Expandable coatings based on polyazamiquel addition chemistry.

Abstract

The rapidly curing, expandable coating composition comprises component A and component B, wherein component A comprises at least one (meth)acrylate compound AcC having one or more acryloyl groups (CH2=CHCO-) ​​and / or methacryloyl groups (CH2=C(CH3)CO-) in its molecule, and component B comprises an amine compound AmC comprising at least one amine group selected from primary amine groups, secondary amine groups and / or blocked amine groups, and the expandable coating composition comprises the expandable coating composition The composition further comprises at least one acid source in an amount of 10-70% by weight based on the total weight, the sum of the acrylate compound AcC and the amine compound AmC (AcC + AmC) is 10-50% by weight based on the total weight of the expandable coating composition, and the molar ratio of the acryloyl group (CH2=CHCO-) ​​and methacryloyl group (CH2=C(CH3)CO-) of AcC and the potentially present epoxy groups of at least one epoxy resin EP to the amine group of the amine compound AmC is 0.5-1.5.

Description

[Technical Field]

[0001] This invention relates to the field of expandable coating compositions. Furthermore, this invention relates to the use of expandable coating compositions for protecting components from heat in the event of a fire, a method for protecting components, and coated components obtained by this method. [Background technology]

[0002] Expandable coatings are coatings that, when exposed to heat, for example in the case of a fire, expand to form a highly insulating carbonaceous layer. Components coated with expandable coatings, such as steel beams or columns in a building, are protected by the passive fire-resistant coating from rapidly rising temperatures for a certain period of time. For example, the temperature rise of the component is delayed up to a critical temperature (>500°C), at least due to the insulating effect of the coating. This allows for more time to evacuate people from a building and take firefighting measures before the component may become dysfunctional. Building regulations in many countries require adequate fire protection for load-bearing structures such as steel columns, beams, and tension rods for a specified protection time, known in the industry as F-class. According to DIN 4102-2, the F-class number represents the approved duration in minutes that allows the fire protection system to withstand a fire without the individual component losing its load-bearing capacity. The certification of these products indicates a specific F-class, or specific coating film thickness required to protect the individual component for a certain protection time.

[0003] Today, a variety of expandable coating products exist on the market, which are based in particular on the following technologies: (i) single-pack aqueous coatings based on vinyl acetate dispersions as coating binders, for example; (ii) two-component coating formulations based on epoxy resin and amine curing agents in the second component; (iii) two-component polyurethane polyaspartate compositions curable with isocyanates; (iv) multi-pack poly(methyl methacrylate) (PMMA) compositions curable with organic peroxides; and (v) one-component and two-component polysiloxanes.

[0004] An example of (ii) is described in European Patent No. 3 527 605(A1) (Nippon Steel Chemical & Material CO.Ltd.), and includes a resin composition suitable for fiber-reinforced composite materials used to manufacture molded articles having high heat resistance. Specifically, it is a two-component resin composition for fiber-reinforced composite materials comprising a main component containing an epoxy resin (A) and a (meth)acrylate compound (B) having three or more (meth)acryloyl groups in its molecule, and a curing agent containing an amine compound (C) represented by the following general formula: X-(CH2NH2), where X is an n-valent organic group having 1 to 16 carbon atoms, and n represents 2 or 3. As a result, the mass ratio of the main component to the curing agent is in the range of 85:15 to 65:35, the epoxy resin (A) contains 75% to 100% by mass of bisphenol A type epoxy resin, the main component has a viscosity of 10,000 mPa·s or less, and the curing agent has a viscosity of 800 mPa·s or less.

[0005] The following references to "weight percentage" ("wt.%)" are based on the provided liquid product.

[0006] Existing epoxy-based fire-retardant compositions generally exhibit excellent mechanical properties. However, they are limited in terms of curing speed, UV resistance, and / or actual filler level. Aqueous dispersion-based expandable coatings are limited primarily by their mechanical fragility and chemical resistance. PMMA-based expandable compositions are advantageous in terms of curing speed and filler level, but have problems with hazardous components (e.g., peroxide storage), irritating odors during application, and their multi-component packaging.

[0007] Therefore, in order to protect the environment and people, there is a need to provide improved solutions for expansive coatings, especially for rapid curing or drying coatings, that have high resistivity and less hazardous formulations. [Overview of the Initiative]

[0008] This specification provides improved solutions for expandable coatings. In particular, the expandable coatings described herein are mechanically robust, rapidly curing, UV resistant, and / or free of problematic substances as much as possible. Furthermore, the expandable coatings are suitable for a wide range of applications and are preferably derived from readily available and inexpensive raw materials.

[0009] The compositions described herein are based on a combination of at least one acrylate compound (AcC), an amine compound (AmC), and a specific functional filler package for improving fire resistance, which may be partially dispersed in AcC and / or AmC. Additional components may be present to adapt the expandable coating composition to specific requirements and applications.

[0010] Surprisingly, the combination of different components made it possible to produce an expandable coating composition with a fast curing rate, good UV resistance, and photostability, which was found to be preferable compared to well-known epoxy compositions.

[0011] While not strictly theoretical, this is thought to be due, in particular, to the relatively rapid Michael addition reaction between the acrylate compound AcC and the amine group of the amine compound AmC, resulting in the formation of an acrylate-amine adduct. This is especially true for primary amine groups.

[0012] Furthermore, the mechanical stability and cost of the required raw materials are comparable to those of well-known epoxy compositions. The coatings of the present invention are not based on PMMA chemistry, use, or radical curing initiators (e.g., peroxides), and can be formulated without isocyanates, thus enabling advantageous hazard classification and safer handling, and avoiding storage problems associated with their different components.

[0013] Furthermore, the compositions described herein have been found to be particularly suitable for a variety of applications, including fire protection, corrosion protection, and flooring. This allows for the application of standard products. Therefore, customers do not need to change their established workflows or acquire special equipment.

[0014] Further aspects of the description provided herein are the subject of further independent claims. Particularly preferred embodiments of the present invention are the subject of dependent claims. [Modes for carrying out the invention]

[0015] The subject of this invention is an expandable coating composition comprising component A and component B.

[0016] In some embodiments, component A comprises at least one monomer, oligomer, or polymer acrylate compound AcC having one or more acryloyl groups (CH2=CHCO-) ​​and / or methacryloyl groups (CH2=C(CH3)CO-) in the molecule. The acrylate compound AcC is also referred to as an acrylate binder.

[0017] A suitable acrylic binder is an acrylate or methacrylate having one, two, or more (meth)acrylate groups, particularly one having low viscosity at room temperature. In a preferred embodiment, a suitable acrylic binder is at least one (meth)acrylate having two or more functional groups. Suitable acrylates include, but are not limited to, methyl acrylate, ethyl acrylate, butyl acrylate, n-amyl acrylate, isobornyl acrylate, isobutyl acrylate, tert-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, 3,5,5-trimethylhexyl acrylate, 2-methoxyethyl acrylate, 2-phenoxyethyl acrylate, 4-tert-butylcyclohexyl acrylate, octyl acrylate, isodecyl acrylate, decyl acrylate, lauryl acrylate, tridecyl acrylate, octadecyl acrylate, behenyl acrylate, and their modifications or combinations. Further examples include diethylene glycol. These acrylates include di(meth)acrylate, triethylene glycol di(meth)acrylate, or higher polyethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, or higher polypropylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, dodecanediol di(meth)acrylate, glycerin di(meth)acrylate, or trimethylolpropane tri(meth)acrylate, with particular preference being trimethylolpropane triacrylate, derivatives thereof, or other acryloyl functional molecules, as well as combinations thereof. These acrylates provide low viscosity and desirable curing properties.

[0018] In particular, at least one acrylate compound AcC has one or more acryloyl groups (CH2=CHCO-) ​​in its molecule. In particular, at least one acrylate compound AcC has at least two, preferably two to four acryloyl groups (CH2=CHCO-) ​​in its molecule.

[0019] In particular, the ratio of acryloyl groups (CH2=CHCO-) to methacryloyl groups (CH2=C(CH3)CO-) in component A is at least 2, particularly at least 3, and especially at least 5.

[0020] In particular, acrylate compound AcC is an acrylate monomer, but in some embodiments, it may be an acrylate oligomer or polymer such as, for example, but not limited to, epoxy acrylate, polyester acrylate, urethane acrylate, acrylic acrylate, melamine acrylate, or derivatives and combinations thereof.

[0021] Preferably, at least one acrylate compound AcC does not contain an acid group selected from the group consisting of carboxyl groups, phosphate groups, and / or sulfonic acid groups.

[0022] Preferably, at least one acrylate compound AcC does not contain an NH2 group.

[0023] In particular, at least one acrylate compound AcC does not contain an acid group and an NH2 group.

[0024] Preferably, at least one acrylate compound AcC is based on an aliphatic skeleton that may contain an ester group and / or an ether group in its skeleton.

[0025] Preferably, at least one acrylate compound AcC is based on a polyol, preferably a polyol selected from the list consisting of, but not limited to, hexanediol, glycerin, trimethylolpropane, isoborneol, ditrimethylolpropane, pentaerythritol, and dipentaerythritol, or an alkoxylated, particularly ethoxylated polyol, and the polyol is preferably selected from the list consisting of glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol.

[0026] Most preferably, at least one acrylate compound AcC is selected from hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, isoborneol acrylate and / or pentaerythritol tetraacrylate.

[0027] In some embodiments, the expandable composition described herein contains component B, and component B contains at least one amine group selected from a primary amine group, a secondary amine group and a blocked amine group, and / or contains a monomer, oligomer or polymeric amine compound AmC containing at least one blocked amine group, whereby the amine compound AmC is preferably a compound of the following formulas (Ia), (Ib) and (Ic), X-(CH2NH2) (Ia) X-(NHCH2) m (Ib) X-(CH2)3N(Ic) In the formula, X represents an n-valent organic group having 1 to 80, preferably 1 to 16 carbon atoms, n represents a number from 1 to 10, preferably 1 to 3, and preferably, X in the general formulas (Ia, b, c) is an n-valent hydrocarbon group having an alicyclic structure with 6 or more carbon atoms, an n-valent hydrocarbon group having an aromatic ring structure, an n-valent hydrocarbon group having an araliphatic structure, an n-valent hydrocarbon group having an aliphatic structure, and an n-valent polyether group, and the n-valent hydrocarbon group may have at least one secondary amine structure inside.

[0028] In particular, the amine compound AmC may be represented by the following formula (II), formula (III), formula (IV), formula (V), formula (VI), formula (VII) and / or formula (VIII),

[0029]

Table 1

[0030] Particularly preferably, the amine compound AmC is represented by formula (II), formula (III), formula (IV), formula (V) and / or formula (VI).

[0031] Substance (VI) can be produced by reacting benzaldehyde with a primary alkyldiamine, such as 1,2-diaminoethane or 1,3-diaminopropane, as described, for example, on pages 34, line 5 to 35, line 20 of International Publication No. WO2017 / 046293(A1). Suitable amine curing agents may be any amino functional species, primary, secondary or tertiary amines, Mannich bases or adducts thereof, oligoamines, polyamidoamines, polyetheramines, polyalkyleneamines (DETA, TETA), phenalkamines, or aliphatic primary amines (isophorone diamines, such as 1,3-bis(aminomethyl)benzol as described in U.S. Patent No. 10,442,937 or 10,131,800). Other protective coatings without fire-retardant properties, containing N-benzyl-1,2-ethanediamine as a curing agent component, are described in European Patent No. 3344677 and exhibit good curing at low temperatures without defects such as whitening. More possible curing agents include diethylenetriamine, triethylenetetramine, tetraethylenepentaamine, polyamidoamine, isophoronediamine, m-xylenediamine, 1,3-bis(aminomethyl)cyclohexane, bis(4-aminocyclohexyl)methane, N-aminoethylpiperazine, and m-phenylenediamine, which can be used alone or in combination. Amino-functional curing agents for compounded polymers, such as, but not limited to, Ancamine by Evonik or Dow Epoxy Hardener (DEH) by Olin, can be used on their own or in combination with any of the examples described above.

[0032] In one embodiment, the described expandable coating composition is a composition in which the sum of the acrylate compound AcC and the amine compound AmC (AcC + AmC) is 5 to 80% by weight, preferably 10 to 50% by weight, based on the total weight of the expandable coating composition. Here, the molar ratio of the acryloyl group (CH2=CHCO-) ​​of the acrylate compound AcC and the potentially present epoxy group of at least one epoxy resin EP to the amine group of the amine compound AmC is 0.5 to 1.5, preferably 0.75 to 1.25, which is similar to the stoichiometric ratio.

[0033] Optionally, the expandable coating composition may contain at least one epoxy resin EP, preferably a liquid epoxy resin, in an amount of >0 to 100% by weight, particularly 0 to 50% by weight, most preferably 0% by weight, based on the total weight of the acrylate compound AcC.

[0034] In particular, the composition does not necessarily contain epoxy resin EP. However, according to a special embodiment, epoxy resin EP may be present.

[0035] Suitable epoxy resins that may be optionally present in the composition are commercially available industrial epoxy resins. These can be obtained by well-known methods, for example, from the oxidation of the corresponding olefin, or from the reaction of epichlorohydrin with the corresponding polyol, polyphenol, or amine.

[0036] Particularly preferred epoxy resins are those called liquid polyepoxy resins, which will be referred to as "liquid epoxy resins" below. These have a glass transition temperature of less than 25°C and an average molecular weight of >700.

[0037] Similarly, possible epoxy resins are solid resins that have a glass transition temperature above 25°C and can be dissolved in a suitable solvent, or reactive thinners for handling as a liquid.

[0038] Suitable epoxy resins include aromatic epoxy resins, more specifically, -These are glycidylation products of bisphenol A, bisphenol F, or bisphenol A / F (wherein A represents acetone and F represents formaldehyde), which functioned as reactants in the preparation of these bisphenols. In the case of bisphenol F, positional isomers derived particularly from 2,4'- or 2,2'-hydroxyphenylmethane may also exist. -Dihydroxybenzene derivatives, such as resorcinol, hydroquinone, or pyrocatechol, - Further bisphenols or polyphenols, e.g., bis(4-hydroxy-3-methylphenyl)methane, 2,2-bis(4-hydroxy-3-methylphenyl)propane (Bisphenol C), bis(3,5-dimethyl-4-hydroxyphenyl)methane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-tert-butylphenyl)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, 2,4-bis(3,5-dimethyl-4-hydroxyphenyl)-2-methylbutane, 1,1-bis(4-hydroxyphenyl)cyclohexane (Bisphenol Z), 1,1-bis(4- Hydroxyphenyl)-3,3,5-trimethylcyclohexane (bisphenol-TMC), 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,4-bis[2-(4-hydroxyphenyl)-2-propyl]benzene (bisphenol P), 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene (bisphenol M), 4,4'-dihydroxybiphenyl (DOD), 4,4'-dihydroxybenzophenone, bis(2-hydroxynaphthalene-1-yl)methane, bis(4-hydroxynaphthalene-1-yl)methane, 1,5-dihydroxynaphthalene, tris(4-hydroxyphenyl)methane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, bis(4-hydroxyphenyl) ether or bis(4-hydroxyphenyl) sulfone, -The condensation product of phenol and formaldehyde obtained under acidic conditions, for example, phenol novolac or cresol novolac (also called bisphenol F novolac), -Aromatic amines, such as aniline, toluidine, 4-aminophenol, 4,4'-methylenediphenyldiamine, 4,4'-methylenediphenyldi-(N-methyl)amine, 4,4'-[1,4-phenylenebis(1-methylethylidene)]bisaniline (bisaniline P) or 4,4'-[1,3-phenylenebis(1-methylethylidene)]bisaniline (bisaniline M) and derivatives thereof (not limited to these) may be included in combination.

[0039] Further preferred epoxy resins include aliphatic or alicyclic polyepoxides, more specifically, -Saturated or unsaturated, branched or unbranched, cyclic or open-chain, bifunctional, trifunctional or tetrafunctional C2~C 30 Alcohols, especially ethylene glycol, propylene glycol, butylene glycol, hexanediol, octanediol, polypropylene glycol, dimethylolcyclohexane, neopentyl glycol, dibromo-neopentyl glycol, castor oil, trimethylolpropane, trimethylolethane, pentaerythritol, sorbitol or glycerol, or glycidyl ethers of alkoxylated glycerol or alkoxylated trimethylolpropane, -Hydrogenated bisphenol A, F, or A / F liquid resin, or a glycidylation product of hydrogenated bisphenol A, F, or A / F, - N-glycidyl derivatives of amides or heterocyclic nitrogen bases, such as triglycidyl cyanurate or triglycidyl isocyanurate, or reaction products of epichlorohydrin and hydantoin, -Epoxy resins derived from the oxidation of olefins, such as vinylcyclohexene, dicyclopentadiene, cyclohexadiene, cyclododecadiene, cyclododecatriene isoprene, 1,5-hexadiene, butadiene, polybutadiene, or divinylbenzene and derivatives thereof (not limited to these), and combinations thereof may be included.

[0040] Preferred epoxy resins are liquid resins based on bisphenol, more specifically bisphenol A, bisphenol F, or diglycidyl ethers of bisphenol A / F, particularly those of the type commercially available from, for example, Dow, Huntsman, or Momentive. These liquid resins have low viscosity relative to epoxy resins and exhibit good coating properties in the cured state. They may also contain fractions of solid bisphenol A, bisphenol F, or novolac resin.

[0041] In some embodiments, the expandable coating composition described herein, - An acid source comprising 10 to 70% by weight of the total weight of the expandable coating composition, comprising at least one acid source acting as a carbonizing agent, selected from, but not limited to, the list of ammonium phosphate, ammonium pyrophosphate, ammonium polyphosphate, melamine phosphate, magnesium sulfate, sodium phosphate, potassium phosphate, or ammonium sulfates, p-toluenesulfonic acid, or boric acid, borate, ammonium pentaborate, zinc borate, sodium borate, lithium borate, aluminum borate, and magnesium borate, and borosilicate, preferably ammonium polyphosphate, and - Preferably, 0 to 15% by weight of the total weight of the expandable coating composition, at least one carbon source for promoting carbonization, selected from, but not limited to, the group consisting of polyhydroxy compounds such as pentaerythritol, dipentaerythritol, tripentaerythritol, pentaerythritol and pentaerythritol-based ester polycondensates, xylitol, sorbitol or mannitol, preferably pentaerythritol and / or dipentaerythritol, their derivatives or combinations, and -Optionally, based on the total weight of the acrylate compound AcC, the further comprises >0 to 40% by weight, particularly 0 to 20% by weight, most preferably 0% by weight, of at least one additive Sol selected from solvents and plasticizers, preferably xylene, isobutanol, benzyl alcohol, other alcohols, acetates, ketones, or other organic solvents, selected from a list including but not limited to these.

[0042] Optionally, the composition may include pentaerythritol, dipentaerythritol, tripentaerythritol, polycondensates of pentaerythritol and pentaerythritol-based esters, and / or polyols such as xylitol, sorbitol, and mannitol, preferably polyhydroxy compounds such as pentaerythritol and / or dipentaerythritol.

[0043] Preferably, the composition contains, or may be in combination with, at least one gas-generating, foaming compound selected from, but not limited to, the group consisting of melamine (1,3,5-triazine-2,4,6-triamine), hexamethoxymethylmelamine, melamine cyanurate, melamine monophosphate, melamine polyphosphate, melamine pyrophosphate, urea-containing compounds, cyanuric acid or isocyanuric acid or its derivatives, cyanamide, dicyanamide, azodicarbonamide, guanidine and its salts, biguanides, cyanurates, cyanuric acid esters and amides, dimelamine pyrophosphate, and derivatives thereof, in an amount of 0 to 20% by weight, based on the total weight of the expandable coating composition. Most preferred is melamine.

[0044] The expandable coating composition exhibits a viscosity of 0.1 to 30 Pa·s, preferably 1 to 20 Pa·s, and more preferably 1.5 to 10 Pa·s, at 23°C after mixing components A and B for 10 seconds. This viscosity is measured using a plate-plate viscometer at a shear rate of 100 s². -1It is measured at [location / method]. Such viscosity is very suitable for a variety of applications. If desired, the viscosity can be adjusted with additives such as Sol.

[0045] In particular, the expandable coating composition contains, based on the total weight of the expandable coating composition, at least one radical polymerization initiator, in less than 1% by weight, preferably less than 0.1% by weight, more preferably less than 0.001% by weight, and most preferably 0% by weight, an azo compound or organic peroxide that generates radicals upon heating.

[0046] According to another preferred embodiment, the expandable coating composition further comprises 0 to 40% by weight, preferably 5 to 30% by weight, of at least one inorganic filler, based on the total weight of the expandable coating composition.

[0047] The inorganic filler, or two or more fillers, is preferably selected from the group consisting of, but not limited to, barite, talc, quartz powder, quartz sand, silicon carbide, iron mica, dolomite, wollastonite, colemanite, kaolin, mica (potassium aluminum silicate), molecular sieves, aluminum oxide, zinc oxide, aluminum hydroxide, magnesium hydroxide, silica, cement, gypsum, fly ash, soot, graphite, graphene, organic or inorganic fibers and hollow spheres, particularly talc, quartz powder, kaolin, titanium dioxide, silicate glass flakes or spheres and aluminum trihydrate, or modified or combined thereof.

[0048] For improved carbide stability, but not limited to, mineral fibers, carbon fibers, or mixtures or combinations thereof based on SiO2, CaO, MgO, and Al2O3 may be present in the formulation at a concentration of 0.1 to 15% of the total formulation or any combination thereof.

[0049] Those skilled in the art know that it may be necessary to use additional components, known as additives, to fine-tune the specific properties of component A, component B, or both.

[0050] These may include, but are not limited to, rheology control agents, dispersion aids, wetting agents, leveling agents, adhesion promoters, defoamers and deaeration agents, and flame retardants.

[0051] Agents for rheological control are used, for example, to improve sagging resistance, meaning that higher layer thicknesses can be applied in a single layer; and to improve sedimentation in wet coating compositions, meaning that different components in the wet coating do not separate during storage or transport. They include, but are not limited to, modified castor oil derivatives, amide waxes, organically modified layered silica, and fumed silica. These can be used alone or in any combination thereof.

[0052] Dispersants are used, for example, to improve the quality of a dispersion, to maintain the quality of an achieved dispersion, or to reduce the viscosity of a coating composition including a binder composition and a filler composition. These include, but are not limited to, unsaturated acidic polycarboxylic acid polyesters, phosphate esters, modified polyurethanes, high molecular weight polyesters, and highly branched polyesters. These can be used alone or in any combination thereof.

[0053] Wetting agents are used, for example, to improve surface wetting. This includes, but is not limited to, wetting solid particles contained in the expandable coating composition, or wetting the surface of any component coated with the prepared coating composition. They include, for example, polyether-modified polydimethylsiloxanes. These can be used alone or in any combination thereof.

[0054] Leveling agents are used, for example, to improve the surface quality of a coating composition applied to any component to be coated with a readily formulated coating composition. They include, for example, polyethers and / or polyester-modified polydimethylsiloxanes, or polyacrylates. These can be used alone or in any combination thereof.

[0055] Defoaming and degassing agents are used, for example, to remove air trapped in a liquid coating composition, either component A or component B, or both thereof. They may also be used to remove air introduced during the process of applying a mixed coating composition to any component coated with the coating composition. These include, but are not limited to, polysiloxanes, polymethylalkylsiloxanes, polyalkylene ethers, and polyolefins. They may be used alone or in any combination thereof.

[0056] Flame retardants are used, for example, to reduce the flammability of coating systems or to capture reactive mixtures when applied to components. They include, but are not limited to, phosphate esters, liquid phosphates, phosphites, and phosphonates with and without halogen moieties. Sources of metal or metalloid ions include, for example, metal oxides, metalloid oxides, metal hydroxides, metalloid hydroxides, metal carbonates or bicarbonates, metal phosphates, metal chlorides, metal nitrates, metal borates, metal sulfates, and metal silicates. They may exist on their own or in any combination or complex. The metals mentioned may be selected from, but are not limited to, Al, B, Ti, Cu, Zn, Mg, Na, Ca, Si, or combinations thereof. Examples used may be, but are not limited to, ZnO, ZnPO4, TiO2, Al2O3, Al(OH)3, AlPO4, MgO, and MgPO4.

[0057] Further embodiments of this specification relate to the use of the above-described expandable coating compositions for protecting components from heat in the event of a fire. The components may be, for example, components of buildings, infrastructure, and / or vehicles.

[0058] The components are, for example, - Glass, glass ceramics, concrete, mortar, brick, tile, gypsum, or natural stones such as granite or marble, - Metals or alloys such as aluminum, iron, steel, and non-ferrous metals, or surface-hardened metals or alloys such as zinc-plated or chromium-plated metals, -Wood materials bonded with leather, textiles, paper, wood, resins, such as phenolic resins, melamine resins, or epoxy resins, such as resin-textile composite materials, or other polymer composite materials, -Plastics, especially rigid or flexible PVC, ABS, polycarbonate (PC), polyamide (PA), polyester, PMMA, epoxy resin, PU, ​​POM, PO, PE, PP, EPM or EPDM (plastics are optionally surface-treated by plasma, corona or flame treatment) and - Fiber-reinforced plastics, such as carbon fiber reinforced plastics (CRP), glass fiber reinforced plastics (GRP), or sheet molding compounds (SMC), -For example, it may include, or consist of, a coated substrate such as a powder-coated or electro-coated metal or alloy for use in vehicle structures.

[0059] Furthermore, in particular, the expandable coating composition can be used as an undercoat, tie coat, or anticorrosion coating.

[0060] A fully or partially cured expandable coating composition may have further coatings, coverings, or paints applied thereto. In this case, the further layer may include different materials, particularly polyurethane, polyurea, or polysiloxane coatings.

[0061] If necessary, the components may be pre-treated before applying the expandable coating composition. Such pre-treatments include, in particular, physical and / or chemical cleaning techniques, such as sanding, sandblasting, shot blasting, brushing and / or blowing, as well as treatment with cleaning agents or solvents, or application of adhesion promoters, adhesion promoter solutions or primers.

[0062] Further aspects of the present invention relate particularly to methods for protecting the above-mentioned components, (i) A step of providing the components, (ii) If necessary, a step of applying a primer to the surface of the component, (iii) The step of applying the above mixed expandable coating composition to the surface of optionally undercoated components within the pot life, (iv) If necessary, a further layer of the mixed expandable coating composition is applied to the cured layer within the pot life, (v) If necessary, repeat step (iv), and (vi) optionally, a step of applying a top coat to the cured expandable coating composition.

[0063] In this way, the components are protected from corrosion and other environmental degradation, but especially from heat in the event of a fire.

[0064] Suitable components include, in particular, steel beams, steel or concrete supports, load-bearing concrete elements such as intermediate floors or ceilings, components made from wood, composite materials or plastics such as insulation panels, supports in vehicle structures or battery boxes for electric vehicles, such as tanks for liquid hydrogen fuel, in particular fiber-reinforced composite tanks, and battery boxes made from steel, aluminum or fiber-reinforced composite materials.

[0065] Preferably, the surfaces of the components are cleaned, in particular by brushing, blasting, vacuuming, or blow-off, and are free from oil, grease, cement skin, oxide layers, rust, and dust.

[0066] When an expandable coating is used to repair an already coated component when the old coating is damaged and / or no longer suitable, the surface is preferably prepared so that the old coating is at least partially removed from the surface, for example, by sweep blasting.

[0067] If necessary, apply the primer to the surface of the components, particularly by spraying, pumping, troweling, or brushing.

[0068] Two-component epoxy primers, which may or may not contain one- or two-component epoxy, alkyd, or acrylic primers, a solvent, or water-based system, are particularly suitable as primers for steel. Some may contain mica-like iron oxide to improve barrier properties. Such primers enable particularly good corrosion protection and excellent adhesion of subsequent expandable coatings.

[0069] Two-component epoxy primers are particularly suitable as concrete primers. Such primers bind to existing dust, seal pores, and enable excellent adhesion of subsequent expansive coatings.

[0070] For the application of the expandable coating, in step (iii), the mixed expandable coating is applied to the surface of optionally primed components within the pot life. Preferably, the application is carried out by a spraying device or by using a brush, roller or squeegee, preferably by an airless spraying method, in particular by a multi-feed or single-feed airless spraying device.

[0071] A layer thickness in the range of 0.5 to 2 mm is preferably applied in a single pass.

[0072] If necessary, the expandable coating is applied in more than one layer. Step (iv) is performed once or several times, in each case waiting until the previous layer has fully cured and produced a dry, non-stick surface.

[0073] Considering all layers, the expandable coating is preferably applied with a layer thickness in the range of 0.5 to 10 mm, preferably 1 to 8 mm, and particularly 2 to 6 mm.

[0074] Preferably, the expandable coating is applied in two or more steps. For example, to achieve a desired layer thickness of 5 mm, it is preferable to apply three layers, each having a thickness slightly less than 1.7 mm.

[0075] If necessary, apply a topcoat to the cured expandable coating. This is particularly preferable when the cured expandable coating maintains a clearly visible appearance and has a particularly decorative, color-stable look.

[0076] The topcoat may be based on polyurethane, polyaspartic acid, acrylic, polysiloxane, or silicone, PVDF, alkyd, or any modification or hybrid thereof is particularly preferred as the topcoat.

[0077] Further aspects of the present invention relate to coated components that can be obtained or obtained by the above-described method.

[0078] Coated components include, in particular, steel beams, supports made of steel or concrete, load-bearing concrete elements such as intermediate floors or ceilings, components made of plastic such as insulation panels, supports in vehicle structures or battery boxes in electric vehicles, in particular battery boxes made of steel or aluminum.

[0079] The coating preferably has a layer thickness in the range of 0 to 50 mm, preferably 0.01 to 30 mm, and particularly 0.1 to 20 mm, depending on the material and dimensions of the constituent elements.

[0080] When exposed to high temperatures in the event of a fire, a rigid, stable, and volatilized porous material with surprisingly high thermal insulation properties is formed from the above-mentioned coating.

[0081] Further aspects of the present invention relate to coated articles produced by the methods described herein.

[0082] Another further aspect of the present invention, as described herein, relates to a coated article comprising a component having an expandable coating composition applied thereon to protect the component from heat in the event of a fire, wherein the component is selected from, for example, weight-bearing metal members, concrete, wood, electrical systems, tanks and / or vehicle parts, to protect the component from heat in the event of a fire.

[0083] This allows, for example, the fire to be selected from cellulose-based, hydrocarbon-based, jet, pool, battery, or other specific and non-specific fire scenarios.

[0084] In this context, coating refers to all kinds of two-dimensionally applied coverings, particularly paints, varnishes, sealants, undercoats or primers, floor coatings or protective coatings, including those for heavy-duty applications. Particularly advantageous, coating compositions are formulated as low-emission coatings that can carry eco-quality labels, such as Emicode (EC1 Plus), AgBB, DIBt, Der Blaue Engel, AFSSET, RTS (M1), and US Green Building Council (LEED).

[0085] Substance names beginning with "poly," such as polyamines, polyols, or polyepoxides, indicate substances that formally contain two or more of the functional group appearing in that name per molecule.

[0086] In this specification, the term "viscosity" refers to dynamic viscosity or shear viscosity, which is defined by the ratio (velocity gradient) between shear stress and shear rate, and is determined as described in the examples.

[0087] "Blocked amine group" means, but is not limited to, an aldimine group or a ketimine group. These are condensation products of a primary amine group with an aldehyde or ketone, respectively. Aldimines and ketimines can be hydrolyzed to form the corresponding amines and aldehydes or ketones, respectively. Therefore, they can be considered protected forms of amines. The use of amine compounds AmC having blocked amines typically reduces the curing rate of expansive coating compositions.

[0088] At least one amine group is, in particular, a primary amine group and / or a secondary amine group. Most preferred is a primary amine group for its rapid reaction with the acrylate compound. In this specification, the term “primary amine group” refers to an NH2- group attached to an organic moiety, and the term “secondary amine group” refers to an NH- group attached to two organic moieties that together may form part of a ring.

[0089] In this specification, "molecular weight" is understood to mean the molar mass (grams per mole) of a molecule. "Average molecular weight" is the number average M of an oligomer or polymer mixture of molecules. n This is typically determined by gel permeation chromatography (GPC) against polystyrene as a standard.

[0090] The acid source of the composition is added to initiate the decomposition of the reacted compounds A and B and / or an optional supplemental carbon source when exposed to heat, particularly in the event of a fire. As a result, ammonium phosphate, ammonium pyrophosphate, ammonium polyphosphate, melamine phosphate, magnesium sulfate, and boric acid are very suitable in combination with compounds A and B. [Examples]

[0091] The following are examples intended to illustrate the described invention in more detail. The invention is, of course, not limited to these examples.

[0092] Substances used:

[0093] [Table 2]

[0094] Manufacturing of expandable coatings Expandable coatings A to E were prepared as follows: an acrylate compound (AcC) and an optional epoxy resin (EP) were mixed in the proportions shown in Table 1 to provide the first component. Similarly, an amine compound (AmC) and an optional additive (Sol) were provided as the second component. Coating E is a comparative example not according to the present invention.

[0095] Subsequently, the two components were mixed in the proportions shown in Table 1 to obtain a homogeneous liquid. The resulting mixture was immediately tested as follows.

[0096] To test the expansion characteristics, a steel upright I-shaped section (= component, open column) with dimensions of height × width × length = 100 cm × 16 cm × 16 cm, wall thickness of 13 mm, and circumference / cross-sectional area ratio of 160 was prepared.

[0097] This was coated with a two-component epoxy resin mica-like iron oxide coating (dry film thickness approximately 40 μm) and maintained in a standard climate for 24 hours. Next, a total of six thermal sensors were placed in the center of each of the undercoated interior contours of the I-shaped cross-section. Subsequently, each expandable coating was applied to the entire component by using a brush to apply three layers of slightly less than 1.7 mm each, with a 24-hour waiting period between layers, so that the component was ultimately completely coated with a 5 mm thickness of each expandable coating covering the mounted thermal sensors.

[0098] After a storage period of 3 days in standard climate, the coated components were subjected to a combustion test in a furnace according to DIN 4102 Part 2, whereby the temperature of the members (= average value from 6 thermocouples) was recorded as a function of time via the attached thermocouples.

[0099] The viscosity of the low-viscosity samples (< 150 mPa·s) was measured with a temperature-controlled cone / plate rheometer, Anton Paar Physica MCR300 (cone diameter 50 mm, cone angle 2°, distance between cone tip / plate 0.05 mm, shear rate 100 s -1 )).

[0100] The pot life was determined as the time until the viscosity doubled.

[0101] As a measure of the curing rate, the times to reach the different drying stages, drying stages 1, 6 and 7, under standard climate conditions according to DIN EN ISO 291 (23 °C / 50% rH) were determined as described in DIN EN ISO 9117-5:2012.

[0102]

Table 3

[0103] As is evident from the data shown in Table 1, coatings A to D are suitable for use as expandable coatings. In contrast, coating E, which has a molar ratio outside the scope of the claims, is characterized by a pot life that is too short for practical applications.

Claims

1. An expandable coating composition comprising component A and component B, The above component A contains one or more acryloyl groups (CH ２ =CHCO-) ​​and / or methacryloyl group (CH ２ = C(CH ３ It comprises at least one (meth)acrylate compound AcC having )CO-) and The component B comprises an amine compound AmC having at least one amine group selected from a primary amine group, a secondary amine group and / or a blocked amine group, wherein the amine compound AmC is preferably a compound of formula (Ia). X-(CH ２ NH ２ ) ｎ (Ia) In the formula, X represents an n-valent organic group having 1 to 80 carbon atoms, preferably 1 to 16, and n represents a number from 1 to 10, preferably 1 to 3. The aforementioned expandable coating composition - The expansion coating composition comprises 10 to 70% by weight of at least one acid source selected from the list consisting of ammonium phosphate, ammonium pyrophosphate, ammonium polyphosphate, melamine phosphate, magnesium sulfate, and boric acid, preferably ammonium polyphosphate and / or its derivatives, but not limited to these, and including combinations of acid sources. Preferably, the composition contains, based on the total weight of the expandable coating composition, 0 to 15% by weight of at least one compound selected from the group consisting of polyhydroxy compounds such as pentaerythritol, dipentaerythritol, tripentaerythritol, polycondensates of pentaerythritol and pentaerythritol-based esters, and / or polyols such as xylitol, sorbitol, or mannitol, but is not limited to these, and preferably includes pentaerythritol and / or its derivatives, but is not limited to these, and may include combinations thereof. Preferably, the composition contains, based on the total weight of the expandable coating composition, 0 to 20% by weight of at least one (foaming) compound selected from the group, for example, but not limited to, melamine (1,3,5-triazine-2,4,6-triamine), hexamethoxymethylmelamine, melamine cyanurate, melamine monophosphate, melamine polyphosphate, melamine pyrophosphate, urea-containing compounds, cyanuric acid or isocyanuric acid or its derivatives, cyanamide, dicyanamide, dicyandiamide, guanidine and its salts, biguanides, cyanurates, cyanuric acid esters and amides, dimelamine pyrophosphate, and its derivatives, and is not limited to these, and may include combinations, most preferably melamine and / or its derivatives, but is not limited to these, and may include combinations. -Optionally, based on the total weight of the acrylate compound AcC, >0 to 100% by weight, particularly >0 to 50% by weight, at least one epoxy resin EP, preferably a liquid epoxy resin. -Optionally, based on the total weight of the acrylate compound AcC, >0 to 40% by weight, particularly 0 to 20% by weight, most preferably 0% by weight, of at least one additive Sol selected from a list of solvents and plasticizers, preferably xylene, isobutanol, other alcohols, acetates, ketones, or other organic solvents. Here, the sum of the acrylate compound AcC and the amine compound AmC (AcC + AmC) is 10 to 40% by weight based on the total weight of the expandable coating composition. The molar ratio of the acryloyl group (CH ２ =CHCO-) and methacryloyl group (CH ２ =C(CH ３ )CO-) of the acrylate compound AcC and the potentially present epoxy groups of the at least one epoxy resin EP to the amine group of the amine compound AmC is 0.5 to 2.5, an expandable coating composition.

2. The expandable coating composition according to claim 1, wherein X in the general formula (I) is selected from the group consisting of an n-valent hydrocarbon group having an alicyclic structure having six or more carbon atoms, an n-valent hydrocarbon group having an aromatic ring structure, an n-valent hydrocarbon group having an aromatic aliphatic structure, an n-valent hydrocarbon group having an aliphatic structure, and an n-valent polyether group, wherein the n-valent hydrocarbon group may have at least one secondary amine structure inside it.

3. The amine compound AmC is represented by the following formulas (II), (III), (IV), (V), (VI), or (VII), Table 1 In the formula, m represents a number from 0 to 6, preferably 2 to 3; p represents a number from 1 to 10, preferably 2 to 3; t represents a number from 0 to 8, preferably 0; and the sum of (x + y + z) represents a number from 3 to 20, preferably 5 to 6. X １ However, it represents an n-valent organic group having 1 to 10 carbon atoms, preferably X １ CH ３ The expandable coating composition according to claim 1 or 2.

4. The expandable coating composition according to claim 3, wherein the amine compound AmC is represented by formula (II), formula (III), formula (IV), formula (V), or formula (VI).

5. The at least one acrylate compound AcC contains one or more acryloyl groups (CH) in its molecule. ２ An expandable coating composition according to any one of claims 1 to 4, having =CHCO-.

6. The aforementioned at least one acrylate compound AcC contains 2 to 5, preferably 2 to 4, acryloyl groups (CH) in its molecule. ２ The expandable coating composition according to claim 5, having =CHCO-).

7. The expandable coating composition according to any one of claims 1 to 6, wherein the at least one acrylate compound AcC does not contain an acid group selected from the group consisting of a carboxyl group, a phosphoric acid group and / or a sulfonic acid group.

8. The at least one acrylate compound AcC has an OH group and / or NH ２ An expandable coating composition according to any one of claims 1 to 7, which does not contain a group.

9. The expandable coating composition according to any one of claims 1 to 8, wherein the at least one acrylate compound AcC is based on an aliphatic skeleton that may contain an ester group and / or an ether group in its skeleton.

10. The expandable coating composition according to any one of claims 1 to 9, wherein the at least one acrylate compound AcC is preferably a polyol selected from the list consisting of hexanediol, glycerol, trimethylolpropane, isoborneol, ditrimethylolpropane, pentaerythritol, and dipentaerythritol, or an alkoxylated, particularly ethoxylated polyol, wherein the polyol is preferably selected from the list consisting of glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol tri(meth)acrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol triacrylate, and is not limited to these, but may include derivatives and combinations thereof.

11. The at least one acrylate compound AcC is based on hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, isobornyl acrylate and / or pentaerythritol tetraacrylate, and methyl acrylate, ethyl acrylate, butyl acrylate, n-amyl acrylate, isobornyl acrylate, isobutyl acrylate, tert-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, 3,5,5-trimethylhexyl acrylate, 2-methoxyethyl acrylate, 2-phenoxyethyl acrylate, 4-tert-butylcyclohexyl acrylate, octyl acrylate, isodecyl acrylate, decyl acrylate, lauryl acrylate, tridecyl acrylate, octadecyl acrylate, behenyl acrylate. An expandable coating composition according to any one of claims 1 to 10, selected from acrylates, their modifiers or combinations, further examples being diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, or higher polyethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, or higher polypropylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, dodecanediol di(meth)acrylate, glycerin di(meth)acrylate, or trimethylolpropane tri(meth)acrylate, with particular preference being trimethylolpropane triacrylate, its derivatives, and combinations thereof.

12. The expandable coating composition, after mixing component A with component B for 10 seconds at 23°C, exhibits a viscosity of 1 to 30 Pa·s, preferably 2 to 20 Pa·s, and more preferably 3 to 15 Pa·s at 23°C, and this viscosity is measured by a parallel plate viscometer at a shear rate of 100 s. －１ An expandable coating composition according to any one of claims 1 to 11, as measured by [method].

13. The expandable coating composition according to any one of claims 1 to 12, wherein the expandable coating composition contains less than 0.1% by weight, preferably less than 0.01% by weight, and more preferably less than 0.001% by weight, of at least one radical polymerization initiator, particularly an azo compound or organic peroxide that generates radicals when heated, based on the total weight of the expandable coating composition.

14. The expandable coating composition according to any one of claims 1 to 13, further comprising 5 to 30% by weight, based on the total weight of the expandable coating composition, preferably barite (barite), talc, quartz powder, quartz sand, silicon carbide, iron mica, dolomite, wollastonite, colemanite, kaolin, mica (potassium aluminum silicate), molecular sieves, aluminum oxide, zinc oxide, aluminum hydroxide, magnesium hydroxide, silica, cement, gypsum, fly ash, soot, graphite, organic and inorganic fibers, and hollow spheres, and further comprising at least one inorganic filler selected from the group consisting particularly talc, quartz powder, kaolin, titanium dioxide and aluminum hydroxide.

15. A coated article comprising a component on which an expandable coating composition according to any one of claims 1 to 14 is applied to protect the component from heat in the event of a fire, wherein the component is a weight-bearing metal member, concrete, wood, electrical system, tank and / or vehicle part, selected from among these, against the heat in the event of a fire.

16. A method for protecting components, (i) A step of providing the above-mentioned components, (ii) Optionally, a step of applying a primer to the surface of the component, (iii) A step of applying the mixed expandable coating composition according to any one of claims 1 to 14 to the surface of the optionally undercoated component within the pot life, (iv) Optionally, a step of applying a further layer of the mixed expandable coating composition according to any one of claims 1 to 14 to the cured layer within the pot life, (v) A step in which step (iv) is repeated at the discretion of the user, and (vi) A method comprising the optional step of applying a top coat to a cured, expandable coating composition.

17. A coated article manufactured by the method described in claim 16.

18. The coated article according to claim 15, wherein the fire is selected from cellulose-based, hydrocarbon-based, jet, pool, battery, or other specific and non-specific fire scenarios.

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