EP4150014A1

EP4150014A1 - Fire protection composition

Info

Publication number: EP4150014A1
Application number: EP21725767.4A
Authority: EP
Inventors: Jochen Grötzinger; Andreas ROTHENGASS; Johannes VIERTEL; Markus WÖHR
Original assignee: Sherwin Williams Coatings Deutschland GmbH
Current assignee: Sherwin Williams Coatings Deutschland GmbH
Priority date: 2020-05-14
Filing date: 2021-05-12
Publication date: 2023-03-22
Also published as: US20230272228A1; WO2021229028A1; CN115996995A

Abstract

The present invention relates to a fire protection composition, comprising a component A and a component B. The component A comprises an epoxy liquid resin and ammonium polyphosphate. The component B comprises: - an adduct B1 of (i) at least one polyamine having at least three amine hydrogens which are reactive with epoxy groups and (ii) at least one epoxy; - an ether-group-containing aliphatic primary diamine B2; and - an aliphatic or cycloaliphatic primary diamine B3. The fire protection composition has good adhesion to metal, still has good fire protection values after passing through baking furnaces in the automotive industry, with low loss of mass, and is suitable for spray application.

Description

Fire protection composition

Technical area

The invention is based on a fire protection composition according to the preamble of the first claim.

The invention is also based on a method for coating heat-stable substrates, particularly preferably heat-stable substrates in the shell construction of means of transport.

State of the art

In the shell of a means of transport, the body passes through a KTL (cathodic dip painting) bath at the end of the shell, in which it is coated with a so-called KTL lacquer, which is then baked in a KTL oven. A good, full-surface KTL painting is a basis for long-term use of the vehicle, as it makes a significant contribution to corrosion resistance. In addition, the body also passes through another furnace in which the paint on the body is baked.

In the manufacture of battery-operated vehicles, the containers se these batteries are provided with fire protection coatings to better protect the vehicle and passengers in the event of a battery fire. However, high demands are placed on these fire protection coatings. So they should have good adhesion to the materials of these Batteriebehäl ter, which are typically made of metal, preferably without pretreatment. On the other hand, the fire protection coatings do not have to suffer any loss of quality when they pass through the baking ovens and, if possible, do not have to show any loss of mass, which leads to an increased VOC load in these ovens. A small loss of mass is typically achieved by reducing the use of solvents, which, however, results in a large increase in the viscosity of the fire protection composition. This should but have a sufficiently low viscosity to be applied to the substrates by spray application.

Ideally, the fire protection coating further contributes to the protection against corrosion, which would make coating with a KTL lacquer obsolete.

Presentation of the invention

The invention is based on the object of providing a fire protection composition that has good adhesion to the materials of this battery container, preferably metal, still has good fire protection values after passing through baking ovens and has a low loss of mass, is suitable for spray application and preferably improve the corrosion resistance of the substrates.

Surprisingly, it has been found that a fire protection composition according to claim 1 is able to solve this problem.

Further aspects are a use of the fire protection composition for coating heat-stable substrates and a method for coating heat-stable substrates.

Preferred embodiments of the invention are the subject of the claims.

Ways of Carrying Out the Invention

In a first aspect, the present invention relates to a fire protection composition comprising a component A and a component B. The two components A and B are preferably present as separate components, in particular before the fire protection composition is used.

Component A includes:

-10-70, in particular 15-50, 15-30, preferably 15-25% by weight of at least one liquid epoxy resin, which on average has more than one A1 has epoxy groups per molecule, based on the total weight of component A; and

-10-70, in particular 20-60, 30-50, preferably 35-45,% by weight of ammonium polyphosphate A2, based on the total weight of component A.

Component B includes:

- At least one adduct B1 of (i) at least one polyamine with at least three amine hydrogens reactive towards epoxide groups with (ii) at least one epoxide: - At least one aliphatic primary diamine containing ether groups

B2, in particular it is a polyoxyalkylenediamine;

- At least one aliphatic or cycloaliphatic primary diamine B3, preferably the at least one aliphatic or cycloaliphatic primary diamine B3 is free of ether groups; - preferably at least one tertiary amine B4.

The weight ratio of B1: B2: B3 is 1: 1.0-2.0: 1.5-3.5, in particular 1: 1.2-1.8: 2.0-3.0, preferably 1: 1.25-1.75: 2.25-2.8, particularly preferably 1: 1.3-1.6: 2.25-2.8.

A “primary hydroxyl group” is an OH group that is bonded to a carbon atom with two hydrogens.

A “primary amino group” is an NH2 group that is bonded to an organic radical and a “secondary amino group” is an NH group that is bonded to two organic radicals which can also be part of a ring together .

In the present document, “molecular weight” means the molar mass (in grams per mole) of a molecule. “Average molecular weight” is the number average M _{n of} an oligomeric or polymeric mixture of molecules, which is usually determined using gel permeation chromatography (GPC) against polystyrene as the standard.

A substance or a composition is referred to as “stable” or “storable” if it is stored in a suitable container at room temperature. binding can be stored for a longer period of time, typically for at least 3 months up to 6 months and more, without its application or usage properties being changed by storage to an extent relevant to its use. A temperature of 23 ° C is referred to as “room temperature”.

A composition is referred to as “two-component” in which the constituents of the composition are present in two different components, which are stored in separate containers and only mixed with one another shortly before or during the application of the composition.

Component A has 10-70% by weight, in particular 15-50, 15-30, preferably 15-25% by weight, of at least one liquid epoxy resin A1, based on the total weight of component A.

The liquid epoxy resin A1 has on average more than one epoxy group per molecule. The term “liquid epoxy resin” is well known to the epoxy specialist and is used in contrast to “solid epoxy resins”. The glass transition temperature of solid resins is above room temperature, i.e. they can be crushed to free-flowing powders at room temperature.

Preferred liquid epoxy resins have the formula (I)

The substituents R 'and R "stand independently of one another either for H or CH3. Furthermore, the index r stands for a value from 0 to 1. Preferably r stands for a value less than 0.2.

They are therefore preferably diglycidyl ethers of bisphenol-A (DGEBA), of bisphenol-F and of bisphenol-A / F. Such liquid resins are, for example, Araldite® GY 250, Araldite® PY 304, Araldite® GY 282 (Huntsman) or DER ™ 331 or DER ™ 330 (Dow) or Epikote 828 (Hexion).

So-called novolaks are also suitable as epoxy liquid resin A1. In particular, these have the following formula: or CH2, R1 =

H or methyl and z = 0 to 2, in particular z = 0 to 1.

In particular, these are phenol or cresol novolaks (R2 = CH ₂ ). Such epoxy resins are commercially available under the trade names EPN or ECN and Tactix®556 from Huntsman or under the DEN ™ product series from Dow Chemical.

The liquid epoxy resin A1 is preferably a liquid epoxy resin of the formula (I).

Component A has 10-70, in particular 20-60, 30-50, preferably 35-45% by weight of ammonium polyphosphate A2, based on the total weight of component A.

The ammonium polyphosphate A2 preferably has a particle size of <100 μm, in particular 50 μm-5 μm.

It is also advantageous if the ammonium polyphosphate A2 is an ammonium polyphosphate of the formula (NH4PO3) n with n from 200-2000, preferably 600-1500. Substance names beginning with “poly” such as polyphosphate or polyol denote substances that formally contain two or more of the functional groups per molecule that appear in their names.

It can also be advantageous if component A 1-15, in particular 1-10, 2-8, preferably 2-5% by weight of at least one epoxy-group-bearing reactive diluent A3, in particular selected from the group consisting of hexanediol diglycidyl ether, cresyl glycidyl ether, p-tert .- butylphenyl glycidyl ether, polypropylene glycol diglycidyl ether and polyethylene glycol diglycidyl ether, based on the total weight of component A.

The reactive diluent A3 carrying epoxide groups is preferably hexanediol diglycidyl ether.

It can also be advantageous if component A has 1-10, in particular 5-10,% by weight of at least one triaryl phosphoric acid ester or trialkyl phosphoric acid ester A4, based on the total weight of component A.

It is preferably a trialkyl phosphoric acid ester, preferably a trialkyl phosphoric acid ester selected from the group consisting of trimethyl phosphate, triethyl phosphate, triisobutyl phosphate, tributyl phosphate, tris-2-chloro-ethyl phosphate, tris-2-ethyl-hexyl phosphate, Tris-2-butoxyethyl phosphate, most preferably triisobutyl phosphate.

It can also be advantageous if component A has 1-10, in particular 1.5-6, preferably 1.5-3% by weight of at least one acrylate A5 with an acrylate functionality of at least 2, based on the total weight of component A. .

The acrylate A5 preferably has an average molecular weight of less than 2,500 g / mol, more preferably less than 1Ό00 g / mol. The acrylate A5 has an acrylate functionality of at least 2, preferably between 2 and 6, more preferably between 3 and 5, most preferably 3.

The acrylate A5 more preferably comprises a polyfunctional acrylate with an acrylate functionality of between 2 and 6, more preferably between 3 and 5, most preferably 3, in an amount of more than 70% by weight, more than 80% by weight, more than 90% by weight, more than 95% by weight, more than 99% by weight, based on the total amount of the acrylate A5.

Preferred acrylates A5 with a functionality of 2 include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, tripropylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,4-butanediol dimethacrylate and polybutylene glycol dimethacrylate.

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, di- (trimethylolpropane) methacrylate (trimethylolpropane) (trimethylolpropane) acrylate (trimethylolpropane) methacrylate (trimethylolpropane) (trimethylolpropane) acrylate (trimethylolpropane) methacrylate tetraacrylate, diproxyethyl tetraacrylate, diphrene-tetra-acrylate, 2-methacrylate tetraacrylate, diphritol-tetra-acrylate, 2-methacrylate-2-tetra-acrylate, diphritol-tetra-methacrylate, diphritol-tetra-acrylate, 2-methacrylate-tetra-acrylate, diprythritol tetra-acrylate, pentaerythritol trimethacrylate, pentaerythritol triacrylate, Trimellitate, tri (2-acryloxyethyl) isocyanurate and their ethoxylated or propoxylated derivatives.

The at least one acrylate A5 with a functionality of at least 2 is particularly preferably trimethylolpropane triacrylate.

Surprisingly, it has been found that it can be advantageous if a component A, which has A1, A2, A3, A4 and A5 in the amounts described above, further 0.5-15, in particular 2-15, 5-13, preferably 8- 12% by weight of at least one melamine compound A6, based on the total weight of component A. It is preferably a melamine compound selected from the group consisting of melamine (1,3,5-triazine-2,4,6-triamine), melamine cyanurates, melamine monophosphates, melamine polyphosphates and melamine pyrophosphates. Melamine is most preferred.

However, it can also be advantageous if component A is completely free from melamine compounds.

Component A preferably has a viscosity of 100-1000 mPa, in particular 300-1000 mPa, in particular 5-00-900 mPa, measured at a shear rate of 100 sec-1 at 20 ° C., in particular determined with a Physica MCR 301 plate rheometer -Plate rheometer at 20 ° C, with a measuring gap of 0.5 mm according to DIN 53019-1.

Component A preferably has constituents A1, A2, A3, A4 and A5, in particular in the amounts mentioned above as preferred. It can furthermore be advantageous for this component A to additionally contain A6, in particular in the amounts mentioned above as being preferred.

It is further preferred if component A consists of more than 60% by weight, more than 70% by weight, more than 75% by weight, preferably more than 80% by weight, of the constituents A1, A2, A3 , A4, A5 and possibly A6, based on the total weight of component A.

Component A optionally contains further constituents, in particular auxiliaries and additives, for example the following:

- Inorganic or organic fillers, in particular ground or precipitated calcium carbonates, which may be coated with fatty acids, especially stearates, barite (barite), talc, quartz flour, quartz sand, iron mica, dolomites, wollastonites, kaolins, mica (potassium aluminum) Silicate), molecular sieves, aluminum oxides, aluminum hydroxides, magnesium hydroxide, silicas, cements, plasters, fly ash, soot, graphite, metal powder such as aluminum, copper, iron, zinc, silver or steel, PVC powder or flea balls; - Fibers, in particular glass fibers, carbon fibers, metal fibers, ceramic fibers or plastic fibers such as polyamide fibers or polyethylene fibers;

- Pigments, in particular titanium dioxide and / or iron oxides;

Rheology modifiers, in particular thickeners or anti-settling agents;

- Adhesion improvers, in particular organoalkoxysilanes;

- Surface-active substances, in particular wetting agents, leveling agents, venting agents or defoamers;

Component A preferably contains further auxiliaries and additives, in particular selected from the list consisting of inorganic or organic fillers, fibers, pigments, rheology modifiers, wetting agents, flow agents, defoamers, stabilizers and accelerators.

The proportion of other auxiliaries and additives mentioned is preferably 5-30% by weight, 10-25% by weight, 15-25% by weight, in particular 20-25% by weight, based on the total weight of the component

A.

Component A preferably 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, am most preferably less than 0.05% by weight of organic solvents, in particular benzyl alcohol, or water, based on the total weight of component A.

Component B comprises at least one adduct B1 composed of (i) at least one polyamine with at least three amine hydrogens which are reactive towards epoxide groups and (ii) at least one epoxide.

Preferred epoxides for such an adduct are diepoxides, such as, in particular, bisphenol A or -F- or -A / F-diglycidyl ethers, poly-1,2-propylene oxide diglycidyl ethers or monoepoxides. Aromatic monoepoxides are particularly preferred, in particular cresyl glycidyl ether, tert-butylphenyl glycidyl ether or the Glycidyl ether of cardanol. Cresyl glycidyl ether is particularly preferred. Suitable cresyl glycidyl ethers are all isomeric cresyl glycidyl ethers or mixtures thereof, in particular commercially available types such as in particular Araldite ^® DY-K (from Huntsman), Polypox ™ R6 (from Dow), Heloxy ™ KR (from Hexion) or Erisys ^® GE-10 ( from CVC Spec. Chem.).

The adduct is preferably produced by slowly metering in the epoxy to the initially charged polyamine, the temperature of the reactants preferably being kept in the range from 40 to 120.degree. C., in particular 50 to 110.degree.

Adducts of (i) at least one polyamine with at least three amine hydrogens reactive towards epoxide groups with (ii) at least one aromatic monoepoxide, which in a molar ratio of approximately 1/1, in particular 1 / 0.9-1.1, particularly preferably 1 / 0.95- 1.05 are implemented. The polyamine may have been present in excess during the reaction and may have been removed by distillation after the reaction.

For such an adduct, the polyamine is preferably selected from the group consisting of ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, 1,3-butylenediamine, 1,2-butylenediamine, 2,3- Butylenediamine, 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, 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-dioxaoctane-1, 8-diamine, DETA, TETA, DPTA, N3-amine, N4-amine and BHMT.

For such an adduct, the aromatic monoepoxide is preferably a cresyl glycidyl ether.

The adduct B1 is preferably an adduct of (i) at least one polyamine with at least three amine hydrogens which are reactive towards epoxide groups and are selected from the list consisting of ethylene di- min, propylenediamine and butylenediamine with (ii) at least one aromatic monoepoxide, particularly preferably it is an adduct of 1,2-propylenediamine with cresyl glycidyl ether.

An adduct of 1,2-propylenediamine with cresylglycidyl ether, which is produced with an excess of 1,2-propylenediamine and subsequent removal of the excess by means of distillation, is particularly preferred.

Also particularly preferred is an adduct of 1,5-diamino-2-methylpentane with cresyl glycidyl ether, which is either produced with an excess of 1,5-diamino-2-methylpentane and subsequent removal of the excess by distillation, or with a slight excess of cresyl glycidyl ether . Also particularly preferred is an adduct of 2,2 (4), 4-trimethylhexamethylenediamine with cresyl glycidyl ether, which is produced with a slight excess of 2,2 (4), 4-trimethylhexamethylenediamine.

In the case of these particularly preferred adducts, the term “excess” does not refer to the reactive groups, but to the molar ratio between the polyamine and the cresyl glycyl ether.

Component B comprises at least one adduct B2 of (i) at least one aliphatic primary diamine B2 containing ether groups.

The at least one aliphatic primary diamine B2 containing ether groups is selected in particular from the group consisting of bis (2-aminoethyl) ether, 3,6-dioxaoctane-1,8-diamine, 4,7-dioxadecane-1,10 diamine, 4,7-dioxadecane-2,9-diamine, 4,9-dioxadodecane-1, 12-diamine, 5,8-dioxadodecane-3,10-diamine, 4,7,10-trioxatridecane-1, 13 -diamin and higher oligomers of these diamines, 3,9-bis- (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, bis- (3-aminopropyl) polytetrahydrofurans and other polytetrahydrofuran-diamines and polyoxyalkylene- Diamines, especially polyoxyalkylene diamines.

The latter represent products from the amination of polyoxyalkylene diols, and are available, for example under the name Jeffamine ^® (of Hunts- man), under the name polyetheramine (from BASF) or under the name PC ^® Amine (from Nitroil). Particularly suitable polyoxyalkylene diamines are Jeffamine ^® D-230, Jeffamine ^® D-400, polyetheramine D 230, polyetheramine D 400, PC 250 and PC amines ^® DA amines ^® DA 400th

They are particularly preferably aliphatic primary diamines B2 containing ether groups with an average molecular weight of 200-600 g / mol, in particular 200-450 g / mol, particularly preferably 250-350 g / mol, in particular polyoxyalkylene diamines with a aforementioned average molecular weight.

Component B comprises at least one aliphatic or cycloaliphatic primary diamine B3; the at least one aliphatic or cycloaliphatic primary diamine B3 is preferably free of ether groups.

These are aliphatic or cycloaliphatic primary diamines B3, in particular selected from the list consisting of 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 (H12- 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 (isophoronediamine 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 ] decane, 1,4-diamino-2,2,6-trimethylcyclohexane (TMCDA), 1,8-menhanediamine, 3,9-bis (3-aminopropyl) - 2,4,8,10-tetraoxaspiro [5.5] undecane. They are preferably cycloaliphatic primary diamines, in particular 1,3-bis (aminomethyl) cyclohexane. Component B preferably comprises at least one tertiary amine B4.

The at least one tertiary amine B4 is preferably a tertiary amine, which can accelerate the reaction between amino groups and epoxy groups.

The tertiary amine B4 is, in particular, a tertiary amine selected from the list consisting of 1,4-diazabicyclo [2.2.2] octane, benzyldimethylamine, a-methylbenzyldimethylamine, triethanolamine, dimethylaminopropylamine, imidazoles such as in particular N-methylimidazole, N-vinylimidazole or 1,2-dimethylimidazole, salts of such tertiary amines, quaternary ammonium salts such as, in particular, benzyltrimethylammonium chloride, amidines such as, in particular, 1,8-diazabicyclo [5.4.0] undec-7-ene, guanidines such as, in particular, 1, 1, 3 , 3-tetramethylguanidine and Mannich bases such as in particular 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol.

The at least one tertiary amine B4 is particularly preferably a Mannich base, in particular 2- (dimethylaminomethyl) phenol or 2,4,6-tris (dimethylaminomethyl) phenol.

Surprisingly, it has been found that other substances which are used as accelerators for the reaction between amino groups and epoxy groups, such as acids or compounds hydrolyzable to acids, in particular organic carboxylic acids, in contrast to the tertiary amines B4, lead to a strong increase in viscosity.

This can be seen, for example, in Table 3 in exchange for salicylic acid in comparison of Z1 with Rf.6.

The weight ratio of B1: B2: B3 is 1: 1.0-2.0: 1.5-3.5, in particular 1: 1.2-1.8: 2.0-3.0, preferably 1: 1.25-1.75: 2.25-2.8, particularly preferably 1: 1.3-1. 6: 2.25-2.8. The weight ratio of B1: B2: B3: B4 is preferably 1: 1.0-2.0: 1.5-3.5: 0.15-1.2, in particular 1: 1.2-1.8: 2.0-3.0: 0.3-1.0, preferably 1: 1.25-1.75: 2.25 -2.8: 0.4-0.8, particularly preferably 1: 1.3-1.6: 2.25-2.8: 0.5-0.6. The aforementioned weight ratios are advantageous in that a fire protection composition is obtained which has a low viscosity, a low loss of mass and good values with regard to adhesion, weathering resistance and fire protection behavior. In Table 3 it can be seen, for example, that too small amounts of adduct B1 lead to a deterioration in adhesion, weather resistance and fire protection behavior.

It can also be seen that too small amounts of aliphatic primary diamine B2 containing ether groups lead to a reduction in weather resistance and fire protection behavior and an increase in viscosity.

It can also be seen from Table 3 that too small amounts of aliphatic or cycloaliphatic primary diamine B3 lead to a reduction in the fire protection behavior and an increase in viscosity.

Component B preferably has a viscosity of 10-2-200 mPa, 50-2-200 mPa, in particular 50-500 mPa, particularly preferably 20-500 mPa, measured at a shear rate of 100 sec-1 at 20 ° C., in particular determined with a Physica MCR 301 rheometer, plate-plate rheometer at 20 ° C., with a measuring gap of 0.5 mm in accordance with DIN 53019-1.

Preferably, the fire protection composition 30 seconds after mixing component A with component B has a viscosity of 2-700-700 mPa, in particular 3-500 mPa, measured at a shear rate of 100 sec-1 at 20 ° C, in particular determined with a Rheometer Physica MCR 301 plate-plate rheometer at 20 ° C, with a measuring gap of 0.5 mm according to DIN 53019-1. Component B preferably has constituents B1, B2, B3 and B4, in particular in the amounts mentioned above as preferred.

It is further preferred if component B consists of more than 80% by weight, preferably more than 90% by weight, most preferably more than 98% by weight, of components B1, B2, B3 and B4 on the total weight of component B.

Components A and B are preferably mixed with one another in a weight ratio A: B of 100: 4-15, in particular 100: 6-10, with the aid of a mixing device.

The stoichiometric ratio of the epoxy-reactive groups to the epoxy groups, in particular epoxy-reactive amine hydrogens to epoxy groups, in the fire protection composition is preferably 0.90-1.15, in particular 0.95-1.10.

A fire protection coating obtained by applying the fire protection composition after mixing component A with component B is preferably applied to the substrate by means of a spray or extrusion device, with a brush or a roller, in particular by means of a spray or extrusion device. The layer thickness is less than 3 mm, preferably less than 2 mm, in particular 0.5 to 1.5 mm.

The combination of the properties found enables, in particular, the use of the composition according to the invention for a fire protection coating in paintable, sprayable or rollable paints.

The fire protection coating obtained from the applied fire protection composition preferably has a layer thickness of 0.1 to 4 mm, preferably 0.3-2 mm, in particular 0.5 to 1.5 mm. In a further aspect, the invention comprises a method for coating heat-stable substrates comprising the steps: i) Applying a fire protection composition as described above to the surface of a heat-stable substrate S1, in particular a metal substrate, particularly preferably an aluminum substrate, around a coated heat-stable one To obtain substrates S1; ii) heating the coated, heat-stable substrate S1 to a temperature of 140-220 ° C., in particular 140-200 ° C., preferably between 160 and 190 ° C., in particular for 10-60 min, particularly preferably for 20-45 min .

Step i) takes place before step ii). In particular, the heat-stable substrate S1 involves metals and plastics such as ABS, polyamide, polyphenylene ether, composite materials such as SMC, unsaturated polyester GRP, epoxy or acrylate composite materials. The substrates are preferably made of metal. The preferred metals are above all steel, in particular electrolytically galvanized, hot-dip galvanized, oiled steel, Bonazink-coated steel, and subsequently phosphated steel, as well as aluminum, in particular in the variants typically found in automobile construction. It is particularly preferably a substrate made of aluminum. It can be advantageous that a step i ′) is carried out before step i) and step ii), the coated heat-stable substrate S1 being brought into contact with a cathodic dip painting solution, in particular at one temperature between 20 and 100 ° C, in particular between 20 and 80 ° C; preferably between 40 and 75 ° C., in particular for 1-15 min, particularly preferably for 1-5 min.Preferred coating solutions are described, for example, as cationic electrodeposition paints in Römpp Chemie Lexikon, online version, Georg Thieme Verlag, accessed on December 14 2018. In Table 3, however, it was found that the composition according to the invention has good corrosion resistance. Because of the cost and time savings, it can therefore be advantageous if no step i ′) is carried out before step i) and ii).

It can also be advantageous that the heat-stable substrate S1 does not undergo any pretreatment before step i), in particular no mechanical pretreatment and / or a pretreatment by applying an adhesion promoter composition, in particular not at the locations on the surface of the heat-stable substrate S1 on which in step i) the fire protection composition is applied.

In Table 3 it was found that the composition according to the invention has good adhesion to aluminum, in particular without the aluminum substrate having undergone mechanical pretreatment or an adhesion promoter composition being applied to it.

It can also be advantageous that after step i) the applied fire protection coating has a layer thickness of 0.1-4 mm, preferably 0.3-2.0 mm, in particular 0.5-1.5 mm.

It can furthermore be advantageous that the heat-stable substrate S1 is a body with a height of 10-60 cm, in particular 20-40 cm, a width of 50-500 cm, in particular 150-300 cm, and a depth from 50 - 700 cm, especially 250 - 500 cm. The body is particularly preferably a container for batteries, in particular batteries for driving means of transport, in particular automobiles.

It can also be advantageous that in step i) the fire protection coating is applied by spraying, brushing or rolling, in particular by spraying. Components A and B are preferably mixed before the fire protection coating is applied. In a further aspect, the invention comprises the use of a fire protection composition as described above for coating heat-stable substrates, especially metal substrates, especially preferably aluminum substrates, especially preferably heat-stable substrates in the shell of means of transport.

Examples

The invention will now be explained in more detail by means of examples. These are intended to further illustrate the invention, but in no way limit the scope of the invention.

Compositions Z7-Z4 and Rf.1-Rf.7 consisting of the ingredients in parts by weight according to the information in Table 2 and Table 3 were produced. The compositions Rf1-Rf.7 are comparative examples.

Table 1, raw materials used

Table 2, composition of component A, quantities in parts by weight

Description Method Mixing and application of the composition Components A and B were mixed in a weight ratio of 13.3: 1.

The two components were mixed briefly by hand, then for 30 seconds at 2000 revolutions / s in a speed mixer and applied. The layer thickness applied to the primed automotive sheet metal was between 500 pm and 2000 pm. The wet layer thickness corresponds to the dry layer thickness.

Component A had an EP value of 0.137 g / 100 g, component B an amine number of 415 mg KOH / g. The stoichiometric ratio of the blended composition was 103%. Description of method and analysis of mass loss

The composition Z1 was examined by means of thermogravimetry (TGA) with the real parameters from the baking cycle of an automobile manufacturer in Germany.

The following parameters were used on a vacuum-tight thermo-microbalance (TG 209 F1 Libra from Netzsch):

Start temperature: 40 ° C, heating rate: 10K / min

Final temperature: 150 ° C, 165 ° C, 175 ° C, 190 ° C and 200 ° C / isothermal hold 50 min each) Weight: approx. 15 mg

Atmosphere: synthetic air crucible: AI2O3 flow rate: 40 ml / min It has been found that the composition Z1 only has a mass loss after heating of 1.6% by weight and after a subsequent isotherm of 50 min. at 175 ° C of 5.6% by weight. Similarly low values were also determined for isotherms of 150, 165, 190 and 200 ° C.

These low mass losses during the baking process are advantageous for the productive value, since hardly any additional emissions result from the composition Z1. State-of-the-art products show significantly higher mass losses.

Description method and analysis viscosity

The viscosity was measured with a Physica MCR 301 plate-plate rheometer at 20 ° C., with a measuring gap of 0.5 mm in accordance with DIN 53019-1. The viscosity was determined at a shear rate of 100 1 / sec. The following evaluation was used in Table 3:

«++» = 20-60 mPas «+» = 15-100 mPas «-» => 150 mPas Description method and analysis Corrosion resistance

For the corrosion protection test according to ISO 9227 NSS and ISO 6270-1, test specimens were produced as follows:

Steel plates with surface preparation Sa 2 and a surface roughness of 50-70 μm were used as substrates. The following tests were then carried out:

- Adhesive tension measurement according to DIN EN ISO 4624,

- Under-rusting at the scratch according to DIN EN ISO 12944,

-Bubble formation (DIN EN ISO 4628-2) / rust formation (DIN EN ISO 4628-3).

In the test of 480h salt fog test and 720h condensed water climate, the composition Z1 proved to be particularly resistant to corrosion and climatic conditions.

The following evaluation was used in Table 3:

«+» = Blistering 0 SO, under-rusting at the scratch <3.0mm «-» = blistering> 0 SO, or under-rusting at the scratch> 3.0mm

Description method and analysis liability

Adhesive tension measurement according to DIN EN ISO 4624. In this case, 20 mm adhesive tension stamps were glued to the coating surface and, after curing for 24 hours at room temperature, peeled off using an Elcometer 510 hydraulic tension test machine. The device automatically displays the adhesive tensile strength in MPa or N / mm ² . The adhesive tensile values of the composition Z1 on blasted steel are in the range of 10 N / mm ² .

The following evaluation was used in Table 3:

«+» = Adhesive tensile values> 8 N / mm ² «-» = adhesive tensile values <8 N / mm ² Description of method and analysis of fire protection

During development, the fire resistance of the composition was initially tested in accordance with EN 13501-2 and the test method from EN13381 -8: 2010. The compositions Z1 and Z4 showed a good insulation effect against the heat input on the substrate and a good stability against falling or flying away due to turbulence in the fire. This was given the rating (+) in Table 3. Compositions which exhibited a reduced insulating effect and / or stability were given the rating (-).

Table 3, compositions of component B and measurement results, quantities in parts (weight), n.a. = not determined.

Claims

Fire protection composition comprising a component A and a

Component B; where component A:

-10-70, in particular 15-50, 15-30, preferably 15-25% by weight of at least one liquid epoxy resin which on average has more than one epoxy group per molecule A1, based on the total weight of component A;

-10-70, in particular 20-60, 30-50, preferably 35-45,% by weight ammonium polyphosphate A2, based on the total weight of component A; and component B:

- At least one adduct B1 from (i) at least one polyamine with at least three amine hydrogens reactive towards epoxide groups with (ii) at least one epoxide:

At least one aliphatic primary diamine B2 containing ether groups, in particular a polyoxyalkylenediamine;

- At least one aliphatic or cycloaliphatic primary diamine B3, preferably the at least one aliphatic or cycloaliphatic primary diamine B3 is free of ether groups;

- preferably at least one tertiary amine B4; comprises, the weight ratio of B1: B2: B3 = 1: 1.0-2.0: 1.5-3.5, in particular 1: 1.2-1.8: 2.0-3.0, preferably 1: 1.25-1.75: 2.25-2.8, particularly preferably 1: 1.3 -1 .6: 2.25-2.8, is.

Fire protection composition according to claim 1, characterized in that the weight ratio of B1: B2: B3: B4 = 1: 1.0-2.0: 1.5-3.5: 0.15-1.2, in particular 1: 1.

2-1.8: 2.0-3.0: 0.3-1.0, preferably 1: 1.25-1.75: 2.25-2.8: 0.4-0.8, particularly preferably 1: 1.3-1 .6: 2.25-2.8: 0.5-0.6.

3. Fire protection composition according to one of the preceding claims, characterized in that the liquid epoxy resin A1, which has an average of more than one epoxy group per molecule, has the formula (I) where the substituents R ′ and R ″ independently of one another either stand for Fl or CFh and the index r stands for a value from 0 to 1, in particular for a value of less than 0.2.

Fire protection composition according to one of the preceding claims, characterized in that component A consists of 1-15, in particular 1-10, 2-8, preferably 2-5,% by weight of at least one epoxy group-bearing reactive diluent A3, in particular selected from the group consisting of of flexandioldiglycidyl ether, cresyl glycidyl ether, p-tert-butylphenyl glycidyl ether, polypropylene glycol diglycidyl ether and polyethylene glycol diglycidyl ether, based on the total weight of component A.

Fire protection composition according to one of the preceding claims, characterized in that component A 1-10, in particular special 5-10,% by weight of at least one triaryl phosphoric acid ester or trialkyl phosphoric acid ester A4, in particular a trialkyl phosphoric acid ester, preferably a trialkyl phosphoric acid ester selected from the group consisting of trimethyl phosphate, triethyl phosphate, triisobutyl phosphate, tributyl phosphate, tris-2-chloro-ethyl phosphate, tris-2-ethyl-hexyl phosphate, tris-2-butoxy-ethyl phosphate, most preferably triisobutyl phosphate on the total weight of component A.

6. Fire protection composition according to one of the preceding claims, characterized in that component A at least 1-10, in particular 2-6, preferably 1.5-3% by weight of at least egg nem acrylate A5 with an acrylate functionality of at least 2, before preferably between 2 and 6, more preferably between 3 and 5, based on the total weight of component A.

7. Fire protection composition according to one of the preceding claims, characterized in that the adduct B1 is an adduct of (i) at least one polyamine with at least three amine hydrogens which are reactive towards epoxide groups and selected from the list consisting of ethylenediamine, propylenediamine and butylenediamine with (ii) at least one aromatic monoepoxide is involved; it is particularly preferably an adduct of 1,2-propylenediamine with cresyl glycidyl ether.

8. Fire protection composition according to one of the preceding claims, characterized in that the at least one aliphatic primary diamine B2 containing ether groups has an average molecular weight of 200-600 g / mol, in particular 200-450 g / mol, particularly preferably 250 -350 g / mol.

9. Fire protection composition according to one of the preceding claims, characterized in that the at least one aliphatic or cycloaliphatic primary diamine B3 is a cycloaliphatic primary diamine, in particular 1,3-bis (aminomethyl) cyclohexane.

10. Fire protection composition according to one of the preceding claims, characterized in that the at least one tertiary amine B4 is a Mannich base, in particular 2- (Dimethylaminomethyl) phenol or 2,4,6-tris (dimethylaminomethyl) phenol.

11. Fire protection composition according to one of the preceding claims, characterized in that the (ii) at least one epoxide of the adduct B1 is aromatic monoepoxides, in particular cresyl glycidyl ether, tert-butylphenyl glycidyl ether or the glycidyl ether of cardanol, particularly preferred is cresyl glycidyl ether.

12. Fire protection composition according to one of the preceding claims, characterized in that the two components A and B, in particular before the use of the fire protection composition, are present as separate components.

13. Use of a fire protection composition according to one of the preceding claims for coating heat-stable substrates, in particular metal substrates, particularly preferably aluminum substrates, particularly preferably heat-stable substrates in the shell construction of means of transport.

14. A method for coating heat-stable substrates comprising the

Steps i) applying a fire protection composition according to any one of claims 1 to 12 to the surface of a heat-stable substrate S1, in particular a metal substrate, particularly preferably an aluminum substrate, in order to obtain a coated, heat-stable substrate S1; ii) heating the coated, heat-stable substrate S1 to a temperature of 140-220 ° C., in particular 140-200 ° C., preferably between 160 and 190 ° C., in particular for 10-60 min, particularly preferably for 20-45 min .

15. The method according to claim 14, wherein a step i ') is carried out before step i) and step ii), the coated heat-stable substrate S1 being brought into contact with a KTL coating solution, in particular at a temperature between 20 and 100 ° C , in particular between 20 and 80 ° C; preferably between 40 and 75 ° C., in particular for 1-15 min, particularly preferably for 1-5 min.

16. The method according to claim 14 or 15, wherein prior to step i) the heat-stable substrate S1 does not undergo any pretreatment, in particular no mechanical pretreatment and / or a pretreatment by applying an adhesion promoter composition, in particular not at the locations on the surface of the heat-stable substrate S1, to which the fire protection composition is applied in step i).

17. The method according to any one of claims 14-16, wherein after step i) the applied fire protection coating has a layer thickness of 0.1-4 mm, preferably 0.3-2.0 mm, in particular 0.5 to 1.5 mm having.