breakage from the substrate are minimized, and a greater measure of protection is provided for the underlying steel. Examples of suitable materials as zinc sources include zinc oxide, zinc salts, such as zinc borate and zinc phosphate, zinc carbonate, and zinc metal can also be used. Suitably, zinc borate is used. The intumescent coating composition of the present application may contain 0 to 25% by weight, suitably 0.5 to 12% by weight of zinc, based on the total solid weight of the composition.

[0108] The source of boron may be selected from ammonium pentaborate or zinc borate, boron oxide, borate salts such as sodium borate, potassium borate and ammonium borate, borate esters such as butyl borate or phenyl borate and combinations thereof. The intumescent coating composition of the present application may comprise boron in an amount of 0 to 10 wt %, suitably 1 to 6 wt %, wherein the weight percentage is based on the total solid weight of the composition.

[0109] The acid source may be selected from ammonium phosphate, ammonium polyphosphate, diammonium diphosphate, diammonium pentaborate, phosphoric acid generating materials, boric acid, metal or organic borates, and combinations thereof.

[0110] The carbon source may generally be selected from polyols such as pentaerythritol, dipentaerythritol, glycerol, oligoglycerols, xylitol, mannitol, sorbitol and polymers such as polyamides, polycarbonates, polyurethanes and combinations thereof.

[0111] It will be appreciated that phosphorus, zinc, boron and expansion gas may each be provided by separate source materials, or alternatively a single material may be a source of more than one of the additional components listed above. For example, melamine pyrophosphate may provide a source of both phosphorus and expansion gas.

[0112] Optional reinforcing fillers may be selected from a wide variety of conventionally used materials, including fiber reinforcements and sheet reinforcements, which are more suitable than other fillers. Examples of fiber reinforcements include glass fibers, ceramic fibers, such as alumina / silicon oxide and graphite fibers. Sheet reinforcements include hammer mill glass flakes, mica and wollastonite. Other suitable fillers include metal oxides, titanium oxide, clay, talc, silica, diatomaceous earth, Fibers and various pigments. It is believed that reinforcing fillers help control the expansion of the fire retardant composition before and during char formation, thereby making the resulting char strong and uniform. When present, reinforcing fillers are typically present in the composition in an amount of 1 to 50 weight percent, based on the total solids weight of the intumescent coating composition.

[0113] The intumescent coating composition may be configured as a two-pack or more pack system, wherein the (a) component and possibly other components in the resin component (A) are in a first pack (I), and the (b) component is placed in a second pack (B), wherein the compound providing an intumescent gas upon thermal decomposition and any additives (if present) are contained in any combination in pack (I) or pack (II), or in both, or in one or more other packs (III). The individual packs are mixed before using the intumescent coating composition.

[0114] In an advantageous embodiment, the first package (I) may contain (a) the α,β-unsaturated carbonyl compound and those compounds that provide expansion gas when thermally decomposed, and the second package (B) may contain (b) the organic amine compound and an optional catalyst component. Optional other additives such as plasticizers or fibers may be included in the first package (I), for example.

[0115] When the intumescent composition of the present application is prepared, it can be in the form of a thick material such as a muddy paste. Solvent-free and spray-coated compositions are particularly suitable. In the present application, the "solvent-free" or "solvent-free coating" refers to the coating containing no more than 1% by weight, preferably no more than 0.5% by weight, more preferably no more than 0.1% by weight, and especially no more than 0.05% by weight of organic solvents or no organic solvents at all, based on the total coating composition.

[0116] The intumescent curable composition of the present application can be applied to a variety of substrates, especially steel substrates, and will not crack when subjected to extreme temperature changes in a short period of time. The intumescent coating composition of the present application has good flexibility and is particularly suitable for protecting steel structures from cellulose fire and hydrocarbon fire.

[0117] The following examples are intended to illustrate the present application but are not intended to be limiting. Example:

[0118] The present application is further described below based on examples. It should be understood that the following examples are illustrative rather than limiting.

[0119] Ingredients

[0120]

[0121] Preparation of the composition

[0122] According to the composition shown in Table 1 below, each composition was prepared according to the following procedure: different α,β-unsaturated carbonyl compounds and plasticizers were placed in a solvent xylene and mixed evenly, and Disperbyk-103, Thixatrol ST and flame retardant components were added to the obtained mixture in sequence after low-speed stirring for 5 minutes. Then, the temperature of the mixed material was higher than 45°C under high-speed stirring, and the discharged material was part (I).

[0123] Different polyamine compounds and catalysts are added into a solvent xylene and stirred gently to mix evenly, which is part (II).

[0124] Then mix the two parts in a certain proportion and stir evenly. Apply the mixture to the steel plate and wait for it to dry. Record the drying time of the test sample according to the measurement method described in the "Test Method". Then test the expansion rate of the sample steel plate according to the measurement method described in the "Test Method".

[0125] Test Method

[0126] The "drying time" is measured as follows: the obtained intumescent coating composition is applied to a steel plate of 75*150*3 mm, and the steel plate is placed under conditions of 23°C and 50% relative humidity. The dry film thickness is between 1500 and 1800 μm. During the drying process, the film surface is touched with a finger. If it is not sticky, it means that the surface is dry. Press the film hard and rotate it 90°. If there is no mark, it is hard dry. The time from the completion of coating to hard dry is recorded as the "drying time".

[0127] The "intumescence" is measured as follows: The obtained intumescent coating composition is applied to a steel plate of 75*150*3 mm. The dry film thickness is between 1500 and 1800 microns. The coating on the steel plate is cured for 7 days and then subjected to a fire test. The dry film thickness of the intumescent layer is measured where the flame will burn the plate. The measurement is performed at least five times.

[0128] Place the steel panel on the insulation and place the blowtorch in the middle of the panel. Light the blowtorch and heat the steel panel coated with the intumescent paint for 3 minutes. After cooling, measure the thickness of the char layer with a ruler in the area where the flame hits the steel panel.

[0129] Expansion rate = dry film thickness of carbon layer after test (mm) / dry film thickness of coating before test (mm)

[0130] The "Shore D hardness" is measured as follows: The obtained intumescent coating composition is applied to a 75*150*3 mm steel plate and the steel plate is placed under conditions of 23° C. and 50% relative humidity. The dry film thickness is between 1500 and 1800 μm.

[0131] Place the test steel plate on the base of the Shore D hardness tester. Insert the pointer of the tester into the test material, with the base of the tester close to the test material. Read the scale value after 1 second. Evaluate the entire test panel five times and calculate the average value.

[0132]

[0133]

Claims

1. An intumescent coating composition comprising: (A) comprising the following resin components: (a) a compound having at least two α,β-unsaturated carbonyl groups, preferably (meth)acryloyl groups, (b) an organic amine compound having at least two NH bonds, and (B) a compound that provides an expansion gas upon thermal decomposition; The stoichiometric ratio of the NH group to the alkenyl group (-C=C-) in the α,β-unsaturated carbonyl group in the compounds (a) and (b) is in the range of 0.6 to 1.

9.

2. An intumescent coating composition according to claim 1, Features The compound having at least two α,β-unsaturated carbonyl groups is a compound having a (meth)acrylate group as shown in the following structural formula (I): in R is a main chain of an n-valent organic group, which optionally contains one or more moieties selected from ether groups, ester groups (-C(O)-O-), carbamate groups (-NH-C(O)-O-), or combinations thereof; R' represents H or methyl; and n represents an integer of 2 or more, such as 3, 4 or 5, and is preferably in the range of 2-10 or 2-6.

3. An intumescent coating composition according to claim 2, Features The organic group includes a hydrocarbon group, wherein one or more -CH 2 - may be replaced by one or more moieties selected from an ether group, an ester group (-C(O)-O-), a carbamate group (-NH-C(O)-O-), or a combination thereof.

4. An intumescent coating composition according to claim 2 or 3, Features The backbone is selected from (i) linear, branched or cyclic substituted or unsubstituted aliphatic, alicyclic and aromatic groups, (ii) a polyurethane backbone, (iii) a polyester backbone or (iv) a polyether backbone.

5. An intumescent coating composition according to claim 2, 3 or 4, Features The n-valent organic group is selected from n-valent linear, branched or cyclic alkyl groups, aryl groups such as phenyl groups or combinations thereof, which are optionally substituted with one or more hydroxyl groups or alkoxy groups or optionally have one or more ether oxygen atoms.

6. An intumescent coating composition according to claim 2, 3, 4 or 5, Features The n-valent organic group includes a C1-C18 group representing an n-valent group, such as a C2-C12 or C2-C8 straight-chain, branched or cyclic alkyl group.

7. An intumescent coating composition according to any one of the preceding claims, Features The compounds having at least two α,β-unsaturated carbonyl groups include linear, branched or cyclic alkyl esters of (meth)acrylic acid optionally having ether oxygen, epoxy (meth)acrylates optionally having ether oxygen, polyether (meth)acrylates, polyester (meth)acrylates and polyurethane (meth)acrylates, provided that they have at least two (meth)acrylic acid residues.

8. An intumescent coating composition according to any one of the preceding claims, Features The compound having at least two α,β-unsaturated carbonyl groups includes ethylene glycol di(meth)acrylate, glycerol tri(meth)acrylate, butanediol di(meth)acrylate, pentanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, hexanediol di(meth)acrylate, heptanediol di(meth)acrylate, octanediol di(meth)acrylate, nonanediol di(meth)acrylate, decanediol di(meth)acrylate, dodecanediol di(meth)acrylate, cyclohexanedimethanol diacrylate, propoxylated neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, di(trimethylolpropane) tetra(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, Acrylates, pentaerythritol tri(meth)acrylate, propoxylated glycerol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, bisphenol A-di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, trihydroxypropyl methacrylate; and also polyester multi(meth)acrylates such as polyester hexa(meth)acrylate, polyurethane multi(meth)acrylates such as polyurethane di(meth)acrylate, epoxidized soybean oil multi(meth)acrylate.

9. An intumescent coating composition according to any one of the preceding claims, Features The compound having at least two α,β-unsaturated carbonyl groups includes hexanediol di(meth)acrylate, trimethylolpropane triacrylate, di(trimethylolpropane) tetraacrylate, polyester hexaacrylate, aliphatic polyurethane acrylate and / or epoxy soybean oil tetraacrylate.

10. An intumescent coating composition according to any one of the preceding claims, Features The organic amine compound includes polyamide, polyetheramine, phenolic amine or multifunctional amine monomer or a combination thereof, preferably phenolic amine.

11. An intumescent coating composition according to any one of the preceding claims, Features The stoichiometric ratio of NH groups in the (a) and (b) compounds in the resin component to alkenyl groups in α,β-unsaturated carbonyl groups (—C═C—) is in the range of 0.7 to 1.8, 0.8 to 1.7 or 0.9 to 1.

6.

12. An intumescent coating composition according to any one of the preceding claims, Features The resin component of the composition further comprises c) a catalyst.

13. An intumescent coating composition according to any one of the preceding claims, Features At least 90 wt %, at least 95 wt %, at least 98 wt % or at least 99 wt % or all of the coating material's binder is composed of the resin component (A), based on the total weight of the coating material's binder.

14. A method of coating a substrate comprising applying an intumescent coating composition according to any one of claims 1 to 13 to a substrate, preferably a steel substrate.

15. A substrate at least partially coated with a coating deposited from an intumescent coating composition according to any one of claims 1 to 13.

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