FIRE PROTECTION COMPOSITION

Abstract

The present invention relates to a fire protection composition comprising a component A and a component B. Component A comprises an epoxy liquid resin and ammonium polyphosphate. Component B comprises an adduct B1 of (i) at least one polyamine having at least three amine hydrogens reactive toward epoxide groups with (ii) at least one epoxide, 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, and after passing through burning-in ovens in the automotive industry still shows good fire protection values with a low mass loss and is suitable for spray application.

Claims

1. A fire protection composition comprising a component A and a component B; wherein the component A comprises: 10-70 wt % of at least one liquid epoxy resin having an average of more than one epoxy group per molecule A1 based on the total weight of the component A; 10-70 35-45 wt % ammonium polyphosphate A2, based on the total weight of the component A, and the component B comprises: at least one adduct B1 from (i) at least one polyamine having at least three amine hydrogens reactive toward epoxide groups with (ii) at least one epoxy: at least one aliphatic primary diamine B2 containing ether groups; at least one aliphatic or cycloaliphatic primary diamine B3; preferably at least one tertiary amine B4, wherein the weight ratio of B1:B2:B3=1:1.0-2.0:1.5-3.5.

2. The fire protection composition of claim 1, wherein the weight ratio of B1 is: B2:B3:B4=1:1.0-2.0:1.5-3.5:0.15-1.2.

3. The fire protection composition of claim 1, wherein the epoxy liquid resin A1 having on average more than one epoxy group per molecule has the formula (I) ##STR00004## wherein the substituents R′ and R″ independently of one another represent either H or CH.sub.3, and the index r represents a value of 0 to 1.

4. The fire protection composition of claim 1, wherein component A has 1-15 wt % of at least one epoxy group-bearing reactive diluent A3 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.

5. The fire protection composition of claim 1, wherein component A has 1-10 wt. % of at least one triaryl phosphoric acid ester or trialkyl phosphoric acid ester A4 selected from the group consisting of trimethyl phosphate, triethyl phosphate, triisobutyl phosphate, tributyl phosphate, tris-2-chloroethyl phosphate, tris-2-ethyl-hexyl phosphate, tris-2-butoxyethyl phosphate, most preferably triisobutyl phosphate, based on the total weight of component A.

6. The fire protection composition of claim 1, wherein component A has at least 1-10 wt % of at least one acrylate A5 having an acrylate functionality of at least 2, based on the total weight of component A.

7. The fire protection composition of claim 1, wherein adduct B1 is an adduct of (i) at least one polyamine having at least three amine hydrogens reactive toward epoxide groups selected from the group consisting of ethylenediamine, propylenediamine and butylenediamine with (ii) at least one aromatic monoepoxide.

8. The fire protection composition of claim 1, wherein the at least one ether group-containing aliphatic primary diamine B2 has an average molecular weight of 200-600 g/mol.

9. The fire protection composition of claim 1, wherein the at least one aliphatic or cycloaliphatic primary diamine B3 is a cycloaliphatic primary diamine, in particular 1,3-bis(aminomethyl)cyclohexane.

10. The fire protection composition of claim 1, wherein the at least one tertiary amine B4 is a Mannich Base.

11. The fire protection composition of claim 1, wherein the (ii) at least one epoxide of the adduct B1 is aromatic monoepoxide.

12. The fire protection composition of claim 1, wherein the two components A and B, in particular before the use of the fire protection composition, are present as components separated from one another.

13. A coated heat-stable article, comprising the fire protection composition of claim 1 applied to a metal substrate.

14. A method for coating heat-stable substrates, comprising the steps of i) applying a fire protection composition according to claim 1 to the surface of a heat-stable substrate S1 in order to obtain a coated heat-stable substrate S1; ii) heating of the coated heat-stable substrate S1 to a temperature of 140-220° C. for 10-60 min.

15. The method according to claim 14, wherein before step i) and step ii) a step i′) is carried out, wherein the coated heat-stable substrate S1 is brought into contact with a CDC coating solution at a temperature between 20 and 100° C. for 1-15 min.

16. The method according to claim 14, wherein before step i) the heat-stable substrate S1 does not undergo any pretreatment at the locations of the surface of the heat-stable substrate S1 on which the fire protection composition is applied in step i).

17. The method according to claim 14, wherein after step i) the applied fire protection coating has a layer thickness of 0.1-4 mm.

Description

EXAMPLES

[0112] The invention will now be explained in more detail with reference to examples. These are intended to further illustrate the invention, but in no way limit the scope of the invention.

[0113] Compositions Z1-Z4 and Rf.1-Rf.7 consisting of the ingredients in parts by weight were prepared according to the data in Table 2 and Table 3. The compositions Rf1-Rf.7 are comparative examples.

TABLE-US-00001 TABLE 1 Raw materials used Trade name, manufacturer Component A Liquid epoxy resin A1 Araldite ® PY 304, Huntsman Ammonium polyphosphate A2 Exolit ® AP 422, Clanant Reactive diluent A3 Araldite ® DY-H, Huntsman Advanced Materials GmbH, Switzerland Triisobutyl phosphate A4 Lanxess AG, Germany Trimethylolpropane triacrylate BASF SE, Germany A5 Melamine (1,3,5-triazine- OCI, Netherlands 2,4,6-triamine) A6 Component B Adduct B1 Adduct of 1,2-propylenediamine with cresyl glycidyl ether Diamine B2-1 Jeffamine ® D-230, Huntsman Advanced Materials GmbH, Switzerland Diamine B2-2 Jeffamine ® D-400, Huntsman Advanced Materials GmbH, Switzerland Diamine B3 1,3-bis(aminomethyl)cyclohexane, Itochu MXDA Aromatic primary diamine Tertiary amine B4 Mannich Base Salicylic acid Salicylic acid

TABLE-US-00002 TABLE 2 Composition component A, quantitative data in parts by weight Component A Wt. % 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 oxide) 6.2 Rheology additive 0.7 Fibers (Carbon and metal fibers) 4.4 Total 100

[0114] Description Method of Mixing and Applying the Composition

[0115] The components A and B were mixed in the weight ratio 13.3:1. The two components were briefly mixed by hand, then for 30 seconds at 2000 rpm in a speed mixer and applied. The applied layer thickness on the primed automobile sheet plates was between 500 μm and 2000 μm. The wet layer thickness corresponds here to the dry layer thickness.

[0116] Component A had an EP value of 0.137 g/100 g, the component B had an amine value of 415 mg KOH/g. The stoichiometric ratio of the mixed composition was 103%.

[0117] Description Method and Analysis of Mass Loss

[0118] Composition Z1 was analyzed by thermogravimetry (TGA) using the real parameters from the burn-in cycle of an automotive manufacturer in Germany.

[0119] The following parameters were used on a vacuum-tight thermo-microbalance (TG 209 F1 Libra from Netzsch): [0120] Start temperature: 40° C. [0121] Heating rate: 10 K/min [0122] End temperature: 150° C., 165° C., 175° C., 190° C. and 200° C./isothermal hold in each case 50 min) [0123] Weight of sample taken: approx. 15 mg [0124] Atmosphere: synthetic air [0125] Crucible: Al.sub.2O.sub.3 [0126] Flow: 40 ml/min

[0127] It has been found that the composition Z1 had only a mass loss after heating of 1.6 wt % and after a subsequent isotherm of 50 minutes at 175° C. of 5.6 wt %. Similarly small values were also determined for isotherms of 150, 165, 190 and 200° C.

[0128] These low mass losses during the burning-in are advantageous for the produced value, since hardly any additional emissions are produced by the composition Z1. Products of the prior art show significantly higher mass losses.

[0129] Description Method and Analysis of Viscosity

[0130] The Viscosity was measured with a Physica MCR 301 plate-plate Rheometer at 20° C. with a measuring gap of 0.5 mm according to DIN 53019-1. The viscosity was determined at a shear rate of 100 1/sec.

[0131] The following evaluation was used in Table 3: [0132] ++=20-60 m Pas [0133] +=15-100 mPas [0134] −=>150 mPas

[0135] Description Method and Analysis of Corrosion Resistance

[0136] For the Corrosion Protection Test According to ISO 9227 NSS and ISO 6270-1, sample bodies were produced as follows: [0137] Substrates used were steel plates with surface preparation Sa 2½ and a roughness depth of 50-70 μm. [0138] Thereafter, the following tests were performed: [0139] Adhesive measurement according to DIN EN ISO 4624, [0140] Rust creepage at the scirbe according to DIN EN ISO 12944, [0141] Blistering (DIN EN ISO 4628-2)/rusting (DIN EN ISO 4628-3).

[0142] In the test of 480 h salt fog test and 720 h condensed water climate, the composition Z1 proved to be particularly resistant to corrosion and climate.

[0143] The following evaluation was used in Table 3: [0144] «+»=Blistering 0 S0, rust creepage at the scirbe<3.0 mm [0145] «-»=Blistering>0 S0, or rust creepage at the scirbe>3.0 mm

[0146] Description Method and Analysis of Adhesion

[0147] Adhesive measurement according to DIN EN ISO 4624. For this purpose, 20 mm adhesive tensile stamps were bonded to the coating surface and, after curing for 24 h at room temperature, removed using a hydraulic adhesive tensile testing machine, type Elcometer 510. The device automatically displays the adhesive tension value in MPa or N/mm.sup.2. The adhesive tensile values of composition Z1, on blasted steel are in the range of 10 N/mm.sup.2.

[0148] The following evaluation was used in Table 3: [0149] +=adhesive tensile values>8 N/mm.sup.2 [0150] −=adhesive tensile values<8 N/mm.sup.2

[0151] Description Method and Analysis of Fire Protection

[0152] In the development, the fire resistance of the composition was first tested according to EN 13501-2 and according to the test method from EN 13381-8:2010. The compositions Z1 and Z4 showed a good insulation effect against the heat input onto the substrate and good stability against falling off or flying away due to turbulence in the fire. This has been given a rating of (+) in Table 3. Compositions which had a reduced insulation effect and/or stability were given a rating of (−).

TABLE-US-00003 TABLE 3 compositions of component B and measurement results, quantitative data in parts (weight), n.d. = not determined. Z1 Rf. 1 Z2 Rf. 2 Z3 Rf. 3 Rf. 4 Rf. 5 Rf. 6 Z4 Rf. 7 Component B Adduct B1 17.5 0 17.5 17.5 17.5 2.9 17.5 17.5 17.5 17.5 17.5 Diamine B2-1 25 25 10 25 25 25 13 25 25 10 25 Diamine B2-2 15 Diamine B3 45 45 45 0 45 45 45 10 45 45 MXDA 45 Tertiary 10 10 10 10 0 10 10 10 10 10 amine B4 Salicylic acid 10 Total (parts) 97.5 80 82.5 52.5 87.5 82.9 85.5 62.5 97.5 97.5 97.5 Weight ratio 1:1.4:2.6:0.6 1:0.6:2.6:0.6 1:1.4:0:0.6 1:1.4:2.6:0 1:8.6:15.5:3.4 1:0.7:2.6:0.6 1:1.4:0.6:0.6 1:1.4:2.6:0.6 B1:B2:B3:B4 Adhesion + − + + + − + + + + n.d. Viscosity ++ + − − + + − − − + − Weathering + − − + + − − + − − + Fire Protection + − − − n.d. − − − n.d. + n.d.