Method for producing fireproof materials based on sodium silicate

Abstract

The present invention concerns a process for the production of a solid fire protection material. The composition for producing the fire protection material contains at least one water glass and microcapsules provided with propellant gas. The fire protection material is formed by expanding the microcapsules or by breaking the polymer material of the shell of the microcapsules by the influence of temperature or by adding an agent which breaks the shell of the microcapsules.

Claims

1. A process for producing a solid fire protection material, the process comprising: (1) providing a composition comprising at least one water glass and at least one propellant-provided microcapsule having a propellant-provided core and a polymer material as a shell, wherein the microcapsules comprise at least 20 wt. % propellant, based on dry weight; and (2) contacting the microcapsules with (a) a swelling agent comprising propylene carbonate or (b) a shell breaking agent comprising propylene carbonate in order to swell the microcapsules and/or break the polymer material of the shell of the microcapsules.

2. The process according to claim 1, wherein the mass ratio between the at least one water glass and the at least one microcapsule provided with the propellant is from 5.0 to 30.0.

3. The process according to claim 1, wherein the polymer material is selected from the group consisting of copolymers, copolymers of acrylonitrile, methacrylate and/or acrylate, vinylidene chloride copolymers and vinylidene chloride-acrylonitrile copolymers.

4. The process according to claim 1, wherein the at least one water glass comprises at least one potassium water glass.

5. The process according to claim 1, wherein a propellant release of the composition takes place after the addition of a shell-breaking agent in a timeframe of 20 seconds to 20 minutes.

6. The process according to claim 1, wherein the composition further comprises at least one of (a) at least one component supporting the ceramization of the composition at elevated temperatures; and (b) at least one organic fibre.

7. The process according to claim 6, wherein the at least one component that supports the ceramization at elevated temperatures is present and is selected from the group consisting of mineral additives, aluminium hydroxide, filter dust, fly ash, ceramic hollow spheres, hollow glass spheres, foam glass granules, slate flour, quartz flour, mica, wollastonite, calcium carbonates, kaolin, vermiculite and ettringite.

8. The process according to claim 6, wherein the at least one organic fibre is present and is selected from the group consisting of polyalkylene fibres, polyethylene fibres, polypropylene fibres; acrylic fibres: aramid fibres; polyamide fibres, polyhexamethylene diadipamide fibres, polycaprolactam fibres, aromatic polyamide fibres, partially aromatic polyamide fibres; partially aromatic polyester fibres, and wholly aromatic polyester fibres.

9. The process according to claim 1, wherein the solid fire protection material is in the shape of a fire protection panel.

10. The process according to claim 1, wherein the composition further comprises at least one of: (1) at least one component which leads to hardening and/or binding of the composition; (2) at least one component which has a moisture-retaining and/or hygroscopic property; and (3) at least one silicic acid.

11. The process according to claim 1, wherein the fire protection material obtained has a density of less than 0.6 g/cm.sup.3.

12. The process according to claim 1, wherein the propellant comprises a propellant gas selected from the group consisting of hydrocarbons, methane, ethane, propane, n-butane, isobutane, pentanes, n-pentane, iso-pentane, neopentane; chlorofluorocarbons, trichlorofluoromethane, dichlorodifluoromethane; dimethyl ether; carbon dioxide, nitrogen, air, and mixtures thereof.

13. A composite material, the composite material comprising: the fire protection material obtained according to claim 1, and at least one carrier material.

14. The composite material according to claim 13, wherein the at least one carrier material is selected from the group consisting of non-woven materials; paper materials and cardboard materials, paper honeycombs; plastic materials; metal materials, metal foils, aluminium foils; glass materials, glass foils, glass wool; cotton fabrics; wood materials; mineral wool; materials of extruded polystyrene foam, polyurethane foam, polyethylene foam and polypropylene foam; materials of jute, flax, hemp and cellulose fibres; and textile materials.

15. The composite material according to claim 13, wherein the fire protection material is in the form of plates, cuboidal bodies, bricks, concave or convex bodies or tubular bodies.

16. The composite material according to claim 13, further comprising at least one layer applied to the at least one carrier material.

17. The composite material according to claim 16, wherein the at least one layer is selected from the group consisting of an aluminium foil, a glass fleece, a paper, and cardboard material.

18. A composite material, the composite material comprising: (1) a first layer selected from the group consisting of an aluminium foil, a glass fleece, a paper, a cardboard material, and a composite thereof; (2) a second layer selected from the group consisting of fleece materials; paper materials and cardboard materials, paper honeycomb; plastic materials; metal materials, metal foils, aluminium foils; glass materials, glass foils and glass wool; cotton fabrics; wood materials; mineral wool; materials made of extruded polystyrene foam, polyurethane foam, polyethylene foam and polypropylene foam; materials made of jute, flax, hemp and cellulose fibres; and textile materials; and (3) a third layer selected from the group consisting of an aluminium foil, a glass fleece, a paper, a cardboard material, and a composite thereof; wherein the composite material is constructed such that that the first layer is provided on a first side of the second layer and the third layer is provided on a second side of the second layer and the fire protection material obtained according claim 16 is provided on one or both sides of the second layer.

19. A fire protection material, the fire protection material comprising: the composition according to (1) or (1′) of claim 1, and at least one carrier material, wherein the composition is either applied to the at least one carrier material, or the at least one carrier material is impregnated with the composition.

20. A method of protecting from fire or heat a surface, structure or object, selected from the group consisting of doors, walls, floors, ceilings, openings, penetrations, tunnels, tubes, ships, vehicles, wagons, containers, cables, electronics, personal protective clothing, furnaces, the method comprising applying to the surface structure or object, fire protection material of claim 1.

21. The process of claim 1, wherein swelling the microcapsules and/or breaking the polymer material of the shell of the microcapsules by the addition of propylene carbonate is effected at ambient temperature, without the application of heat.

22. The process of claim 1, wherein one sodium silicate glass is present, and wherein a weight ratio of SiO.sub.2 to Na.sub.2O is within the range of 2.3 to 3.8.

23. The process of claim 22, wherein a density of the solid fire protection material is within the range of 1300 to 1600 kg/m.sup.3.

24. The process of claim 22, wherein a water content of the solid fire protection material is within the range of 50 to 70 wt. %.

25. The process of claim 1, wherein the composition comprises at least two different sodium silicate glasses, the first sodium silicate glass having a viscosity of 1000 to 2400 mPa*s (20° C.) and the second sodium silicate glass having a viscosity of 75 to 250 mPa*s (20° C.).

26. The process of claim 25, wherein the first sodium silicate glass has at least one other of the following properties: (1) weight ratio of SO.sub.2 to Na.sub.2O within the range of 2.3 to 2.6; and/or (2) density within the range of 1500 to 1600 kg/m.sup.3; and/or (3) water content within the range of 50 to 55 wt. %.

27. The process of claim 25, wherein the second sodium silicate glass has at least one of the following characteristics: (1) weight ratio of SiO.sub.2 to Na.sub.2O, within the range of 2.8 to 3.8; and/or (2) density within the range of 1300 to 1500 kg/m.sup.3.

Description

EXPERIMENTS

(1) Viscosity Measurement and Viscosities of Water Glasses

(2) The viscosities of the water glasses used were measured as follows:

(3) TABLE-US-00001 TABLE 1 Details on the determination of viscosity and viscosities of various water glasses. Water Measuring glass Spindle RPM range Temperature Viscosity Na-WG1 L 3 100 47.50% 20° C. 569 mPa * s Na-WG2 L 2 100 51.90% 20° C. 156 mPa * s K-WG1 L 2 200 48.90% 20° C. 73 mPa * s K-WG2 L 2 200 26.60% 20° C. 39 mPa * s
Definition of the Water Glasses Used

(4) Na-WG1 is a sodium silicate glass which, in addition to the above viscosity, has a sodium silicate content of about 50% to a maximum of 100% and a density (at 20° C.) of about 1.5 g/mL. The pH value (100 g/L at 20° C.) is about 13.

(5) Na-WG2 is a sodium silicate glass which, in addition to the above viscosity, has a sodium silicate content of about 25% to a maximum of 40% and a density (at 20° C.) of about 1.4 g/mL. The pH value (100 g/L at 20° C.) is about 11.

(6) K-WG1 is a potassium water glass which, in addition to the above viscosity, has a density (at 20° C.) of about 1.3 g/mL. The pH value (100 g/L at 20° C.) is about 11.

(7) K-WG2 is a potassium water glass which, in addition to the above viscosity, has a density (at 20° C.) of about 1.3 g/mL. The pH value (100 g/L at 20° C.) is about 11.

(8) Definition of the Used Other Components (in the Experiments)

(9) The component “Al(OH).sub.3 mixture” is a mixture of Al(OH).sub.3 with various other oxides, such as sodium oxide, iron oxide and silicon dioxide. Al(OH).sub.3 is the main component with over 99%.

(10) The component “expanded granules A” are (surface-treated) hollow glass spheres whose material consists of >95% silicon dioxide and which start to soften at about 1300° C. (in the cluster). Expanded granulate A has a pH value of 5 to 8.

(11) The component “expanded granulate B” is an expanded glass granulate with the following properties: grain size of 0.25 to 0.5 mm, bulk density of 340 (±30) kg/m.sup.3, raw grain density of 700 (±80) kg/m.sup.3, whereby the raw grain density was tested according to DIN V 18004 and calculated according to EN 1097-6, average grain strength of 2.6 N/mm2, whereby the grain strength was determined according to DIN EN 13055-1. The expanded granulate B consists (based on a sample dried at 105° C.) of about 70 to 75% SiO2, 10 to 15% Na.sub.2O, 7 to 11% CaO, 0.5 to 5% Al.sub.2O.sub.3, 0 to 5% MgO and 0 to 4% K.sub.2O. The “expanded granulate B” begins to soften at about 700° C. It has a pH value of 8 to 11.

(12) The component “microcapsule A” is a dry, unexpanded microcapsule filled with propellant gas. They comprise about 20 to 30% of the propellant isobutane, about 1 to 5% magnesium hydroxide and about 60 to 80% of a copolymer. The average particle size is 10 to 16 μm and the density is ≤12 kg/m.sup.3. The propellant gas is released in a temperature range of 80 to 95° C.

(13) The component “microcapsule B” is a dry, non-expanded microcapsule filled with propellant gas. They comprise about 13% of a propellant gas, about 0 to 20% amorphous silica and about 60 to 90% of a copolymer. The average particle size is 10 to 16 μm and the density is ≤17 kg/m.sup.3. The propellant gas is released in a temperature range of 94 to 99° C.

(14) The component “microcapsule C” is a dry, unexpanded microcapsule filled with propellant gas. They contain about 15 to 20% of the propellant isopentane and over 75% of a copolymer. The average particle size is 10 to 16 μm and the density is ≤17 kg/m.sup.3. The propellant gas is released in a temperature range from 123 to 133° C.

(15) The component “microcapsule D” is a dry, unexpanded microcapsule filled with propellant gas. They contain about 15 to 20% of the propellant isopentane, over 60% of a copolymer and about 0 to 20% magnesium hydroxide. The average particle size is 28 to 38 μm and the density is ≤14 kg/m.sup.3. The propellant gas is released in a temperature range of 122 to 132° C.

(16) The component “copolymer dispersion A” is an aqueous copolymer dispersion based on vinyl acetate/vinyl ester. Emulsifiers and cellulose derivatives serve as stabilizers for the dispersion.

(17) The component polyethylene fibre A is a fibre made of HD-PE.

(18) The component “dispersant A” is a solution of a high molecular anionic copolymer in water.

(19) The component “surfactant mixture A” is a medium viscous mixture of various polyglycol esters. The density of the mixture (at 20° C.) is about 1.0 g/mL, the dynamic viscosity (at 20° C., measured according to DIN EN ISO 3219) is about 120 mPas and the pH value (of 2% in distilled water) is about 6.5.

(20) The component “marble powder A” is a marble powder with a mean particle diameter of 2.5 μm.

(21) The component “marble powder B” is a marble powder with a mean particle diameter of 5 μm.

(22) The component “marble powder C” is a marble powder with a mean particle diameter in a range of 12 μm to 15 μm.

(23) The component vermiculite is expanded vermiculite. The main components of this aluminium magnesium iron silicate are (approx.) 43% to 46% SiO.sub.2, 9% to 12% Al.sub.2O.sub.3, 7% to 9% Fe.sub.2O.sub.3, 1% to 3% CaO, 24% to 27% MgO and 4% to 6% K.sub.2O. The particle size distribution is (each approx.): 50-75% of the product has a particle size smaller than 0.050 mm, 25-50% of the product has a particle size between 0.050 and 0.071 mm, 15-50% of the product has a particle size between 0.071 and 0.1 mm. The rest has larger grain sizes, whereby the proportion of product with grain sizes larger than 1 mm is at most (approx.) 1%.

(24) The component vermiculite powder is a corresponding vermiculite powder. The particle size is smaller than 50 micrometres and the specific surface is about 2.6 m.sup.2/g.

(25) The component glass fibre is a glass fibre with the following chemical composition (approx.): 62-68% SiO2, 26-32% CaO+MgO, less than 1% other components.

(26) The component ‘polyurethane dispersion’ is a non-ionic polyurethane system in water, the ratio of polyurethane to water being approximately 25 to 75. The polyurethane dispersion has a density (at 20° C.) of about 1.04 g/mL. The dynamic viscosity of the polyurethane dispersion is about 25000 mPas (according to DIN EN ISO 3219) and the pH value (2% in distilled water) is about 6.5.

Experiments

(27) The following experiments demonstrate the advantage of the method according to the invention.

(28) 1—Component System

(29) The following experiments relate to processes in which the expansion of the microcapsules takes place through the action of temperature.

(30) Test Group Water Resistance

(31) The increase in water resistance when potassium water glass is added to sodium silicate or when potassium water glass is used exclusively is illustrated by the following experiments (Tables 2A and 2B):

(32) TABLE-US-00002 TABLE 2A Water resistance of water glasses (* = non-inventive tests). Component 1-WR-1* 1-WR-2* 1-WR-3 1-WR-5 1-WR-6 1-WR-7 1-WR-8 Na—Si1 64 — — — — — — Na—Si2 — 64 32 28.2 25.6 22.4 19.2 K-WG1 — — 32 35.2 38.4 41.6 44.8 Al(OH).sub.3 mixture 10.4 10.4 10.4 10.4 10.4 10.4 10.4 Microcapsule A 6.4 6.4 6.4 6.4 6.4 6.4 6.4 Expanded 32 32 32 32 32 32 32 granulate A Copolymer 4.16 4.16 4.16 4.16 4.16 4.16 4.16 Dispersion Mass in g: 116.96 116.96 116.96 116.96 116.96 116.96 116.96 Amount potassium — — 27.36 30.10 32.83 35.57 38.30 water glass in relation to total formulation in %: Amount potassium — — 50 55 60 65 70 water glass in relation to total binding agent in %: Water resistance: 5 5 4 4 3-4 3-4 3-4

(33) TABLE-US-00003 TABLE 2B Water resistance of water glasses (* = non-inventive tests). Component 1-WR-9 1-WR-10 1-WR-11 1-WR-12 1-WR-13 1-WR-4* Na—Si1 — — — — — — Na—Si2 16 12.8 9.6 6.4 3.2 — K-WG1 48 51.2 54.4 57.6 60.8 64 Al(OH).sub.3 mixture 10.4 10.4 10.4 10.4 10.4 10.4 Microcapsule A 6.4 6.4 6.4 6.4 6.4 6.4 Expanded 32 32 32 32 32 32 granulate A Copolymer 4.16 4.16 4.16 4.16 4.16 4.16 Dispersion Mass in g: 116.96 116.96 116.96 116.96 116.96 116.96 Amount potassium 41.04 43.78 46.51 49.25 51.98 54.72 water glass in relation to total formulation in %: Amount potassium 75 80 85 90 95 100 water glass in relation to total binding agent in %: Water resistance: 3-4 2 2 2 2 2

(34) The composition of the respective tests was provided according to the mass ratios of the components given in the table and process step (2′) was carried out thermally at a furnace temperature of 86° C.

(35) The mouldings obtained were tested for water resistance. The evaluation was carried out on a scale from 1 (very good) to 6 (insufficient).

(36) The proportions of the individual components were identical in the experiments, or when several water glasses (1-WR-3 and 1-WR-5 to 1-WR-13) were used, the mass sum of the water glasses used was identical to the respective water glass of the other experiments. Therefore a direct comparison of the resulting fire protection materials is possible.

(37) The ratio of potassium water glass to sodium silicate glass was gradually increased in this test series from 0%, i.e. no potassium water glass present (in the experiments 1-WR-1 and 1-WR-2), to 100%, i.e. no sodium silicate glass present (in the experiment 1-WR-4).

(38) The water resistance improved (compared to pure sodium silicate glass in 1-WR-1 and 1-WR-2) with poor water resistance when the potassium water glass content was increased. This improvement can be divided into three groups:

(39) Group 1: When using 50% to 55% potassium water glass (1-WR-3 and 1-WR-5) a slight improvement is achieved, the resulting water resistance is sufficient.

(40) Group 2: A further improvement in water resistance was observed when using 60% to 75% potassium water glass. The water resistance is in the range between satisfactory and sufficient.

(41) Group 3: When using 80% to 100% potassium water glass (compared to all other groups) a significant improvement of water resistance was observed. The water resistance in this group is good.

(42) These experiments clearly show the increased water resistance of the mouldings increase the potassium water glass content in the composition. The use of at least 50% potassium water glass (based on the sum of the water glasses) is preferred, further preferred is the use of at least 60% potassium water glass, even further preferred is the use of more than 75% potassium water glass.

(43) Test Group Temperature

(44) The experiments in the following tables (Table 3, 4, 5a, 5b and 6) show the influence of microcapsules, water glass and temperature on the resulting moulding. In the experiments summarized in these tables, the respective composition (as listed) was provided (process step (1′)) and the consistency assessed. The compositions were then hardened in a ring (Ø4.5 cm) at the temperatures listed (process step (2′)).

(45) The temperature of the experiments in Table 3 is in accordance with the invention and amounts to 85° C., the temperature in the tables (4, 5a and 5b) is not in accordance with the invention (temperatures of greater than or equal to 90° C.). Table 6 contains comparative tests of a composition at different temperatures.

(46) After the process step (2′) the evaluation of the obtained mouldings is carried out. The evaluation included the assessment of the structure of the bottom area, the remaining structure, the colour, the swelling behaviour (which was carried out via the foam height, whereby a foam height of more than approx. 2 cm was evaluated as “strongly swelled”) and the consistency. The consistency was divided into powdery, brittle, granularly and soft.

(47) TABLE-US-00004 TABLE 3 Process at 85° C. and characterisation of the mouldings obtained (* = experiments not according to the invention). 1-Temp-1 1-Temp-2 (*) K-WG1 8 — Na-WG2 — 8 Al(OH).sub.3 mixture 1 1 Microcapsule A   0.8 0.8 Expanded granulate B 2 2 Consistency (before step (2′)) liquid, granular fluid Reaction temperature 85° C. 85° C. Bottom structure smooth smooth Remaining structure good uniform good uniform structure structure Colour creme white creme white Foam height ca. 2.4 cm ca. 2.2 cm swelling behaviour strongly swollen strongly swollen Consistency (after step (2′)) non-powdery light powdery

(48) TABLE-US-00005 TABLE 4 Comparative experiments (* = experiments not according to the invention) at 97° C. and characterization of the obtained mouldings. 1-CE- 1-CE- 1-CE- Temp-1(*) Temp-2(*) Temp-3(*) Na-WG1 — — 8 Na-WG2 — 8 — K-WG1 8 — — Al(OH).sub.3 mixture 1 1 1 Microcapsule B 0.8   0.8   0.8 Expanded granulate B 2 2 2 Consistency (before liquid, fluid viscous step (2′)) granular Reaction temperature 97° C. 97° C. 97° C. Bottom structure smooth hollow smooth Remaining structure internally large compact hollow rupture in structure the middle Colour faint faint faint reddish reddish reddish Foam height ca. 3.3 cm ca. 3.1 cm ca. 1.7 cm swelling behaviour strongly strongly little swollen swollen swollen Consistency (after non- non- non- step (2′)) powdery powdery powdery

(49) TABLE-US-00006 TABLE 5a Comparative experiments (* = experiments not according to the invention) at 125° C. and characterisation of the mouldings obtained. 1-CE- 1-CE- 1-CE- Temp-4(*) Temp-5(*) Temp-6(*) Na-WG2 — — 8 K-WG1 8 8 — Al(OH).sub.3 mixture 1 1 1 Microcapsule C   0.8 —   0.8 Microcapsule D —   0.8 — Expanded granulate B 2 2 2 Consistency (before liquid, liquid, fluid step (2′)) granular granular Reaction temperature 125° C. 125° C. 125° C. Bottom structure smooth smooth smooth Remaining structure good great great uniform rupture at rupture in structure the top the middle Colour strong red below faint red colour reddish, colour creme white at top Foam height ca. 1.5 cm ca. 3 cm ca. 1.6 cm swelling behaviour little strongly strongly swollen swollen swollen Consistency (after non- powdery Light step (2′)) powdery powdery

(50) TABLE-US-00007 TABLE 5b Comparative experiments (* = experiments not according to the invention) at 125° C. and characterisation of the mouldings obtained. 1-CE- 1-CE- 1-CE- Temp-7(*) Temp-8(*) Temp-9(*) Na-WG1 — 8 8 Na-WG2 8 — — Al(OH).sub.3 mixture 1 1 1 Microcapsule C —   0.8 — Microcapsule D   0.8 —   0.8 Expanded granulate B 2 2 2 Consistency (before fluid viscous viscous step (2′)) Reaction temperature 125° C. 125° C. 125° C. Bottom structure smooth smooth hollow Remaining structure large collapsed good uniform rupture in foam structure the middle Colour below strong red below reddish, colour reddish, creme creme white at white at top top Foam height ca. 2.5 cm ca. 1.0 cm ca. 1.5 cm swelling behaviour strongly approx, little swollen strongly swollen swollen, but collapsed Consistency (after powdery non-powdery non-powdery step (2′))

(51) Ideally, the product should be highly swollen, with a smooth bottom area and a residual structure that is good and uniform. Further preferred is the moulding not powdery or at most slightly powdery. Normally a creamy white colour of the moulded body is preferred.

(52) While the invention-related experiment 1-Temp-1 (Table 3) results in a product with ideal characteristics, mouldings from the comparative experiments (Tables 3, 4, 5a and 5b) are not ideal and exhibit various defects in one or more of the points bottom structure, remaining structure, swelling behaviour and consistency. The two tests in Table 3 differ from each other only in the type of glass used and show that the use of a potassium water glass results in a better consistency of the moulding compared to a sodium silicate glass.

(53) The significance of temperature is further illustrated by the following experiments. In these experiments, the experiment is performed with the same composition used in the “1-Temp-1” experiment at different temperatures:

(54) TABLE-US-00008 TABLE 6 Experiments with identical composition at different temperatures and characterization of the obtained mouldings (* = experiments not according to the invention). 1-Temp- 1-Temp- 1-Temp- Component 1-Temp-1 1A(*) 1B(*) 1C(*) K-WG1 8 8 8 8 Al(OH).sub.3 mixture 1 1 1 1 Microcapsule A 0.8 0.8 0.8 0.8 Expanded granulate B 2 2 2 2 Consistency liquid, liquid, liquid, liquid, (before granular granular granular granular step (2′)) Reaction 85° C. 90° C. 100-106° C. 110° C. temperature Bottom smooth rippled smooth rippled structure Remaining structure good uniform hollow at completely completely structure the bottom hollow hollow Colour creme creme creme creme white white white white Foam height approx. irregular, 2.5 cm 3.0 cm 2.4 cm one side 2.2 cm, another side 0.7 cm swelling strongly irregularly strongly strongly behaviour swollen swollen swollen swollen Consistency non-powdery soft, brittle soft, (after crumbly crumbly step (2′))

(55) These comparative experiments clearly show that the moulding obtained by the method according to the invention (1-Temp-1) has ideal properties.

(56) An increase of the temperature in process step (2′) to temperatures not in accordance with the invention of 90° C. (1-Temp-1A), 100-106° C. (1-Temp-1B) or 110° C. (1-Temp-1C) results in a deterioration of the properties of the mouldings obtained.

(57) 2—Component System

(58) The following experiments deal with processes in which the polymer material of the shell of the microcapsules is broken up by the addition of an agent.

(59) In preliminary experiments it was shown that microcapsules with different solvents can be broken open and release gas. Initially, good combinations were determined. For this purpose, different microcapsules with different solvents (each in the same mass ratio) were combined with each other and the reaction was evaluated or the absence of a reaction was noted (see table below).

(60) TABLE-US-00009 TABLE 7 Reaction between microcapsules and solvents. Experiment Component 2-M-1 2-M-2 2-M-3 2-M-4 2-M-5 2-M-6 2-M-7 Microcapsule A X X — — — — — Microcapsule B — — X X X — — Microcapsule C — — — — — X — Microcapsule D — — — — — — X Propylencarbonate S X — X — — X X Acetone — — — X — — — Turpentine substitute — — — — X — — Propylencarbonate/ — X — — — — — Water (2.4 g/7.6 g) Reaction +++ +++ ++ + + — — (after (immediately) approx. 30 sec.)

(61) In the above table, an “X” indicates the presence of the corresponding component and an “−” indicates the absence of this component. The reaction (the release of gas from the microcapsule) was divided into excellent reactions (+++), good reactions (++), minimal reaction (+) and no reaction (−). In case of excellent reactions, the start of the reaction (after the components were combined) was also noted.

(62) The experiments 2-M-1 and 2-M-2 resulted in an excellent reaction. Due to these preliminary experiments, the subsequent experiments, which use a component to break open the microcapsules, focused on combinations of microcapsule A and propylene carbonate.

(63) Inventive examples are listed in the following table.

(64) TABLE-US-00010 TABLE 8 Experiments to break open the microcapsules with an agent. Mixture Ingredient A B C Component 1 Na-WG1 80 — — Na-WG2 14 — — K-WG1 — 16 16 Al(OH).sub.3 mixture 4 0.8 0.8 Polyethylene fiber A 0.9 0.18 0.18 Microcapsule A 4 0.4 0.1 Expanded granulate B 2.4 — — Vermiculite 1 0.6 0.6 Vermiculite Powder 5 — — Density: 1.35 g/cm.sup.3 1.21 g/cm.sup.3 1.13 g/cm.sup.3 Volume Used [mL] 10 10 10 Component 2 Propylene carbonate S 18 18 18 Dispersing agents A 0.0449 — — Surfactant mixture A 0.1403 0.1144 0.126 Marble powder A 19 19 4 Vermiculite — 1.72 — Marble powder B — — 11 Consistency: liquid thixotropic, creamy, creamy thixotropic Density: 1.61 g/cm.sup.3 1.65 g/cm.sup.3 1.61 g/cm.sup.3 Volume Used [mL] 1 1 1 Miscibility of ++ ++ ++ the components Start of the reaction approx. ≥1 min. ≥2 min. 1 min.

(65) The ingredients of component 1 were presented in the ratios listed above and the density was determined. The ingredients of component 2 were presented in another container and the density was determined as well as the consistency assessed. Afterwards, the respective components (in the indicated volume ratio, 10 mL to 1 mL) were combined and mixed. The miscibility of the components was assessed and the start of the reaction—i.e. the beginning of the gas release—was determined.

(66) In all cases the components are well miscible and the reaction starts after approx. 1 min. (mixture A), ≥1 min (mixture B) or ≥2 min (mixture C).

(67) Based on these preliminary tests, solid fire protection materials were produced (see tables below):

(68) TABLE-US-00011 TABLE 9a Experiments according to the invention for the production of fire protection materials. Ingredients/ Mixture Characteristic 2-1 2-2 2-3 2-4 Component 1 Na-WG1 16 16 16 16 Na-WG2 2.7 2.7 2.7 2.7 Al(OH).sub.3 mixture 0.8 0.8 0.8 0.8 Polyethylene fiber A 0.18 0.18 0.18 0.18 Micrcapsule A 0.6 0.6 0.6 0.6 Vermiculite 0.6 0.6 0.6 0.6 Copolymer dispersion A — 1.02 — 1.02 Glass fiber — — 0.129 0.129 Density [g/cm.sup.3] 1.34 1.43 1.47 1.44 Volume Used [mL] 5 5 5 5 Component 2 Polyurethane dispersion/ 6 6 6 6 Water, 1/1 Surfactant mixture A 0.2 0.2 0.2 0.2 Propylene carbonate, 10 10 10 10 Jeffsol Marble powder C 6 6 6 6 Marble powder A 6 6 6 6 Density [g/cm.sup.3] 1.45 1.45 1.45 1.45 Volume Used [mL] 1 1 1 1 Mixture of component 1 and 2 Consistency of well well well slightly the mixture flowing flowing flowing viscous Start of reaction 3 2.5 2.5 2 [in minutes], approx. Swelling time: 10-12 min 10-12 min 10-12 min 10-12 min Structure very good and uniform

(69) TABLE-US-00012 TABLE 9b Experiments according to the invention for the production of fire protection materials. Ingredients/ Mixture Characteristic 2-5 2-6 2-7 2-8 Component 1 Na-WG1 16 16 16 16 Na-WG2 2.7 2.7 2.7 2.7 Al(OH).sub.3 mixture 0.8 0.8 0.8 0.8 Polyethylene fiber A 0.18 0.18 0.18 0.18 Micrcapsule A 0.4 0.4 0.6 0.5 Vermiculite — — — — Copolymer dispersion A 1.02 1.02 1.02 1.02 Glass fiber — 0.129 0.129 0.129 Density [g/cm.sup.3] 1.43 1.41 1.41 1.42 Volume Used [mL] 5 5 5 5 Component 2 Polyurethane dispersion/ 6 6 6 6 Water, 1/1 Surfactant mixture A 0.2 0.2 0.2 0.2 Propylene carbonate, 10 10 10 10 Jeffsol Marble powder C 6 6 6 6 Marble powder A 6 6 6 6 Density [g/cm.sup.3] 1.45 g/cm.sup.3 1.45 g/cm.sup.3 1.45 g/cm.sup.3 1.45 g/cm.sup.3 Used Volume [mL] 1 1 1 1 Mixture of component 1 and 2 Consistency of well well foamy, well the mixture flowing flowing fluent flowing Start of reaction 3 3 3 3 [in minutes], approx. Swelling time, approx.: 10-12 min   10-12 min   10-12 min   10-12 min   Structure Very good and uniform

(70) Component 1 was a mixture of two different sodium silicate glasses with microcapsules. In addition, component 1 contained different additives, depending on the mixture. The density of component 1 was determined in each case and is listed.

(71) The ingredients of component 2 are identical in these experiments. Component 2 contained, among other things, propylene carbonate, which serves to break open the shell material of the microcapsules. The density of component 2 was determined and is listed in the table.

(72) Afterwards component 1 and component 2 were mixed in a constant volume ratio (5 mL to 1 mL) at room temperature. The consistency of the mixture was evaluated, the time to the start of the reaction and the expansion time (reaction duration) were measured. The structure obtained was then evaluated.

(73) The consistency of the mixture was liquid in all cases, with the mixture 2-4 being slightly viscous. The start of the reaction in all mixtures was between about 2 to about 3 minutes after mixing the two components and the reaction time was about 10 to 12 minutes. In all cases, the structure of the resulting moulding was evaluated as very good and uniform.

(74) In a further series of experiments, four of the mixtures defined above were scaled up to fill a cavity with the dimensions 10 cm*10 cm*2.5 cm (=250 cm.sup.3) and the resulting fire protection panels were then evaluated.

(75) The constituents of components 1 and 2 as well as the corresponding densities are listed in the tables above.

(76) TABLE-US-00013 TABLE 10 Experiments according to invention for the production of fire protection materials. Mixture 2-2-G 2-4-G 2-6-G 2-8-G Component 1 see see see see component component component component 1 in 1 in 1 in 1 in mixture mixture mixture mixture 2-2 2-4 2-6 2-8 Mass Component 1 [g] 111.0  116.0  129.7  130.6  Component 2 see see s see see component component component component 2 in 2 in 2 in 2 in mixture mixture mixture mixture 2-2 2-4 2-6 2-8 Component 2 [g] 22.5 23.4 26.8 26.8 Component 1 [mL] 77.6 80.6 92.0 92.0 Component 2 [mL] 15.5 16.1 18.5 18.5 Volume ratio  5.0  5.0  5.0  5.0 Mixture of the Component 1 and 2 Consistency of well well well well the mixture flowing flowing flowing flowing Start of reaction 2  2  3  3  [in minutes], approx. Swelling time, approx.: 30   30   30   20   Structure very good and uniform Consistency of no structural changes the mixture

(77) Analogous to the series of experiments with the mixtures 2-1 to 2-8, in the experiments 2-2-G, 2-4-G, 2-6-G and 2-8-G a component 1 was also mixed with a component 2 in a volume ratio of 5 to 1. Component 1 comprises a water glass and gas-filled microcapsules, component 2 comprises the agent for breaking up the shell of the microcapsules (propylene carbonate).

(78) After the two components were combined, the consistency of the mixture was evaluated, the time until the start of the reaction and the swelling time (reaction duration) were measured. The structure obtained was then evaluated.

(79) The consistency of the mixture was liquid in all cases. While mixture 2-4 was evaluated as slightly viscous, the analogue mixture 2-4-G was evaluated as well liquid. The reaction started at between 2 and 3 minutes, whereas the reaction time was between 20 and 30 minutes. The relatively longer reaction time between the mixtures 2-2-G, 2-4-G, 2-6-G, 2-8-G and the analogous mixtures 2-2, 2-4, 2-6 and 2-8 is probably due to the fact that the first-mentioned mixtures are upscales of the second-mentioned mixtures. Accordingly, it is easier to determine a reaction in the upscaled mixtures; that is, in the small-scale reactions the reaction is simply no longer optically perceptible after the approx. 12 minutes listed there.

(80) In all cases a very good and uniform structure was obtained.

(81) The four moulded parts were then stored at room temperature and the structure was evaluated. After storage over one night, the structure was still very good and uniform and the volume was virtually unchanged. After several days of storage at room temperature, a slight decrease in volume of the mouldings was observed. After three days of storage at room temperature, the mouldings obtained from mixture 2-2-G were also stored in the oven at 96° C., with a considerable volume decrease observed.