Fireproofing composition

Abstract

The invention relates to a fireproofing composition comprising a component A and a component B. The component A comprises a liquid epoxy resin and ammonium polyphosphate. The component B comprises (i) at least one adduct B1 of at least one polyamine having at least three amine hydrogens reactive towards epoxy groups and (ii) at least one epoxide, an ether group containing aliphatic primary diamine B2 and an aliphatic or cycloaliphatic primary diamine B3. The fireproofing composition has a good adhesion to metals, shows a good fireproofing value with low mass loss after passing through the drying oven of the automotive industry and is suitable for spraying.

Description

Technical Field

[0001] The present invention is based on a fire-retardant composition according to the preamble of claim 1.

[0002] The present invention is also based on a method for coating a heat-stabilized substrate, and particularly preferably based on a method for coating a heat-stabilized substrate in the outer shell structure of a transport vehicle. Background Technology

[0003] In the vehicle's outer shell structure, the body undergoes a KTL (cathode immersion) bath upon completion, in which so-called KTL paint is applied to the body, followed by drying in a KTL oven. A good, full-surface KTL coating is fundamental to the vehicle's long-term service life as it greatly contributes to corrosion resistance. Additionally, the body also passes through another oven where the paint on the body is dried.

[0004] In the manufacture of battery-powered vehicles, fire-retardant coatings are applied to the battery containers to better protect the vehicle and passengers in the event of a battery fire. However, these fire-retardant coatings place high demands on the materials used in the battery containers, which are typically made of metal and preferably not pre-treated. On the other hand, the quality of the fire-retardant coating must not be affected during drying in the oven, and mass loss must be as low as possible, as mass loss would lead to an increase in VOC load in these ovens. Low mass loss is typically achieved by reducing the amount of solvent; however, this results in a significant increase in the viscosity of the fire-retardant composition. However, the fire-retardant composition should have a sufficiently low viscosity to be applied to the substrate by spraying.

[0005] Ideally, fire-retardant coatings also help prevent corrosion, which makes coatings with KTL paint obsolete. Summary of the Invention

[0006] The object of the present invention is to provide a fire-retardant composition that has good adhesion to the materials of these battery containers, preferably metals, retains good fire resistance after being dried in an oven, has low mass loss, is suitable for spraying, and preferably improves the corrosion resistance of the substrate.

[0007] Surprisingly, the fire-retardant composition according to claim 1 is able to achieve this purpose.

[0008] Other aspects have led to the use of a fire-retardant composition for coating a heat-stabilized substrate and a method for coating a heat-stabilized substrate.

[0009] Preferred embodiments of the present invention are the subject of the dependent claims. Detailed Implementation

[0010] In a first aspect, the present invention relates to a fire-retardant composition comprising component A and component B. Preferably, components A and B are present as separate components, particularly prior to the use of the fire-retardant composition.

[0011] Component A includes:

[0012] -Based on the total weight of component A, 10% to 70% by weight, particularly 15% to 50% by weight, 15% to 30% by weight, preferably 15% to 25% by weight of at least one liquid epoxy resin A1, wherein each molecule of the liquid epoxy resin has an average of more than one epoxy group; and

[0013] - Based on the total weight of component A, 10% to 70% by weight, particularly 20% to 60% by weight, 30% to 50% by weight, preferably 35% to 45% by weight of ammonium polyphosphate A2.

[0014] Component B includes:

[0015] - At least one adduct B1, consisting of (i) at least one polyamine having at least three amine hydrogens that are reactive to epoxy groups and (ii) at least one epoxide;

[0016] - At least one ether-containing aliphatic primary diamine B2, especially polyoxyethylenediamine;

[0017] - At least one aliphatic or alicyclic primary diamine B3, preferably the at least one aliphatic or alicyclic primary diamine B3 without an ether group;

[0018] - Preferably at least one tertiary amine B4.

[0019] The weight ratio of B1:B2:B3 is 1:1.0 to 2.0:1.5 to 3.5, particularly 1:1.2 to 1.8:2.0 to 3.0, preferably 1:1.25 to 1.75:2.25 to 2.8, and especially preferably 1:1.3 to 1.6:2.25 to 2.8.

[0020] An OH group that is bonded to a C atom with two hydrogen atoms is called a "primary hydroxyl group".

[0021] An NH2 group that is bound to one organic residue is called a "primary amino group", and an NH2 group that is bound to two organic residues (which may also be part of a ring) is called a "secondary amino group".

[0022] In this article, "molecular weight" refers to the molar mass of a molecule (in grams per mole). "Average molecular weight" refers to the number-average Maverage of a mixture of oligomers or polymers. n It is usually determined by gel permeation chromatography (GPC) using polystyrene as a standard.

[0023] A substance or composition is described as "storage stable" or "storable" if it can be stored at room temperature in a suitable container for a long period of time, typically at least 3 to 6 months and longer, without any change in its application or use characteristics due to storage that affects its use.

[0024] "Room temperature" refers to a temperature of 23°C.

[0025] A composition is called "two-component" if its components exist as two different components, which are stored in separate containers and are only mixed together shortly before or during the application of the composition.

[0026] Based on the total weight of component A, component A has 10% to 70% by weight, particularly 15% to 50% by weight, 15% to 30% by weight, preferably 15% to 25% by weight of at least one liquid epoxy resin A1.

[0027] Liquid epoxy resin A1 has an average of more than one epoxy group per molecule. The term "liquid epoxy resin" is familiar to epoxy resin experts and is used in contrast to "solid epoxy resin." Solid resins have a glass transition temperature above room temperature, meaning they can be pulverized into a pourable powder at room temperature.

[0028] The preferred liquid epoxy resin has formula (I).

[0029]

[0030] Here, the substituents R' and R” independently represent H or CH3. Furthermore, the subscript r represents a value from 0 to 1. Preferably, r represents a value less than 0.2.

[0031] Therefore, bisphenol-A (DGEBA), bisphenol-F, and diglycidyl ethers of bisphenol-A / F are preferred. Such liquid resins can, for example, be used as… GY 250 PY 304 GY 282 (Huntsman) or DER TM 331 or DER TM Purchased for 330 (Dow) or Epikote 828 (Hexion).

[0032] Furthermore, so-called phenolic varnishes are also suitable as liquid epoxy resin A1. These phenolic varnishes specifically have the following formula:

[0033] in Or CH2, R1 = H or methyl, z = 0 to 2, especially z = 0 to 1.

[0034] Specifically, this refers to phenolic varnish or cresol varnish (R2=CH2).

[0035] Such epoxy resins can be traded under names such as EPN or ECN, as well as Huntsman's. 556 or DowChemical's DEN TM Commercial purchase.

[0036] Preferably, the liquid epoxy resin A1 is represented as the liquid epoxy resin of formula (I).

[0037] Based on the total weight of component A, component A has 10% to 70% by weight, particularly 20% to 60% by weight, 30% to 50% by weight, and preferably 35% to 45% by weight of ammonium polyphosphate A2.

[0038] Preferably, the ammonium polyphosphate A2 has a particle size of ≤100 μm, particularly 50 μm to 5 μm.

[0039] A further advantage is that ammonium polyphosphate A2 has the formula (NH4PO3). n The ammonium polyphosphate, wherein n is 200 to 2000, preferably 600 to 1500.

[0040] Substances whose names begin with "Poly," such as polyphosphates or polyols, are substances whose each molecule formally contains two or more functional groups that appear in their name.

[0041] It is further advantageous that, based on the total weight of component A, component A has 1% to 15% by weight, particularly 1% to 10% by weight, 2% to 8% by weight, preferably 2% to 5% by weight, at least one reactive diluent A3 with an epoxy group, particularly selected from the group consisting of hexanediol diglycidyl ether, tolyl glycidyl ether, p-tert-butylphenyl glycidyl ether, polypropylene glycol diglycidyl ether and polyethylene glycol diglycidyl ether.

[0042] Preferably, the reactive diluent A3 with epoxy groups is hexanediol diglycidyl ether.

[0043] It is further advantageous that, based on the total weight of component A, component A has 1% to 10% by weight, particularly 5% to 10% by weight, at least one triaryl phosphate or trialkyl phosphate A4.

[0044] Preferably, it is a trialkyl phosphate, more preferably a trialkyl phosphate selected from the group consisting of trimethyl phosphate, triethyl phosphate, triisobutyl phosphate, tributyl phosphate, tri-2-chloroethyl phosphate, tri-2-ethylhexyl phosphate, and tri-2-butoxyethyl phosphate, and most preferably triisobutyl phosphate.

[0045] It is further advantageous that, based on the total weight of component A, component A has 1% to 10% by weight, particularly 1.5% to 6% by weight, preferably 1.5% to 3% by weight of at least one acrylate A5, which has an acrylate functionality of at least 2.

[0046] Preferably, acrylate A5 has an average molecular weight of less than 2,500 g / mol, more preferably less than 1,000 g / mol.

[0047] The acrylate A5 has an acrylate functionality of at least 2, preferably between 2 and 6, more preferably between 3 and 5, and most preferably 3.

[0048] More preferably, based on the total amount of acrylate A5, acrylate A5 includes a polyfunctional acrylate in amounts greater than 70% by weight, greater than 80% by weight, greater than 90% by weight, greater than 95% by weight, and greater than 99% by weight, wherein the polyfunctional acrylate has an acrylate functionality between 2 and 6, more preferably between 3 and 5, and most preferably 3.

[0049] Preferred acrylates A5 with a functionality of 2 include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, and polybutylene glycol dimethacrylate.

[0050] Preferred acrylates A5 with a functionality of 3 or higher include glycerol triacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolmethane tetraacrylate, di-(trimethylolpropane)tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tris(2-methacryloyloxyethyl)trimethacrylate, tris(2-acryloyloxyethyl)isocyanurate, and their ethoxylated or propoxylated derivatives.

[0051] Particularly preferred is that at least one acrylate A5 with a functionality of at least 2 is trimethylolpropane triacrylate.

[0052] Surprisingly, it was found that, advantageously, based on the total weight of component A, component A having the above-mentioned amounts of A1, A2, A3, A4 and A5 also has 0.5% to 15% by weight, particularly 2% to 15% by weight, 5% to 13% by weight, and preferably 8% to 12% by weight of at least one melamine compound A6.

[0053] Preferably, the melamine compound is selected from the group consisting of melamine (1,3,5-triazine-2,4,6-triamine), melamine cyanurate, melamine monophosphate, melamine polyphosphate, and melamine pyrophosphate. Melamine is the most preferred.

[0054] However, an advantage is that component A contains no melamine compounds at all.

[0055] Preferably, component A has a viscosity of 1,000 mPa to 10,000 mPa, particularly 3,000 mPa to 10,000 mPa, particularly 5,000 mPa to 9,000 mPa, measured at a shear rate of 100 sec⁻¹ at 20°C, and particularly determined using a Physica MCR 301 plate-to-plate rheometer at 20°C with a measuring gap of 0.5 mm according to DIN 53019-1.

[0056] Preferably, component A has components A1, A2, A3, A4, and A5, particularly in the amounts described in the preferred embodiments above. It may be further advantageous that component A also additionally has A6, particularly in the amounts described in the preferred embodiments above.

[0057] More preferably, based on the total weight of component A, component A is composed of components A1, A2, A3, A4, A5 and A6 (optionally) at a weight of 60% or more, 70% or more, 75% or more, and preferably 80% or more.

[0058] Where appropriate, component A may contain other components, particularly auxiliaries and additives, such as the following components:

[0059] - Inorganic or organic fillers, especially ground or precipitated calcium carbonate (which may optionally be coated with fatty acids, especially stearates), barite, talc, quartz powder, quartz sand, iron mica, dolomite, wollastonite, kaolin, mica (potassium aluminum silicate), molecular sieves, alumina, aluminum hydroxide, magnesium hydroxide, silicic acid, cement, gypsum, fly ash, soot, graphite, metal powders such as aluminum, copper, iron, zinc, silver or steel, PVC powder or hollow spheres;

[0060] - Fibers, especially glass fibers, carbon fibers, metal fibers, ceramic fibers or plastic fibers such as polyamide fibers or polyethylene fibers;

[0061] - Pigments, especially titanium dioxide and / or iron oxide;

[0062] - Rheology modifiers, especially thickeners or anti-settling agents;

[0063] - Adhesion improvers, especially organoalkoxysilanes;

[0064] -Surface-active substances, especially wetting agents, leveling agents, degassing agents or defoamers;

[0065] Preferably, component A comprises other auxiliaries and additives, particularly selected from the list of inorganic or organic fillers, fibers, pigments, rheology modifiers, wetting agents, leveling agents, defoamers, stabilizers and accelerators.

[0066] Preferably, based on the total weight of component A, the proportions of the other auxiliaries and additives mentioned are 5% to 30% by weight, 10% to 25% by weight, 15% to 25% by weight, and particularly 20% to 25% by weight.

[0067] Preferably, based on the total weight of component A, component A has less than 5% by weight, preferably less than 3% by weight, less than 1% by weight, less than 0.5% by weight, less than 0.2% by weight, less than 0.1% by weight, and most preferably less than 0.05% by weight of an organic solvent, particularly benzyl alcohol or water.

[0068] Component B includes at least one adduct B1, which is composed of (i) at least one polyamine having at least three amine hydrogens that are reactive to epoxy groups and (ii) at least one epoxide.

[0069] Diepoxides are preferred as epoxides for such adducts, such as, in particular, bisphenol-A- or bisphenol-F- or bisphenol-A / F- diglycidyl ether, poly-1,2-epoxypropane diglycidyl ether, or monoepoxides. Aromatic monoepoxides are especially preferred, particularly tolyl glycidyl ether, tert-butylphenyl glycidyl ether, or glycidyl ether of cashew nut kernel. Tolyl glycidyl ether is particularly preferred. All isomeric tolyl glycidyl ethers or mixtures thereof are suitable as cresol glycidyl ethers, especially commercially available types, such as… DY-K (Huntsman), Polypox TM R6 (Dow), Heloxy TM KR (Hexion) or GE-10 (CVC Spec. Chem.).

[0070] The adduct is preferably prepared by slowly metering the epoxide into the initially prepared polyamine, wherein the temperature of the reactants is preferably maintained in the range of 40°C to 120°C, particularly in the range of 50°C to 110°C.

[0071] (i) an adduct of at least one polyamine having at least three amine hydrogens reacting with an epoxy group and (ii) at least one aromatic monoepoxide is preferred, the adduct being obtained at a molar ratio of about 1 / 1, particularly 1 / 0.9 to 1.1, and especially preferably 1 / 0.95 to 1.05. The polyamine may be present in excess during the reaction and is removed by distillation after the reaction.

[0072] For such adducts, the polyamine is preferably selected from ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,3-butanediamine, 1,2-butanediamine, 2,3-butanediamine, 2-methyl-1,3-propanediamine, DAMP, 2,2-dimethyl-1,3-propanediamine, 1,5-pentanediamine, MPMD, 1,6-hexanediamine, 2,5-dimethyl-1,6-hexanediamine, TMD, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, etc. The group consisting of cyclohexane, 1,4-diaminocyclohexane, IPDA, 2-methyl-1,3-diaminocyclohexane and 4-methyl-1,3-diaminocyclohexane and mixtures thereof, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)benzene, bis(2-aminoethyl) ether, 3,6-dioxane-1,8-diamine, DETA, TETA, DPTA, N3-amine, N4-amine and BHMT.

[0073] For such adducts, the aromatic monoepoxide is preferably tolyl glycidyl ether.

[0074] Preferably, adduct B1 is (i) an adduct of at least one polyamine having at least three amine hydrogens that are reactive to epoxy groups and (ii) at least one aromatic monoepoxide, wherein the amine hydrogens are selected from the list consisting of ethylenediamine, propylenediamine and butylenediamine, and particularly preferably an adduct formed by the addition of 1,2-propanediamine and tolyl glycidyl ether.

[0075] The adduct of 1,2-propanediamine and tolyl glycidyl ether is particularly preferred. It is prepared with an excess of 1,2-propanediamine, which is then removed by distillation.

[0076] The adduct of 1,5-diamino-2-methylpentane with tolyl glycidyl ether is further particularly preferred. It is prepared either with an excess of 1,5-diamino-2-methylpentane, followed by removal of the excess 1,5-diamino-2-methylpentane by distillation, or with a slight excess of tolyl glycidyl ether.

[0077] The adduct of 2,2(4),4-trimethylhexamethylenediamine with tolyl glycidyl ether is further particularly preferred, and is prepared with a slight excess of 2,2(4),4-trimethylhexamethylenediamine.

[0078] In these particularly preferred adducts, the term "excess" does not refer to the reactive group, but rather to the molar ratio of the polyamine to tolyl glycine.

[0079] Component B includes at least one adduct B2, which consists of (i) at least one aliphatic primary diamine B2 containing an ether group.

[0080] The at least one ether-containing aliphatic primary diamine B2 is particularly selected from the group consisting of bis(2-aminoethyl) ether, 3,6-dioxane-1,8-diamine, 4,7-dioxane-1,10-diamine, 4,7-dioxane-2,9-diamine, 4,9-dioxane-1,12-diamine, 5,8-dioxane-3,10-diamine, 4,7,10-trioxatridecane-1,13-diamine and higher oligomers of these diamines, 3,9-bis-(3-aminopropyl)-2,4,8,10-tetraoxaspiro-[5,5]-undecane, bis-(3-aminopropyl)polytetrahydrofuran and other polytetrahydrofuran-diamines and polyoxyethylenediamines, particularly polyoxyethylenediamines.

[0081] The latter is a product derived from the amination of polyoxyethylene glycol and can be, for example, named... (Huntsman), Polyetheramine (BASF) or PC Purchased from (Nitroil). Particularly suitable polyoxyethylene diamine is... D-230 D-400, Polyetheramine D 230, Polyetheramine D 400, PC DA250 and PC DA 400.

[0082] Particularly preferred are aliphatic primary diamines B2 containing ether groups, having an average molecular weight of 200 g / mol to 600 g / mol, particularly 200 g / mol to 450 g / mol, especially preferably 250 g / mol to 350 g / mol, particularly polyoxyethylene diamines having the above-mentioned average molecular weight.

[0083] Component B includes at least one aliphatic or alicyclic primary diamine B3, preferably the at least one aliphatic or alicyclic primary diamine B3 without an ether group.

[0084] Specifically, it is selected from 2,2-dimethyl-1,3-propanediamine, 1,3-pentanediamine (DAMP), 1,5-pentanediamine, 1,5-diamino-2-methylpentane (MPMD), 2-butyl-2-ethyl-1,5-pentanediamine (C11 neodiamine), 1,6-hexanediamine, 2,5-dimethyl-1,6-hexanediamine, 2,2(4),4-trimethylhexamethylenediamine (TMD), 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,2-, 1,3- or 1,4-diaminocyclohexane, bis(4-aminocyclohexyl)methane (H 12 -MDA), bis(4-amino-3-methylcyclohexyl)methane, bis(4-amino-3-ethylcyclohexyl)methane, bis(4-amino-3,5-dimethylcyclohexyl)methane, bis(4-amino-3-ethyl-5-methylcyclohexyl)methane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (isophorone diamine or IPDA), 2- or 4-methyl-1,3-diaminocyclohexane or mixtures thereof, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 2,5(2,6)-bis(aminomethyl)bicyclo[2.2.1]heptane (NBDA), 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.0] 2,6 [Aliphatic or alicyclic primary diamine B3 consisting of decane, 1,4-diamino-2,2,6-trimethylcyclohexane (TMCDA), 1,8-menthol diamine, and 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5.5]undecane.]

[0085] Preferably, it is an alicyclic primary diamine, especially 1,3-bis(aminomethyl)cyclohexane.

[0086] Component B preferably includes at least one tertiary amine B4.

[0087] At least one tertiary amine B4 is preferably a tertiary amine that can promote the reaction between amino and epoxy groups.

[0088] Tertiary amine B4 is particularly a salt of 1,4-diazabicyclo[2.2.2]octane, benzyl dimethylamine, α-methylbenzyl dimethylamine, triethanolamine, dimethylaminopropylamine, imidazoles such as especially N-methylimidazolium, N-vinylimidazolium or 1,2-dimethylimidazolium, quaternary ammonium salts such as especially benzyltrimethylammonium chloride, amidines such as especially 1,8-diazabicyclo-[5.4.0]undecyl-7-ene, guanidines such as especially 1,1,3,3-tetramethylguanidine, and Mannich bases such as especially 2-(dimethylaminomethyl)phenol and 2,4,6-tri-(dimethylaminomethyl)phenol.

[0089] At least one tertiary amine B4 is particularly preferably a Mannich base, especially 2-(dimethylaminomethyl)phenol or 2,4,6-tri-(dimethylaminomethyl)phenol.

[0090] Surprisingly, other substances used as promoters of the reaction between amino and epoxy groups, such as acids or compounds that can be hydrolyzed into acids, especially organic carboxylic acids, resulted in a significant increase in viscosity, unlike tertiary amine B4.

[0091] This can be seen, for example, in Table 3 by comparing the exchange of Z1 with Rf.6 and salicylic acid.

[0092] The weight ratio of B1:B2:B3 is 1:1.0 to 2.0:1.5 to 3.5, particularly 1:1.2 to 1.8:2.0 to 3.0, preferably 1:1.25 to 1.75:2.25 to 2.8, and especially preferably 1:1.3 to 1.6:2.25 to 2.8.

[0093] Preferably, the weight ratio of B1:B2:B3:B4 is 1:1.0 to 2.0:1.5 to 3.5:0.15 to 1.2, particularly 1:1.2 to 1.8:2.0 to 3.0:0.3 to 1.0, more preferably 1:1.25 to 1.75:2.25 to 2.8:0.4 to 0.8, and especially preferably 1:1.3 to 1.6:2.25 to 2.8:0.5 to 0.6.

[0094] The advantages of the above weight ratio are as follows: a fire-retardant composition with low viscosity, low mass loss, and excellent performance in adhesion, weather resistance and fire resistance is obtained.

[0095] As can be seen in Table 3, for example, insufficient amount of adduct B1 can lead to a decrease in adhesion, weather resistance and fire resistance.

[0096] It can be further seen that too little ether-containing aliphatic primary diamine B2 will lead to reduced weather resistance and fire resistance, and increased viscosity.

[0097] Table 3 also shows that,

[0098] Insufficient amounts of aliphatic or alicyclic primary diamine B3 can lead to reduced fire resistance and increased viscosity.

[0099] Preferably, component B has a viscosity of 10 mPa to 2,000 mPa, 50 mPa to 2,000 mPa, particularly 50 mPa to 500 mPa, especially preferably 20 mPa to 500 mPa, measured at a shear rate of 100 sec⁻¹ at 20 °C, and particularly determined using a Physica MCR 301 plate-to-plate rheometer at 20 °C with a measuring gap of 0.5 mm according to DIN 53019-1.

[0100] Preferably, the fire-retardant composition has a viscosity of 2,000 mPa to 7,000 mPa, particularly 3,000 mPa to 5,000 mPa, after mixing component A and component B for 30 seconds, measured at a shear rate of 100 sec⁻¹ at 20°C, and particularly determined using a Physica MCR 301 plate-to-plate rheometer at 20°C with a measuring gap of 0.5 mm according to DIN 53019-1.

[0101] Preferably, component B has components B1, B2, B3 and B4, particularly in the amounts described above.

[0102] More preferably, based on the total weight of component B, 80% by weight or more, preferably 90% by weight or more, and most preferably 98% by weight or more of component B is composed of components B1, B2, B3 and B4.

[0103] Components A and B are preferably mixed together with a stirring device at a weight ratio of A:B of 100:4 to 15, particularly 100:6 to 10.

[0104] Preferably, the stoichiometric ratio of epoxy reactive groups to epoxy groups, particularly epoxy reactive amine hydrogens to epoxy groups, in the fire-retardant composition is 0.90 to 1.15, particularly 0.95 to 1.10.

[0105] The fire-retardant coating obtained by mixing component A and component B and then applying the fire-retardant composition is preferably applied to the substrate using a brush or roller via a spraying or extrusion device, particularly via a spraying or extrusion device. The layer thickness is less than 3 mm, preferably less than 2 mm, and particularly 0.5 to 1.5 mm.

[0106] The discovered combination of properties makes, in particular

[0107] It becomes possible to use the compositions according to the invention in fire-retardant coatings in paints that can be brushed, sprayed, or rolled.

[0108] Preferably, the fire-retardant coating obtained from the applied fire-retardant composition has a thickness of 0.1 mm to 4 mm, preferably 0.3 mm to 2 mm, and particularly 0.5 mm to 1.5 mm.

[0109] In another aspect, the present invention includes a method for coating a heat-stabilized substrate, the method comprising the following steps:

[0110] i) Apply the fire-retardant composition as described above to the surface of a heat-stabilized substrate S1, particularly a metal substrate, especially preferably an aluminum substrate, to obtain a coated heat-stabilized substrate S1.

[0111] ii) Heat the coated heat-stable substrate S1 to 140°C to 220°C, particularly 140°C to 200°C, preferably between 160°C and 190°C, for 10 min to 60 min, particularly preferably for 20 min to 45 min.

[0112] Step i) is performed before step ii).

[0113] Specifically, the heat-stabilized substrate S1 is a metal and plastic such as ABS, polyamide, polyphenylene ether, composite material such as SMC, unsaturated polyester GFK, epoxy resin, or acrylate composite material. Preferably, it is a substrate made of metal. Preferred metals are primarily steel, especially electrolytically galvanized steel, hot-dip galvanized steel, oiled steel, Bonazink-coated steel, and subsequently phosphated steel, as well as aluminum, particularly variants commonly used in automotive manufacturing. A substrate made of aluminum is particularly preferred.

[0114] Advantageously, step i') is performed before steps i) and ii), wherein the coated heat-stable substrate S1 is brought into contact with the KTL coating solution (cathode immersion coating), particularly at a temperature between 20°C and 100°C, especially between 20°C and 80°C; preferably between 40°C and 75°C, for a period of 1 to 15 minutes, particularly preferably 1 to 5 minutes. A preferred coating solution is, for example, in… Chemie Lexikon, online version, described as a cationic electrodeposition coating in Georg ThiemeVer-lag, retrieved on December 14, 2018.

[0115] However, Table 3 shows that the composition according to the invention has good corrosion resistance. Therefore, it may be advantageous not to perform step i') before steps i) and ii) due to cost and time savings.

[0116] It is further advantageous that the heat-stabilized substrate S1 is not pretreated before step i), in particular not mechanically pretreated and / or pretreated by applying a tackifier composition, especially not on the surface of the heat-stabilized substrate S1 at the locations where the fire-retardant composition will be applied in step i).

[0117] Table 3 shows that the compositions according to the invention have good adhesion to aluminum, especially when the aluminum substrate has not been mechanically pretreated or no tackifier composition has been applied to the aluminum substrate.

[0118] It is further advantageous that the fire-retardant coating applied after step i) has a thickness of 0.1 mm to 4 mm, preferably 0.3 mm to 2.0 mm, and particularly 0.5 mm to 1.5 mm.

[0119] Further advantageously, the heat-stabilized substrate S1 has a height of 10cm to 60cm, particularly 20cm to 40cm, a width of 50cm to 500cm, particularly 150cm to 300cm, and a depth of 50cm to 700cm, particularly 250cm to 500cm. This substrate is particularly preferably used as a container for batteries, especially for batteries in vehicles, particularly the drive units of automobiles.

[0120] It is further advantageous that, in step i), the fire-retardant coating is applied by spraying, brushing, or rolling, particularly by spraying. Preferably, components A and B are mixed before the fire-retardant coating is applied.

[0121] In another aspect, the present invention includes the use of the fire-retardant composition as described above for coating a heat-stabilized substrate, particularly a metal substrate, especially preferably an aluminum substrate, and particularly preferably for coating a heat-stabilized substrate in the housing structure of a transport vehicle.

[0122] Example

[0123] The invention will now be further illustrated with reference to embodiments. These embodiments are intended to further illustrate the invention, but in no way limit the scope of the invention.

[0124] Compositions Z1 to Z4 and Rf.1 to Rf.7 were prepared, and these compositions consist of the components in parts by weight as described in Tables 2 and 3. Compositions Rf1 to Rf.7 are comparative examples.

[0125]

[0126]

[0127] Table 1: Raw Materials Used

[0128] Component A weight% Liquid epoxy resin A1 18.3 Ammonium polyphosphate A2 42.4 Reactive diluent A3 3.1 Triisobutyl phosphate A4 6.0 Trimethylolpropane triacrylate A5 1.6 Melamine A6 11.5 Filler (kaolin) 5.8 Pigment (titanium dioxide) 6.2 Rheology Additives 0.7 Fibers (carbon fiber and metal fiber) 4.4 total 100

[0129] Table 2: Composition of Component A, by weight parts

[0130] Description of the method for mixing and applying the composition

[0131] Components A and B are mixed in a weight ratio of 13.3:1.

[0132] The two components were simply mixed manually, then mixed at 2000 rpm for 30 seconds in a high-speed mixer and applied. The thickness of the layer applied to the primer-coated automotive metal sheet was between 500 μm and 2000 μm. The wet layer thickness was equal to the dry layer thickness.

[0133] Component A has an EP value of 0.137 g / 100 g, and component B has an amine value of 415 mg KOH / g. The stoichiometric ratio of the mixed composition is 103%.

[0134] Methods for describing and analyzing quality loss

[0135] Composition Z1 was analyzed using real parameters from a drying cycle from a German automobile manufacturer via thermogravimetric analysis (TGA).

[0136] Use the following parameters on a vacuum-sealed thermal microbalance (Netzsch TG 209 F1 Libra):

[0137] Starting temperature: 40℃

[0138] Heating rate: 10K / min

[0139] Final temperatures: 150℃, 165℃, 175℃, 190℃ and 200℃ (each isothermally held for 50 min)

[0140] Weight: Approximately 15mg

[0141] Gaseous environment: Synthetic air

[0142] crucible: Al2O3

[0143] Flow rate: 40ml / min

[0144] It was found that composition Z1 exhibited only a 1.6% wt% mass loss after heating and only a 5.6% wt% mass loss after subsequent isothermal treatment at 175°C for 50 min. Furthermore, similar low values ​​were measured for isothermal treatments at 150°C, 165°C, 190°C, and 200°C.

[0145] This low mass loss during drying is advantageous for production value because composition Z1 produces virtually no additional emissions. Existing technology products, on the other hand, exhibit significantly higher mass loss.

[0146] Viscosity methods for description and analysis

[0147] Viscosities were measured using a Physica MCR 301 plate-to-plate rheometer at 20°C with a measuring gap of 0.5 mm according to DIN 53019-1. Viscosities were determined at a shear rate of 100 1 / sec.

[0148] The following rating methods were used in Table 3:

[0149] <++> = 20mPas to 60mPas

[0150] + = 15 mPas to 100 mPas

[0151] - => 150mPas

[0152] Corrosion resistance method description and analysis

[0153] The following sample bodies were manufactured for corrosion resistance testing according to ISO 9227 NSS and ISO 6270-1:

[0154] The surface is treated to Sa 2. Furthermore, steel plates with a roughness of 50μm to 70μm are used as the substrate.

[0155] The following tests were then conducted:

[0156] -According to the adhesion pull-out test of DIN EN ISO 4624,

[0157] - According to the rust test under scratch according to DIN EN ISO 12944,

[0158] - Blistering (DIN EN ISO 4628-2) / rusting (DIN EN ISO 4628-3).

[0159] Composition Z1 demonstrated exceptional resistance to corrosion and climate change in 480h salt spray and 720h condensation climate tests.

[0160] The following rating methods were used in Table 3:

[0161] "+" = Bubbling 0S0, Rust under scratches <3.0mm

[0162] <-> = Bubbling >0S0, or rust under scratches >3.0mm

[0163] Adhesion method description and analysis

[0164] Adhesion pull-out tests were conducted according to DIN EN ISO 4624. A 20 mm adhesion test specimen was adhered to the coating surface and cured at room temperature for 24 hours. The specimen was then pulled off using an Elcometer 510 hydraulic tensile testing machine. The equipment automatically displayed the results in MPa or N / mm². 2 The adhesion value is expressed in units of N / mm². The adhesion value of composition Z1 on sandblasted steel is 10 N / mm². 2 Within the range.

[0165] The following rating methods were used in Table 3:

[0166] "+" = Adhesion value > 8 N / mm 2

[0167] - = Adhesion value < 8 N / mm 2

[0168] Fire prevention methods description and analysis

[0169] During development, the fire resistance of the compositions was first tested according to EN 13501-2 and EN 13381-8:2010. Compositions Z1 and Z4 exhibited good insulation against heat input transferred to the substrate and good stability against detachment or fly-off due to turbulence in the fire. This was rated (+) in Table 3. Compositions with reduced insulation and / or stability were rated (-).

[0170]

Claims

1. A fire-retardant composition comprising component A and component B; The component A includes: - Based on the total weight of component A, 10% to 70% by weight of at least one liquid epoxy resin A1, wherein each molecule of the at least one liquid epoxy resin has an average of more than one epoxy group; -Based on the total weight of component A, 10% to 70% by weight of ammonium polyphosphate A2 -Based on the total weight of component A, 1% to 15% by weight of at least one reactive diluent A3 containing an epoxy group. And component B includes: - At least one adduct B1, consisting of (i) at least one polyamine having at least three amine hydrogens that are reactive to epoxy groups and (ii) at least one epoxide; - At least one aliphatic primary diamine B2 containing an ether group; -At least one aliphatic or alicyclic primary diamine B3; -At least one tertiary amine B4 The weight ratio of B1:B2:B3 is 1:1.0 to 2.0:1.5 to 3.

5. The fire-retardant composition is formed by mixing component A and component B, and the fire-retardant composition formed therefrom has a viscosity of 3000 mPa·s to 5000 mPa·s at 20°C after mixing for 30 seconds, and the fire-retardant composition formed therefrom has a mass loss of 1.6 wt% after heating at 175°C.

2. The fire-retardant composition according to claim 1, characterized in that, The weight ratio of B1:B2:B3:B4 is 1:1.0 to 2.0:1.5 to 3.5:0.15 to 1.

2.

3. The fire-retardant composition according to claim 1, characterized in that, Component A includes: - Based on the total weight of component A, 15% to 50% by weight of at least one liquid epoxy resin A1, wherein each molecule of the at least one liquid epoxy resin has an average of more than one epoxy group.

4. The fire-retardant composition according to claim 1, characterized in that, Component A includes: - Based on the total weight of component A, 15% to 30% by weight of at least one liquid epoxy resin A1, wherein each molecule of the at least one liquid epoxy resin has an average of more than one epoxy group.

5. The fire-retardant composition according to claim 1, characterized in that, Component A includes: - Based on the total weight of component A, 15% to 25% by weight of at least one liquid epoxy resin A1, wherein each molecule of the at least one liquid epoxy resin has an average of more than one epoxy group.

6. The fire-retardant composition according to claim 1, characterized in that, Component A includes: - Based on the total weight of component A, 20% to 60% of ammonium polyphosphate A2.

7. The fire-retardant composition according to claim 1, characterized in that, Component A includes: - Based on the total weight of component A, 30% to 50% by weight of ammonium polyphosphate A2.

8. The fire-retardant composition according to claim 1, characterized in that, Component A includes: - Based on the total weight of component A, 35% to 45% by weight of ammonium polyphosphate A2.

9. The fire-retardant composition according to claim 1, characterized in that, Component A includes: -Based on the total weight of component A, 1% to 10% by weight of at least one reactive diluent A3 containing an epoxy group.

10. The fire-retardant composition according to claim 1, characterized in that, Component A includes: - Based on the total weight of component A, 2% to 8% by weight of at least one reactive diluent A3 containing an epoxy group.

11. The fire-retardant composition according to claim 1, characterized in that, Component A includes: - Based on the total weight of component A, 2% to 5% by weight of at least one reactive diluent A3 containing an epoxy group.

12. The fire-retardant composition according to claim 1, characterized in that, Component B includes: - Polyoxyethylenediamine as at least one aliphatic primary diamine B2 containing an ether group.

13. The fire-retardant composition according to claim 1, characterized in that, The at least one aliphatic or alicyclic primary diamine B3 does not contain an ether group.

14. The fire-retardant composition according to claim 1, characterized in that, The weight ratio of B1:B2:B3 is 1:1.2 to 1.8: 2.0 to 3.

0.

15. The fire-retardant composition according to claim 1, characterized in that, The weight ratio of B1:B2:B3 is 1:1.25 to 1.75: 2.25 to 2.

8.

16. The fire-retardant composition according to claim 1, characterized in that, The weight ratio of B1:B2:B3 is 1:1.3 to 1.6:2.25 to 2.

8.

17. The fire-retardant composition according to claim 1, characterized in that, The weight ratio of B1:B2:B3:B4 is 1:1.2 to 1.8: 2.0 to 3.0: 0.3 to 1.

0.

18. The fire-retardant composition according to claim 1, characterized in that, The weight ratio of B1:B2:B3:B4 is 1:1.25 to 1.75: 2.25 to 2.8: 0.4 to 0.

8.

19. The fire-retardant composition according to claim 1, characterized in that, The weight ratio of B1:B2:B3:B4 is 1:1.3 to 1.6: 2.25 to 2.8: 0.5 to 0.

6.

20. The fire-retardant composition according to any one of claims 1-2, characterized in that, The liquid epoxy resin A1, having an average of more than one epoxy group per molecule, has formula (I). The substituents R' and R'' independently represent H or CH3, and the subscript r represents a value from 0 to 1.

21. The fire-retardant composition according to claim 20, characterized in that, The subscript r represents a value less than 0.

2.

22. The fire-retardant composition according to any one of claims 1-2, characterized in that, The at least one reactive diluent A3 containing an epoxy group is selected from the group consisting of hexanediol diglycidyl ether, tolyl glycidyl ether, p-tert-butylphenyl glycidyl ether, polypropylene glycol diglycidyl ether, and polyethylene glycol diglycidyl ether.

23. The fire-retardant composition according to any one of claims 1-2, characterized in that, Based on the total weight of component A, component A has 1% to 10% by weight of at least one triaryl phosphate or trialkyl phosphate A4.

24. The fire-retardant composition according to claim 23, characterized in that, Based on the total weight of component A, component A has 5% to 10% by weight of at least one triaryl phosphate or trialkyl phosphate A4.

25. The fire-retardant composition according to claim 23, characterized in that, The at least one triaryl phosphate or trialkyl phosphate A4 is a trialkyl phosphate.

26. The fire-retardant composition according to claim 23, characterized in that, The at least one triaryl phosphate or trialkyl phosphate A4 is a trialkyl phosphate selected from the group consisting of trimethyl phosphate, triethyl phosphate, triisobutyl phosphate, tributyl phosphate, tri-2-chloroethyl phosphate, tri-2-ethylhexyl phosphate, and tri-2-butoxyethyl phosphate.

27. The fire-retardant composition according to claim 23, characterized in that, The at least one triaryl phosphate or trialkyl phosphate A4 is triisobutyl phosphate.

28. The fire-retardant composition according to any one of claims 1-2, characterized in that, Based on the total weight of component A, component A has at least 1% to 10% by weight of at least one acrylate A5, wherein the acrylate has an acrylate functionality of at least 2.

29. The fire-retardant composition according to claim 28, characterized in that, Based on the total weight of component A, component A has at least 2% to 6% by weight of at least one acrylate A5.

30. The fire-retardant composition according to claim 28, characterized in that, Based on the total weight of component A, component A has at least 1.5% to 3% by weight of at least one acrylate A5.

31. The fire-retardant composition according to claim 28, characterized in that, The acrylate has an acrylate functionality between 2 and 6.

32. The fire-retardant composition according to claim 28, characterized in that, The acrylate has an acrylate functionality between 3 and 5.

33. The fire-retardant composition according to any one of claims 1-2, characterized in that, The adduct B1 is (i) an adduct of at least one polyamine having at least three amine hydrogens that are reactive to epoxy groups and (ii) at least one aromatic monoepoxide, wherein the amine hydrogens are selected from the group consisting of ethylenediamine, propylenediamine and butanediamine.

34. The fire-retardant composition according to any one of claims 1-2, characterized in that, The adduct B1 is an adduct of 1,2-propanediamine and tolyl glycidyl ether.

35. The fire-retardant composition according to any one of claims 1-2, characterized in that, The at least one ether-containing aliphatic primary diamine B2 has an average molecular weight of 200 g / mol to 600 g / mol.

36. The fire-retardant composition according to any one of claims 1-2, characterized in that, The at least one aliphatic primary diamine B2 containing an ether group has an average molecular weight of 200 g / mol to 450 g / mol.

37. The fire-retardant composition according to any one of claims 1-2, characterized in that, The at least one ether-containing aliphatic primary diamine B2 has an average molecular weight of 250 g / mol to 350 g / mol.

38. The fire-retardant composition according to any one of claims 1-2, characterized in that, The at least one aliphatic or alicyclic primary diamine B3 is an alicyclic primary diamine.

39. The fire-retardant composition according to any one of claims 1-2, characterized in that, The at least one aliphatic or alicyclic primary diamine B3 is 1,3-bis(aminomethyl)cyclohexane.

40. The fire-retardant composition according to any one of claims 1-2, characterized in that, The at least one tertiary amine B4 is a Mannich base.

41. The fire-retardant composition according to any one of claims 1-2, characterized in that, The at least one tertiary amine B4 is 2-(dimethylaminomethyl)phenol or 2,4,6-tris-(dimethylaminomethyl)phenol.

42. The fire-retardant composition according to any one of claims 1-2, characterized in that, (ii) of the adduct B1 is an aromatic monoepoxide.

43. The fire-retardant composition according to any one of claims 1-2, characterized in that, In the adduct B1 (ii), at least one epoxide is tolyl glycidyl ether, tert-butylphenyl glycidyl ether, or glycidyl ether of cashew phenol.

44. The fire-retardant composition according to any one of claims 1-2, characterized in that, (ii) of the adduct B1, at least one epoxide is tolyl glycidyl ether.

45. The fire-retardant composition according to any one of claims 1-2, characterized in that, The two components, A and B, exist as separate components.

46. ​​Use of a fire-retardant composition according to any one of claims 1 to 45 for coating a heat-stabilized substrate.

47. The use according to claim 46, wherein, The thermally stable substrate is a metal substrate.

48. The use according to claim 46, wherein, The heat-stabilized substrate is an aluminum substrate.

49. The use according to claim 46, wherein, The heat-stabilized substrate is a heat-stabilized substrate coated in the outer shell structure of a transportation vehicle.

50. A method for coating a heat-stabilized substrate, the method comprising the following steps: i) Apply the fire-retardant composition according to any one of claims 1 to 45 to the surface of the heat-stabilized substrate S1 to obtain a coated heat-stabilized substrate S1; ii) Heat the coated heat-stable substrate S1 to a temperature between 140°C and 220°C for 10 min to 60 min.

51. The method of claim 50, wherein the thermally stable substrate is a metal substrate.

52. The method according to claim 50, wherein, The heat-stabilized substrate is an aluminum substrate.

53. The method according to claim 50, wherein, The method includes the following steps: heating the coated heat-stabilized substrate S1 to a temperature between 140°C and 200°C.

54. The method according to claim 50, wherein, The method includes the following steps: heating the coated heat-stabilized substrate S1 to a temperature between 160°C and 190°C.

55. The method according to claim 50, wherein, The method includes the following steps: heating the coated heat-stable substrate S1 for 20 min to 45 min.

56. The method of claim 50, wherein step i') is performed before step i) and step ii), wherein the coated heat-stable substrate S1 is brought into contact with the KTL coating solution at a temperature between 20°C and 100°C for 1 min to 15 min.

57. The method of claim 56, wherein the coated heat-stable substrate S1 is contacted with the KTL coating solution at a temperature between 20°C and 80°C.

58. The method of claim 56, wherein the coated heat-stable substrate S1 is contacted with the KTL coating solution at a temperature between 40°C and 75°C.

59. The method of claim 56, wherein the coated heat-stable substrate S1 is kept in contact with the KTL coating solution for 1 min to 5 min.

60. The method according to claim 50, wherein the thermally stable substrate S1 is not pretreated before step i).

61. The method according to claim 50, wherein the thermally stable substrate S1 prior to step i) is not subjected to mechanical pretreatment and / or pretreatment by applying a tackifier composition.

62. The method of claim 50, wherein prior to step i), the heat-stabilized substrate S1 is not pretreated at the locations on the surface of the heat-stabilized substrate S1 where the fire-retardant composition will be applied in step i).

63. The method according to claim 50 or 56, wherein the fire-retardant coating applied after step i) has a thickness of 0.1 mm to 4 mm.

64. The method according to claim 50 or 56, wherein the fire-retardant coating applied after step i) has a thickness of 0.3 mm to 2.0 mm.

65. The method according to claim 50 or 56, wherein the fire-retardant coating applied after step i) has a thickness of 0.5 mm to 1.5 mm.

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