EP3732147A1

EP3732147A1 - Method for producing fireproof materials based on sodium silicate

Info

Publication number: EP3732147A1
Application number: EP18774071.7A
Authority: EP
Inventors: Heike HUTH; Diederik Cuylits
Original assignee: Cuylits Holding GmbH
Current assignee: Cuylits Holding GmbH
Priority date: 2017-09-29
Filing date: 2018-10-01
Publication date: 2020-11-04
Also published as: WO2019129398A1; US11834376B2; US20200239367A1

Abstract

The present invention relates to a method for producing a solid fireproof material. The composition for producing the fireproof material contains at least one sodium silicate and microcapsules provided with propellant gas. The fireproof material is made by inflating the microcapsules or breaking open the polymer material of the casing of the microcapsules, wherein this takes place by means of the thermal action or by adding an agent breaking open the casing of the microcapsules.

Description

Process for the preparation of waterglass-based fire protection materials Description

The present invention relates to a process for the preparation of fire protection materials based on water glass, as well as their use.

Fire protection materials in the sense of the invention here means materials which (as far as possible) are non-flammable, have a temperature-insulating or heat-insulating effect and thus provide heat or flame protection, and optionally even contribute, for example by releasing water, to suppressing fires can.

The gas impermeability of fire protection materials may, in specific situations, be desirable, since on the one hand prevents the supply of oxygen to the source of fire and on the other hand suppresses the escape of potentially dangerous combustion gases.

In order to enable better processing or application, fire protection materials in general, in addition to their structural strength, which they preferably retain even at elevated temperatures, preferably have a low density and a certain hardness. The structural strength, even at elevated temperatures, enables the fire protection of specific, selected areas. The low density simplifies the transport, as well as the attachment of these materials in the desired positions (for example, on objects). The low density of the fire protection materials also causes a small overall weight increase of an object after attachment of the fire protection material. The hardness of the fire protection materials facilitates the processing (for example, the cutting into shapes of desired size and shape), the transport, storage and attachment to objects. In addition to the subsequent trimming of fire protection materials, the direct production of the fire protection materials in the desired shapes is also of interest, as this eliminates the subsequent step of trimming.

Trimming in the sense of the invention means any form of processing, such as milling, cutting, etching or other methods familiar to those skilled in the art to obtain a fire protection material of the desired size and shape.

Due to the different fields of application of the fire protection materials, such as outdoors, a high stability to the prevailing environmental conditions at the site, such as temperature fluctuations, direct sunlight, wind, water and moisture, of these materials is essential. The requirements for fire protection materials vary depending on the place of use and may therefore differ from this.

Corresponding materials are used in various branches of industry, such as the construction industry and in particular in preventive, structural fire protection. But also outside the fire protection fire protection materials, in particular due to their temperature-insulating properties, have a potentially broad field of application. The application areas of fire protection materials and materials for thermal insulation often overlap due to their very similar requirement profiles.

As applications with (high) temperature differences (outside of a fire), for which also fire protection materials can be used, the metallurgy or the metalworking industry in general, as well as the thermal insulation of furnaces in particular serve. Even the "usual" thermal insulation of buildings, such as houses, while maintaining the aforementioned fire protection properties by fire protection materials is conceivable. Further fields of application are obvious to the person skilled in the art.

The development of improved fire protection materials is promoted and influenced both by legal requirements and by the usual market mechanisms. Therefore, the production of the fire protection materials which possess the properties mentioned should be as cost-effective, low-energy and easy as possible. A shape of the fire protection materials which can be set as individually as possible or a slight processing to obtain the desired shape should also be given. In addition, safe, easily accessible and inexpensive starting materials should be used.

The provision of fire protection materials and processes for their production, which possess the abovementioned properties in whole or in part or fulfill the stated requirements in whole or in part, is therefore obviously of great interest.

Intumescent or bulking compositions are well known in fire protection; they form a thick, relatively flame-retardant, insulating material. As part of such compositions, for example, water glasses are suitable because they are non-combustible and have a high water content, among other things. The bloating of the compositions can be carried out, for example, by adding gas. The resulting moldings can be used directly or after further processing as fire protection materials.

The term "intumescent" or "bloating" - as used in the context of the present invention - denotes the mode of action of special materials which can be inflated and thereby form an insulating body. A fine, uniform structure of this blowing mass is of particular interest in order to obtain a uniform and high protective effect over the entire range of the blowing mass. Any kind of cracks and larger cavities are undesirable. Furthermore, an increase in volume is necessary since, if these or only a minimal increase are absent, the bodies obtained usually have an inadmissibly high density. Accordingly, in the context of the present invention, a "poor swelling layer" or a "poor swelling behavior" means that the volume increase was not sufficient and / or the structure of the inflatable body does not have a fine, uniform structure. The use of water glass for the production of moldings for fire protection purposes is disclosed in many documents.

No. 5,194,087 discloses the production of moldings from compositions with at least one water glass. The use of propellant-engineered microcapsules for manufacturing is not disclosed.

EP 2 571 829 discloses a process for the production of moldings for fire protection materials from compositions consisting of at least two different Natron waterglasses of specific viscosity. EP 2 571 829 further discloses the simultaneous use of propellant gas-filled microcapsules to inflate this composition, wherein the swelling occurs under the action of energy. The use of more energy-efficient methods for gas release, as well as the advantage of the inflation in a specific temperature range, are not disclosed.

In the disclosed prior art, the water resistance and the structure of the obtained fire protection materials can be improved. The swelling behavior of the disclosed compositions is in part suboptimal. Furthermore, the manufacturing processes are quite energy intensive.

The object of this invention is to provide a method for the production of fire protection panels which fulfill the abovementioned properties completely or at least partially. In particular, it is an object of this invention to produce a low-cost, low-energy, simple process for the production of low-density fire-resistant materials and good, uniform structure, which have a certain hardness and water resistance.

These aspects are at least partially fulfilled by the method now described:

Process for producing a solid fire-protection material, in particular in the form of a fire-protection board, characterized by the following process steps (1) and (2):

(1) providing a composition comprising at least one water glass and propellant-provided microcapsules with a propellant gas core and a polymeric material as a shell, wherein the microcapsules, based on the dry weight, of at least 20% by weight propellant gas respectively;

(2) inflating the microcapsules and / or rupturing the polymeric material of the shell of the microcapsules by the addition of propylene carbonate; or by the following method steps (T) and (2 '):

(T) providing a composition containing at least one Kaliwas- water glass and propellant gas provided with a microcapsules with propellant gas provided core and a polymeric material as a shell;

(2 ') Inflating the microcapsules and / or breaking up the polymer material of the shell of the microcapsules by the action of temperature of 60 to below 90 ° C.

The term "solid fire protection material" used in the context of this invention means, as is clear from the intended use as a fire protection board, a solid material. This material is preferably not powdery, and the presence of a few powdery residues on the otherwise non-pulverulent and solid fire protection material is to be understood as a solid material.

Temperatures below 90 ° C for the purposes of this patent means temperatures below 90 ° C, preferably below 89 ° C, more preferably below 88 ° C, more preferably below 87 ° C, more preferably below 86 ° C.

When used in the following description, the terms "fire-resistant materials" and "fire-resistant panels" mean, unless otherwise indicated, fire-resistant materials and fire-resistant panels produced by the above method.

Unless the term "composition" is used in the following description, it is meant, unless otherwise indicated, a composition according to the above process.

If viscosities were determined or indicated in the context of this invention, they were determined using a Haake Viskotester C, the L version at 20 ° C using the spindles L3 or L2 at 100 U / min or 200 U / min and a measuring range between 20 to 60%. The parameters used in each case are further executed during the experiments. In general, the spindle and the torque for determining viscosities are adjusted and selected by the "trial and error" method until a measurement range of 15-95%, preferably 20-60%, is obtained.

The color of the fire protection material which is produced by the process according to the invention is preferably white.

In particular, this invention describes a process in which the breaking up of the polymeric material of the shell of the microcapsules with the agent propylene carbonate occurs.

For the purposes of the invention, propylene carbonate includes both the pure isomers ((R) - propylene carbonate and (S) propylene carbonate), and mixtures of these isomers (such as, for example, the racemate).

steps

In the context of this application, a reference to procedural step (1) also includes procedural step (T) and vice versa, if not clear from the respective factual context it can be seen that the corresponding statement refers explicitly only to method step (1) or (1 '). The same applies analogously to method steps (2) and (2 ').

Process step (1) or ~ composition

glasses of water

Water glass contains chemically and physically bound water, which extracts heat in the event of fire due to the evaporation of this water. On the other hand, the bloating behavior of water glass leads to a ceramic foam, which acts as an insulator. The proportion of water in the water glass and the swelling behavior are of the type of water glass (soda, potassium water glass, etc.), and the respective molar or weight ratio (Si0 ₂ : K ₂ 0; Si0 ₂ : Na ₂ 0) The use of at least two different water glasses in the inflating compositions often results in a more favorable for the cooling effect Blähbild, whereby a better insulating effect is achieved.

The composition according to the invention comprises at least one water glass.

N atron wasserg I as

In one embodiment, the composition contains at least one soda water glass. When using only one soda water glass, this preferably has the following properties:

(1) Weight ratio of Si0 ₂ to Na ₂ 0 equal to 2.30 to 3.80, preferably 3.00 to 3.60, more preferably 3.10 to 3.50

(2) density of 1300 to 1600 kg / m ³ , preferably 1300 to 1500 kg / m ³ , more preferably 1340 to 1380 kg / m ³ ; and

(3) Water content of 50 to 70% by weight, preferably 60 to 65% by weight, more preferably 63.2 to 64.8% by weight.

The use of two different water glasses often proved to be advantageous for the swelling behavior of the obtained fire protection material.

Therefore, the composition preferably contains at least two different soda water glasses, wherein the first soda water glass has a viscosity of 1000 to 2400 mPa ^* s (20 ° C) and the second soda water glass has a viscosity of 75 to 250 mPa ^* s (20 ° C).

The first soda water glass, which has a viscosity of 1000 to 2400 mPa ^* s (20 ° C), preferably has at least one of the following properties: (1) weight ratio of Si0 ₂ to Na ₂ 0 equal to 2.30 to 2.60, preferably 2.32 to 2.56, particularly preferably 2.34 to 2.54;

(2) density of 1500 to 1600 kg / m ³ , preferably 1520 to 1580 kg / m ³ , more preferably 1540 to 1565 kg / m ³ ; and

(3) Water content of 50 to 55% by weight, preferably 51 to 54% by weight, more preferably 51.9 to 53.6% by weight.

The viscosity of this glass is more preferably from 1200 to 2200 mPa ^* s (20 ° C), and more preferably from 1400 to 2000 mPa ^* s (20 ° C).

The second soda water glass has a viscosity of 75 to 250 mPa ^* s (20 ° C) and preferably has at least one of the following properties:

(1) weight ratio of Si0 ₂ to Na ₂ 0 equal to 2.80 to 3.80, preferably 3.00 to 3.60, more preferably 3.10 to 3.50;

(2) density of 1300 to 1500 kg / m ³ , preferably 1330 to 1450 kg / m ³ , more preferably 1365 to 1375 kg / m ³ ; and

(3) Water content of 55 to 70% by weight, preferably 60 to 65% by weight, more preferably 63.2 to 64.6% by weight.

The viscosity of this glass is more preferably from 85 to 225 mPa ^* s. (20 ° C) and most preferably from 100 to 200 mPa ^* s (20 ° C)

As soda water glasses, for example, a soda water glass with a weight ratio of 2.3 as the first soda water glass and a soda water glass with a weight ratio of 3.3 as a second soda water glass can be used. The ratio of the two water glasses can preferably be between 120-200 parts by weight of a sodium water glass with a weight ratio of 2.3 to 10-50 parts by weight of a sodium waterglass with a weight ratio of 3.3, more preferably 140-180 wt. Parts to 15-40 parts by weight, particularly preferably 155-165 parts by weight to 20-30 parts by weight.

In the composition, the content of water glasses, in particular soda water glasses, in each case based on the total mass of the composition, is generally 60 to 98 wt.%, Preferably 70 to 97 wt.%, More preferably 80 to 96 wt. ,

Potassium silicate

It has surprisingly been found that the use of at least one potash water glass in the composition has a positive effect on the water resistance of the fire protection materials obtained in the context of the process according to the invention. Therefore, the composition preferably comprises a potash water glass.

The use of at least one potassium silicate in compositions in which the gas release in process step (2) takes place by adding a further agent often also has an influence on the kinetics of the gas release. Thus, for example, after the addition of the agent, an earlier (or later) gas release can take place and / or the total duration of the period in which gas release can take place can be shortened (or extended). For example, earlier gas release often occurs using propylene carbonate as a gas release agent in the presence of potash water. This influence on the kinetics of the gas release can be disadvantageous or irrelevant (depending on the situation).

Therefore, the two aspects - a potential influence on the kinetics of gas release and a higher water resistance of the resulting fire protection materials - have to be considered. Such a consideration is to be made by the expert. While the water resistance depends strongly on the intended use and the place of use of the obtained fire protection material, the period of gas release and the time interval until the release of gas are predetermined by the production process used.

If a potash water glass is used, it preferably has the following properties: a viscosity of 10 to 200 mPa ^* s, preferably between 20 to 100 mPa ^* s; a weight ratio of Si0 ₂ to K ₂ 0 between 1.7 to 3.5, preferably between 1.9 to 2.5, a density between 1200 to 1500 kg / m ³ , preferably between 1250 to 1400 kg / m ³ and a Water content between 50 to 80% by weight, preferably between 55 to 75% by weight.

If a potassium silicate glass is used, the proportion of potassium silicate, based on the total sum of water glasses, in particular based on the total amount of potassium silicate and sodium water glass, at least 30 wt .-%, more preferably at least 40 wt .-%, more preferably at least 50% by weight, more preferably at least 55% by weight, more preferably at least 60% by weight, more preferably at least 65% by weight, more preferably at least 70% by weight, further preferably at least 75% by weight %, more preferably at least 80 wt .-%, more preferably at least 85 wt .-%, more preferably at least 90 wt .-%, more preferably at least 95 wt .-%.

The use of potassium water glasses, in particular to the extent of the above quantities, is indicated in particular when using the method steps (1 ') and (2').

Other mixtures of water glasses

In addition, other water glasses or mixtures of water glasses can be used.

In a further preferred embodiment, the composition contains at least one soda water glass and at least one potash water glass. In this case, the soda water glass preferably has the following properties:

(1) weight ratio of Si0 ₂ to Na ₂ 0 equal to 2.30 to 2.60, preferably 2.32 to 2.56, particularly preferably 2.34 to 2.54;

(4) Viscosity of 1000 to 2400 mPa ^* s (20 ° C), more preferably 1200 to 2200 mPa ^* s (20 ° C), more preferably 1400 to 2000 mPa ^* s (20 ° C).

The potash water glass preferably has the following properties:

(4) Viscosity of 75 to 250 mPa ^* s (20 ° C), preferably from 85 to 225 mPa ^* s (20 ° C) and more preferably from 100 to 200 mPa ^* s (20 ° C).

microcapsules

The composition comprises at least one propellant consisting of propellant microcapsules.

By using this ingredient, when foaming in process step (2) or (2 '), a very compact microfoam with good thermal insulation properties is produced. The resulting foam is not as brittle as a pure water glass foam, which was produced without the use of appropriate microcapsules. A positive influence on the swelling volume is often achieved with the use of such microcapsules.

The propellant-supplied microcapsules which serve as propellants generally contain a propellant gas which is selected from the group consisting of hydrocarbons, such as methane, ethane, propane, n-butane, isobutane, and pentanes, such as n-butane. Pentane, isopentane and neopentane; Chlorofluorocarbons, such as trichlorofluoromethane and dichlorodifluoromethane; dimethyl ether; carbon dioxide; Nitrogen and air, as well as mixtures of these propellants. The propellant particularly preferably comprises a hydrocarbon, in particular isobutane, isopentane or mixtures thereof.

The blowing agent can be used dry, as a dispersion or with different degrees of drying. In one embodiment, the microcapsule is present as a dispersion in another embodiment, the microcapsule is dried or with different degrees of drying before. In another embodiment, the microcapsule is partly dried and partially present in a dispersion. As a dispersion medium is used in particular What water.

The propellant-containing microcapsules have, in each case based on the dried microcapsule, a content of 2 to 35 wt .-%, preferably 5 to 30 wt .-%, more preferably 10 to 30 wt .-%, on preferably 20 to 30 wt .-% propellant. In one embodiment, the dried microcapsules have a content of at least 20% by weight of propellant gas.

The outer shell of the microcapsules may be formed of any polymeric material as long as the material is capable of trapping a corresponding propellant gas and expanding upon energization or breaking up by the addition of an agent and releasing this propellant gas.

Possible shell materials for the microcapsules used are, for example, copolymers such as, for example, copolymers of acrylonitrile, methacrylate and / or acrylate, vinylidene chloride copolymers and vinylidene chloride / acrylonitrile copolymers.

The propellant-capped microcapsules, based in each case on the dried microcapsules, generally have a shell material content of from 50 to 95% by weight, preferably from 50 to 90% by weight, more preferably from 60 to 90% by weight, more preferably 60 to 80 wt .-%, on.

The microcapsules provided with propellant gas may also contain further ingredients such as magnesium hydroxide and / or silica in the core and / or in the shell material.

The propellant-containing microcapsules have such further ingredients, in each case based on the dried microcapsule, in a content of 0 to 30 wt.%, Preferably 0 to 25 wt.%, More preferably 0 to 20 wt. more preferably 1 to 5 wt .-% on.

The propellant-provided microcapsules may have any average particle size. Average particle sizes are for example 1 to 90 mhh, preferably 1 to 50 mhh, more preferably 5 to 20 mhh, more preferably 10 to 16 pm.

The microcapsules provided with propellant, in each case based on the dried microcapsules, generally have a density of <20 kg / m ³ , preferably of <17 kg / m ³ , more preferably of <14 kg / m ³ , more preferably of <12 kg / m ³ . In the composition, the content of at least one blowing agent consisting of propellant-provided microcapsules, in each case based on the total mass of the composition, is generally from 0.5 to 15% by weight, preferably from 1.0 to 8.0% by weight. -%, more preferably 2.0 to 7.0 wt .-%.

According to the invention, the mass ratio between water glass (or water glasses) and the propellant-provided microcapsules is 5.0 to 35.0, preferably 6.0 to 25.0, more preferably 8.0 to 24.0.

Corresponding propellants are commercially available. The different types of microcapsules differentiate in terms of size, the type of propellant gas, the shell material, the additives and the blowing agent content. In the context of the present invention, various types of microcapsules can be used, wherein the microcapsule type is adapted to the other constituents and the bloating behavior of the composition.

In the context of the present invention is preferably on the use of other propellants, such as azo compounds that are expensive on the one hand and on the other hand problematic and environmentally questionable in their handling omitted. The use of expandable graphite can also be dispensed with within the scope of the present invention.

In one embodiment, the composition is free of expandable graphite. In another embodiment, the composition is free of conventional blowing agents such as triancine derivatives. In a preferred embodiment, the composition is free of expandable graphite and triazine derivatives.

Other components of the composition

In the context of the present invention, it has surprisingly been found that the composition of process step (1) or (T), which has further constituents, is advantageous for the fire protection material obtained by the process according to the invention.

The ceramization of the composition at elevated temperatures supporting component

These components can already support the ceramization of the fire protection material during the temperatures of the method according to the invention and / or develop this effect in case of fire.

A constituent which promotes ceramization of the composition at elevated temperatures is preferably selected from the group consisting of mineral additives, aluminum hydroxide, filter dust, fly ash, ceramic hollow spheres, glass hollow balls, foam glass granules, slate meal, quartz flour, mica, wollastonite, calcium carbonates, kaolin, vermiculite and ettringite.

Particularly preferred is the use of aluminum hydroxide, vermiculites, glass hollow spheres, ceramic hollow spheres and calcium carbonate, and mixtures thereof.

The proportion by weight of this constituent promoting the ceramization, based in each case on the total mass of the composition, is generally 1 to 15% by weight, preferably 3 to 13% by weight, more preferably 6 to 12% by weight.

fiber

The composition preferably comprises at least one fiber. This fiber is preferably an organic fiber.

The use of a fiber reduces brittleness, making the fire protection material less susceptible to breakage.

By choosing a suitable fiber, the swelling behavior of the composition as a whole is improved. The resulting foam has finer pores and shows a better insulating effect.

Preferably, the at least one fiber is selected so as to also aid in plasticizing the composition at elevated temperature.

The at least one fiber is generally selected from the group consisting of polyalkylene fibers such as polyethylene fibers and polypropylene fibers; polyacrylic fibers; Aramid fibers; Polyamide fibers such as polyhexamethylene di-amide fibers, polycaprolactam fibers and aromatic or partially aromatic polyamide fibers; and fibers of partly aromatic or wholly aromatic polyesters and glass fibers.

The at least one fiber may be a solid or hollow fiber.

It is particularly preferred if the at least one fiber is a polyalkylene fiber, such as a polyethylene fiber or a polypropylene fiber. The use of a polyethylene fiber is particularly preferred.

The content of the at least one fiber, in each case based on the total mass of the composition, is generally from 0.1 to 4% by weight, preferably from 0.2 to 3% by weight, more preferably from 0.5 to 1, 5% by weight.

The positive effects when using an organic fiber is also to be regarded as surprising, since due to the organic content of the fiber material actually a component is incorporated, which would have to accelerated fire behavior of the obtained fire protection materials. However, this is not the case and is achieved in particular by the small amount of fiber material. In addition, the use of a corresponding fiber in the composition increases the ability to bond to adjacent substrates or materials during inflation. This aspect is particularly relevant for composite materials.

Preferably, the composition comprises at least one further constituent selected from the group consisting of at least one component which promotes ceramization of the composition at elevated temperatures; and / or at least one fiber.

Borax / water glass / borax hardener

Another preferred constituent of the composition is disodium tetraborate decahydrate (borax), the content of disodium tetraborate decahydrate, based in each case on the total mass of the composition, generally from 0.1 to 10% by weight, preferably from 0.25 to 7.5 Wt .-%, more preferably 0.5 to 5.0 wt .-% is

The composition may additionally comprise at least one further constituent which results in curing and / or setting of the composition.

The further constituent is generally selected from the group consisting of phosphate-containing water glass hardeners, glyoxal, triacetin, ethylene carbonate and propylene carbonate.

The content of a curing agent, based in each case on the total mass of the composition, is generally from 0.5 to 10% by weight, preferably from 1.0 to 7.5% by weight, more preferably from 2.0 to 5.0% by weight. -%.

Hygroscopic component

The composition may additionally comprise at least one further constituent which has a moisture-retaining and / or hygroscopic property. By adding an appropriate component, the residual moisture of the fire protection material can be adjusted and kept constant.

This further component is preferably selected from the group consisting of glycerol, Epsom salt (magnesium sulfate), calcium chloride, zeolites and sugar (also in the form of molasses). Especially advantageous is the use of Epsom salt, since the high proportion of water of crystallization has particularly positive properties on the cooling effect in case of fire.

Other further ingredients

In addition, the composition may additionally comprise at least one silica.

Further constituents customary for inflating compositions may also be present in the composition. The composition has a water content of generally from 15 to 65 wt .-%, preferably 20 to 55 wt .-%, particularly preferably 25 to 50 wt .-%; in each case based on the total mass of the composition. This content of water in the composition can be realized by the specific choice of the individual ingredients or by the addition of water.

By adding more water, it is also possible to achieve higher levels of water, for example up to 95% by weight.

The water content of the composition can be increased by the addition of substances having a high content of water of crystallization, such as ettringite. Also, by the addition of substances having a high vapor pressure such as glycerin, the drying out of the mass can be reduced or prevented. The addition of such substances also promotes the residual moisture content of the fire protection material.

Process step (2) or - swelling and / or rupture of the microcapsules

In process step (2) or (2 '), the microencapsules are inflated and / or broken open and thus the composition swells. This results in a compact microfoam with good thermal insulation properties, which is not brittle.

It has surprisingly been found that the swelling of the microcapsules in a temperature range below 90 ° C results in particularly advantageous fire protection materials. More preferably, this temperature range is between 60 and below 90 ° C.

In one embodiment, the puffing of the microcapsules, by temperature effect of 65 to below 90 ° C, preferably from 70 to below 90 ° C, more preferably from 75 to below 90 ° C, more preferably from 80 to below 90 ° C on preferably from 85 to below 90 ° C.

In one embodiment, the swelling of the microcapsules takes place by the effect of temperature of from 65 to below 80 ° C., preferably from 65 to below 75 ° C., more preferably from 65 to below 70 ° C.

As an alternative to the swelling of the microcapsules by the action of temperature, it has surprisingly been found that specific agents cause the composition to expand due to the breaking up of the microcapsules. The agent here comprises individual substances such as solvents, but also mixtures of several individual substances.

The proportion by weight of the composition, based on the total mass of the composition, is generally from 1 to 20% by weight, preferably from 2 to 15% by weight, more preferably from 3 to 10% by weight.

This agent is to be chosen in this case in particular depending on the microcapsules used. The breaking up of the microcapsules with an agent is, in comparison to puffing obviously energy-efficient, a more energy-efficient method. As a result, this approach opens up the use of lower process temperatures, for example room temperature, than in the case of swelling due to energy input.

The breaking up of the microcapsules with an agent can take place here in various ways. For example, a chemical reaction between the agent and the microcapsule, which results in the release of gas, or a physical interaction between the agent and the microcapsule, for example swelling of the capsules and thus the release of the propellant, are conceivable. Of course, further interactions to break up the microcapsules are possible and an interaction of different interactions is not excluded.

In one embodiment of the invention, propylene carbonate or a mixture containing propylene carbonate is used as a gas release agent.

Particularly in the case of microcapsules which, based in each case on the dried microcapsule, contain from 2 to 35% by weight, preferably from 5 to 30% by weight, more preferably from 10 to 30% by weight, more preferably from 20 to 30% by weight. Propylene carbonate or a mixture containing propylene carbonate is used as a gas release agent.

In particular, in the case of microcapsules which, based in each case on the dried microcapsule, a shell material content of 50 to 95% by weight, preferably 50 to 90% by weight, more preferably 60 to 90% by weight, more preferably 60 to 80 Wt .-%, is propylene carbonate or a mixture containing propylene carbonate, used as a means for gas release.

In particular, in the case of microcapsules, which, based in each case on the dried microcapsule, further ingredients, such as magnesium hydroxide and / or silicates, in a content of 0 to 30 wt .-%, preferably 0 to 25 wt .-%, more preferably 0 to 20 wt %, more preferably 1 to 5% by weight, propylene carbonate or a mixture containing propylene carbonate is used as the gas release agent.

Particularly in the case of microcapsules which, based in each case on the dried microcapsule, have average particle sizes of, for example, 1 to 90 mhh, preferably 1 to 50 mhh, more preferably 5 to 20 mhh, more preferably 10 to 16 pm, propylene carbonate or a mixture containing propylene carbonate, used as a gas release agent.

In particular, in microcapsules, which, in each case based on the dried microcapsule, in general a density of <20 kg / m ³ , preferably of <17 kg / m ³ , more preferably of <14 kg / m ³ , more preferably of <12 kg / m ³ , propylene carbonate or a mixture containing propylene carbonate is used as the gas release agent. The gas release preferably begins after addition of the agent in a period of between 20 seconds to 20 minutes, more preferably between 20 seconds to 10 minutes, more preferably between 30 seconds to 5 minutes, more preferably between 1 minute to 3 minutes.

The resulting fire protection material is substantially dimensionally stable.

It generally has a density of less than 0.6 g / cm ³ , preferably less than 0.5 g / cm ³ , more preferably less than 0.4 g / cm ³ .

If the composition is provided in process step (1) or (1 ') in a specific form and subsequently undergoes process step (2) or (2'), the resulting fire-protection materials are preferably readily and substantially residue-free and dimensionally stable remove this shape. The mold used can then be reused without extensive cleaning.

In contrast to the problem-free removal of the fire protection materials from the specific forms is the production of composite materials. Here, during the process step (2) or (2 '), the compositions are in contact with carrier materials or contact these carrier materials after flattening. After bloating, the fire protection material and the carrier materials thereby form a solid composite material (or a composite body). Thus, the composition has sufficient adhesive properties, so that in the production of composite materials preferably no additional adhesive materials must be used. This aspect will be further discussed in the section on the production of composite materials.

The breaking up and / or swelling of the shell of the microcapsules in process step (2) takes place with propylene carbonate, it is preferably a mixture of propylene carbonate with further additives. For example, these are mixtures of propylene carbonate with dispersant and / or kaolin and / or fly ash and / or vermiculite and / or calcium carbonate. Others, in particular the ingredients listed in the composition, may be part of these mixtures.

Use of fire protection materials

The fire protection materials obtained by the process according to the invention find use, for example, in the construction industry, for example in the lining and / or lining of doors, walls, floors and ceilings, for openings, passages and other openings. In addition to building construction, as well as, for example, in the lining of tunnels and pipes, the fire protection materials can also be used in shipbuilding and vehicle construction, such as in wagons or in transport, such as in containers. Also, the protection of cables and other Elekt ronik, as well as the use of personal protective clothing are possible. The fire protection materials according to the invention can be used, for example, for the protection of a "black box" or similar sensitive electronics. A black box is a computer used, for example, in manned and / or unmanned air, land and water vehicles. Examples of aircraft are airplanes and helicopters. Examples of land vehicles are trains and cars. Examples of watercraft are ships, boats and submarines. The black box records various parameters during operation, such as the speed and position of the vehicle, but can also be used to record further parameters, such as sounds, such as conversations. If necessary, the recorded data can be read out. This is particularly in accidents, such as a plane crash, and / or near-misses of interest to reconstruct the accident and / or the cause of the accident using the recorded data.

Since extreme conditions often prevail in accidents, the black box must be protected against such conditions. From an economic point of view, this protection should be as space-saving as possible and have a low density. The extreme conditions include, for example, high thermal energies, for example due to a fire, and high kinetic energies, such as in a high-speed impact. It may also be necessary to protect the Black Box against various chemicals which, in particular due to an accident, can contact the electronics of the Black Box and compromise the stored data so that the data can not be read or only partially read. Such chemicals include, for example, water, which contacts the black box, for example, by extinguishing a fire or by leakage of a watercraft, but also other chemicals, for example other chemicals which can be used in the fight against fire, or chemicals, for example by the high thermal energies of a fire, to be released.

Due to their low density, the fire protection properties and their water resistance, the fire protection materials according to the invention are an ideal material for protecting such a black box, or it is advisable to use the fire protection materials according to the invention in combination with other materials for protecting a black box.

It is therefore an object of the present invention to design a housing for a data processing unit, such as a black box, with the fire protection material according to the invention in such a way that the most effective possible thermal insulation effect is obtained with as little space as possible.

This can be achieved with one or more, at least partially overlapping, inventive fire protection materials, which surround the data processing unit, preferably completely, or are connected directly to it. Completely circumscribed in this sense includes the presence of smaller seams and / or the presence of at least one heat transfer element if the cross-sectional area of this heat transfer element and the seams is sufficiently small; ie, significantly less than the area of the surrounding fire protection material. For example the cross-sectional area of the heat-transfer element and any seams present is less than 10%, preferably less than 5% and in particular less than 2% of the area of the surrounding fire-resistant material according to the invention.

In addition to the fire protection materials according to the invention, it is also possible to use further materials, such as vacuum insulation board materials, these usually consisting of an open-pored support core, which is surrounded by an envelope which is as air-tight as possible. The material used for the support core can be, for example, open-pored plastic foams, pyrogenic silicas or perlites, each having a low thermal conductivity of, for example, less than 0.01 W m ¹ K ¹ . The envelope surrounding the support core consists, for example, of one or more layers of a metallized plastic film, where each of these films is coated with one or more layers of a metal coating, for example an aluminum coating. Desiccants and / or binders may additionally be incorporated in the support core or between the support core and the shell, which can bind penetrating gas molecules, for example water vapor.

In order to enable a covering of as few segments as possible or with as few gaps or joints between segments as possible, it is optionally provided to form the sheathing from two half-shells, each consisting of such a vacuum insulating panel material.

To improve the thermal insulation is provided according to an embodiment that exists between two sheaths of Vakuumdämmplattenmaterial or on at least one side of the Vakuumdämmplattenmaterials another thermal barrier coating; this is preferably the fire protection material according to the invention.

Optionally, a heat-insulating layer made of an aluminum layer is arranged on an inner side of a housing wall. In this case, this aluminum layer can be a separately produced aluminum foil, which is subsequently arranged and fixed on the inside of the housing wall. It is also possible that the aluminum layer is applied as an optionally multi-layer coating on the inside of the housing wall. The arranged on the inside of the housing aluminum layer acts as a comparatively poor heat radiator and are only a small heat radiation in an interior of the housing. With regard to the highest possible mechanical strength and temperature resistance, the housing can have a housing wall made of metal, in particular of a stainless steel, so that the housing wall has a comparatively high thermal conductivity. By means of the aluminum layer arranged on the inside of the housing wall, high heat radiation into the interior of the housing and thus to the data processing unit is prevented when the metallic housing wall heats up.

Additionally or alternatively, a heat-insulating layer made of an aluminum layer can be arranged on an outer side of a housing wall. The externally arranged aluminum In this case, the layer has a heat-reflecting effect and prevents rapid heating of the housing wall as a result of increased ambient temperatures.

It is preferably provided that a, preferably according to the invention thermal barrier layer, comprises a layer of an airgel. Such an airgel is a highly porous solid with a volume fraction of up to more than 99.9% of pores. Corresponding silicate-based aegels are commercially available, but other materials such as plastic or carbon based may also be used. The pore size of conventional aerogels is in the nanometer range, with the aerogels having inner surfaces of up to 1000 m ² per gram of solid. Due to these properties, aerogels generally have a very high thermal insulation effect and a very low density and are particularly suitable, in addition to the inventive fire protection materials, as protection for such a data processing unit or black box.

It is also possible that a thermal barrier coating, preferably a erfindungsge-, having a layer of a nonwoven, a knitted fabric, a fabric or a scrim of ceramic or mineral fibers. Due to the high degree of flexibility and the simple deformability, such a thermal insulation layer can be adapted to the shape of the housing and, in particular, to the usable space for the thermal insulation device around the data processing unit in the interior of the housing.

The intumescent material described below may be a composition as also described in relation to process step (1) or (1 ') of the fire protection material according to the invention.

According to one embodiment, the thermal barrier coating according to the invention also comprises at least one layer of an intumescent material which expands when heated above a threshold temperature. This intumescent material then forms an additional insulating layer with a low thermal conductivity, as a result of which undesirable heat transfer through the thermal barrier coating can additionally be considerably reduced. In addition, this additional heat-insulating layer of the intu meszierenden material initially fill only a relatively small proportion of the interior of the housing, so that "empty" spaces remain. These allow effective heat exchange during normal operation. When exposed to heat from the environment above the threshold value, the intumescent material then expands and at least partially fills in the previously existing "empty" spaces so that ideal thermal insulation is achieved.

In addition, the intumescent material undergoes an endothermic reaction upon such expansion, thereby "consuming" heat so that a cooling effect occurs. In addition, the intumescent material may additionally or alternatively release or form a flame-retardant active substance in the case of a temperature-related foaming. Corresponding active compounds may be, for example, various flame retardants, for example halogenated compounds such as tetrabromobisphenol A or polybrominated diphenyl ether, nitrogen-based flame retardants such as melamine or inorganic flame retardants such as aluminum hydroxide.

According to one embodiment, the intumescent material is arranged on a heat-insulating carrier layer, wherein this carrier layer is preferably a layer according to the invention. Due to the use of this separate carrier layer, the intumescent material need not be arranged or applied on the inside of the housing wall or directly on the data processing unit. As a result of the arrangement and orientation of the carrier layer, it can be simply specified in which preferred direction the intumescent material expands during expansion or foaming. For its part, said support layer expediently consists of a heat-insulating material such as the fire protection material according to the invention, which has sufficient dimensional stability and the lowest possible thermal conductivity.

Optionally, it is provided that the intumescent material is arranged between an inner side of a housing wall and the, preferably according to the invention, carrier layer. As soon as, due to an increased ambient temperature, an increased heat input through the housing wall into the interior of the housing takes place and the intumescent material heats above a threshold temperature, it expands and forms a heat-insulating layer immediately adjacent to the inside of the housing wall, which further heat transfer additionally reduced in the interior of the housing. In addition, the expansion of the intumescent material as an endothermic reaction may result in an additional cooling effect.

According to one embodiment, the housing wall has at least one opening through which the intumescent material can penetrate with a temperature-induced foaming and exit from the housing. In this way it is possible that the housing has comparatively small dimensions during normal operation. In the case of excessive heat, the intumescent material expands, escapes through said at least one opening and forms a heat-insulating layer on the outside. This at least one opening is preferably a plurality of openings arranged regularly or irregularly; For example, can it be holes with a diameter of a few millimeters. It is also possible to use a housing which has a few, comparatively large, holes.

As an alternative or in addition thereto, a heat-insulating layer with an intumescent material arranged on the inside of the housing wall or in the interior of the housing, preferably according to the invention, may be provided. This lathers at over- On the outside of the housing forms a thermal barrier coating, with which also the heating of the housing wall is reduced or delayed. The intumescent material can substantially completely encase the housing, so that after foaming the housing is surrounded by the foamed up thermal insulation layer. Since the intumescent material before foaming has a comparatively small space requirement, can be formed with a thin coating of the housing, by which the outer dimensions only minimally increased, if necessary, a thick and effective thermal insulation envelope.

According to one embodiment, it is possible for a heat-insulating layer, preferably according to the invention, to comprise a layer of a material which, when heated, performs an endothermic reaction, whereby cooling is effected.

If the data processing unit itself generates heat during regular operation, this heat must be dissipated to prevent overheating of the data processing unit during its intended use. Therefore, it is optionally provided that a heat transfer element is arranged in the housing, which forms a heat-transmitting connection of the data processing unit with a heat-conducting housing interface in a housing wall of the housing, in order via the heat transfer element during operation of the data processing unit - testified to be able to dissipate heat. The heat transfer element can be, for example, a thin metal sheet or a metal foil, which allows efficient heat removal from the housing. It is also conceivable that a heat-transferring fluid is guided in a circuit through the housing or a heat exchanger is used for heat dissipation.

In order to prevent heat from the environment from being transmitted into the housing at an excessively high ambient temperature via the heat transfer element, as a result of which the data processing unit could be overheated and damaged, it is provided according to an embodiment that the heat transfer element - Ment has a separator. This separator is at an excessive heat input to the data processing unit or at high temperatures outside the housing active and separates the connection between the housing interior and the environment.

The separating device has, for example, an element which can be changed in shape by the action of heat and which changes at a corresponding temperature in such a way that the connection between the housing interior and the surroundings is separated. This separation can be done for example by a deformation or by a break at a predetermined breaking point.

Preferably, the data processing unit is coated with a moisture-proof coating, which consists, for example, of a lacquer coating of an electrically insulating plastic material which protects the data processing unit from moisture, but also protects against dust and other impurities. However, this function can also be done by the fire protection material according to the invention.

If the data processing unit consists of several components, such as a microprocessor and one or more memory units, which are arranged on a common printed circuit board, a moisture-proof coating can be applied directly to the printed circuit board and the components arranged thereon, for example by suitable immersion. or spray method. Due to the moisture-proof coating, the data processing unit can be protected not only against splashing water or small amounts of moisture, but also against water penetrating into the housing with a high water pressure, for example more than 10 bar or 20 bar.

When using a heat transfer element as described above, the moisture-proof coating may also surround the heat transfer element at least in a region around the data processing unit and may provide additional definition and additional protection of the heat transfer element at the data processing unit.

A separate moisture-proof or watertight covering or sealing of the housing is therefore not necessary, but can also be used alternatively.

In one embodiment, the data processing unit has a digital data storage device. Preferably, it is provided that the memory device has a solid-state drive. Flash memory-based or SDRAM-based semiconductor chips suitable for use as a solid-state drive are known, which can store a very large amount of data of more than 100 gigabytes in a comparatively small chip housing. A data processing unit having at least one microprocessor and a plurality of semiconductor chips can be accommodated on a printed circuit board with dimensions of less than 50 mm x 50 mm. A thermal insulation according to the invention, with which such a data processing unit is protected against damage even in the event of a fire, can be accommodated in a housing with a small useful volume and small external dimensions.

According to one embodiment, it is provided that the housing has dimensions that are smaller than or equal to a standardized 3.5-inch housing with dimensions less than or equal to 146 mm × 102 mm × 25 mm. The housing may have a standardized shape, so that the data processing unit arranged therein and protected by a heat insulation device can be used, for example, instead of a commercially available hard disk in a data processing system. It is also possible to exchange a hot-swap hard disk during operation and to replace it with a data processing unit which is arranged in a housing provided with the thermal insulation device according to the invention and permits retrospective fire and fire protection of the computer data processing system. Due to the small dimensions and the high data transfer rates that are possible with a data processing unit described above during normal operation, such a data processing unit in the housing according to the invention is also suitable for use as a tachograph and black box in autonomous vehicles ,

It is currently assumed that a tachograph with which gap-free monitoring and logging of a drive operation lasting about 24 hours of a vehicle and in particular of a partially or completely autonomously operated vehicle is possible, record and store a data volume of about 5 terabytes should be able. Solid-state drives have been developed which have a memory capacity of 6 terabytes or more with little space requirement and also low heat generation during operation and which are advantageously autonomous as a data processing unit in a housing according to the invention for use as a black box moving vehicles are suitable. Such a black box, with adequate protection against fire, water and vibration for most possible accidents, can be housed in a housing that has only the external dimensions of a standardized 3.5-inch housing, or even made smaller ,

In addition to the lining / cladding of materials, the fire protection materials can also completely form or partially replace the component to be clad. For example, it is possible to erect a door exclusively or partially from the fire protection materials.

In addition to being used in areas subject to unplanned and spontaneously high temperatures (such as in a fire) and by their presence slowing down and fire retardant, the fire protection materials are also generally used in areas in which normally (high) temperature differences prevail and a thermal insulation is desired. Examples of this are metallurgy and the metalworking industry in general, as well as the insulation of furnaces in particular. Even the "usual" thermal insulation of buildings, such as houses, while maintaining the aforementioned fire protection properties by fire protection materials is conceivable. Further fields of application are obvious to the person skilled in the art.

The fire protection material is either cut for the particular application or already produced in the desired shape.

Commonly useful forms of the fire protection materials are obvious to those skilled in the art and include, for example, plates, cuboid bodies such as bricks, concave or convex bodies, for example, for the lining or sheathing of cables and tubes, as well as tubular bodies, which are for example hollow inside and as Can serve cable.

Due to the adhesive properties of the composition already described, it is also possible not to cut a desired target body from the fire protection material, still to make it directly from a mold, but to glue this target body together. This is of particular interest when the shape of the desired target is "complex".

The size of the fire protection materials is (each dimension is independent of each other) usually from a few centimeters to several meters.

composite materials

The fire protection material produced by the process according to the invention can be used in the form of composite materials. Composite material, comprise such a fire protection material and at least one carrier material.

The composition in process step (1) or (T) has not only inflating properties, but also adhesive properties. The composition is therefore particularly suitable for the bonding of materials.

Accordingly, the present invention also relates to composite materials comprising a composition as in process step (1) or (T) and at least one Trägermateri- al, wherein the composition is either applied to the carrier material or the carrier material is impregnated with this composition. Subsequently, process step (2) or (2 ') takes place for the production of the fire protection material. Due to the adhesive properties, a composite material is obtained in this case.

The support material is selected from the group consisting of nonwoven materials, in particular nonwoven materials of glass fibers, polyester, natural fibers, rayon / cellulose or polyamide; Fabrics of glass fibers or blended fabrics; Gridding of glass fibers; Mineral wool, in particular mineral wool of glass or stone; Cellulosic materials such as paper materials and cardboard materials, in particular paper honeycomb, fibreboard or honeycomb constructions; Plastic materials; Metal materials, such as metal foils and sheets, in particular aluminum foils and sheets or stainless steel foils and sheets; Glass materials, such as glass foils and glass wool; Cotton fabrics; Wood materials and wood-based panels such as MDF, HDF and chipboard; Foams of polyurethane, polystyrene, glass or stone foam, PVC or phenol; Extruded polystyrene foam materials; Polyethylene foam, polypropylene foam, polyurethane foam and polypropylene foam materials; Polypropylene, polyethylene, polyurethane or silicone films and general decorative surfaces such as HPL or CPL. Other suitable materials include flax, jute, hemp and cellulosic materials, and more generally, textile materials.

It is hereby preferably selected from the group consisting of: nonwoven materials; Paper and cardboard materials, such as paper honeycomb; Plastic materials; Metal materials, such as metal foils, in particular aluminum foils; Glass materials such as glass foils and glass wool; Cotton fabrics; Wood materials; Mineral wool; Extruded polystyrene foam, polyurethane foam, polyethylene foam and polypropylene foam materials; Jute, flax, hemp and cellulose fiber materials; and textile materials. It is also possible to use composite structures made of, for example, glass fabric / aluminum or HPL / glass fleece) as support material.

In addition, the carrier materials can be perforated, slit or otherwise structured for specific applications.

In the context of the present invention, the support material can be impregnated with the inflating composition and subsequently, according to process step (2) or (2 '), the composition is converted into the fire protection material. Impregnation of the carrier material is possible by using a dip bath which is filled with the composition and immersing the carrier material in the dipping bath.

Impregnation of corresponding carrier materials, in particular of paper or cardboard materials, such as paper or cardboard honeycomb, leads to penetration of the composition between the fibers of the carrier material, so that even cutting correspondingly impregnated carrier materials does not lead to a loss of the fire protection effect. In addition, impregnation of the composition into corresponding carrier materials can be improved by the use of surface-active agents. Process step (2) or (2 ') can be carried out before or after the impregnation of the impregnated materials.

If paper honeycombs are impregnated with the composition, non-flammable composite materials are obtained, after application of process step (2) or (2 '), from which, for example, walls, ceilings or other structural elements can be manufactured.

The fire protection effect of these composite materials can be further increased by the following measures:

1. The paper used for the paper honeycomb is previously perforated. As a result, the percentage of combustible material is reduced and the composition is better absorbed. Furthermore, the composition also accumulates in the perforated cavities, whereby their proportion is increased.

2. As cover layers for the paper honeycomb is impregnated with composition impregnated glass, paper or plastic fleece. These cover layers on the one hand increase the mechanical stability of the paper honeycombs and on the other hand increase the fire protection effect. The amount of applied fire protection compound can be varied as required.

3. Subsequently, the inventive method step (2) or (2 ').

Instead of fleece, cover layers of perforated paper perfused with fire protection compound can also be used. Furthermore, the cover layers produced in this way can additionally be provided with aluminum foil, which improves the heat reflection and reduces the water vapor diffusion.

Sandwich structure

Another object of the present invention is a composite body comprising a carrier material according to the above definition, which was provided with the composition, and at least one further layer, which is formed by an aluminum foil, a glass mat or a paper or cardboard material and which is applied to the carrier material.

The carrier material may preferably be a paper or a cardboard honeycomb.

The further layer can be formed, for example, by a perforated paper fleece or a perforated cardboard material or glass fleece.

This further layer formed by a perforated paper web or a perforated cardboard material may further preferably be impregnated with the composition.

After provision of such a sandwich structure in process step (1) or (T), a fire protection material is obtained after process step (2) or (2 '), which has the structure described above. Composite bodies with such a structure are also referred to as sandwich structures in the context of the present invention.

These sandwich structures not only have excellent fire retardant properties, but are sufficiently bonded due to the adhesive properties of the composition without the use of an additional adhesive.

Particularly when using cardboard honeycomb as a second layer, the covering of the cardboard honeycomb with the fire protection material produced by the method according to the invention prevents the passage of heat through convection and at the same time (for example in case of fire) by evaporating the water from the fire protection compound a cooling effect achieved.

In the case of fire, the resulting sandwich structures remain intact and there is no cleavage of individual layers from the sandwich.

Sandwich structures according to the invention comprise the following structure:

(1) a first layer of an aluminum foil, a glass mat, a paper or cardboard material or a composite thereof;

(2) a second layer of nonwoven material; Paper material or cardboard material, such as a paper honeycomb; Plastic material; Metal material, such as a metal foil, in particular an aluminum foil; Glass material, such as a glass sheet or glass wool; Cotton material, wood material or mineral wool material; Polyethylene foam materials; Materials of extruded polystyrene foam; Polyurethane foam materials; Materials of polypo- pylene foam; Flax, jute, hemp and cellulose materials;

(3) a third layer of an aluminum foil, a glass mat, a paper or cardboard material or a composite thereof; wherein the composite material is constructed such that the first layer is provided on one side of the second layer and the third layer is provided on the other side of the second layer and the fire protection material of the composition according to the inventive method on one side or at - was applied to the sides.

tries

Viscosity determination and viscosities of water glasses

The viscosities of the waterglasses used were determined as follows:

Table 1: Details on viscosity determination and viscosities of various water glasses. Definition of used water glasses

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

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

K-WG1 is a potash water glass which, in addition to the above viscosity, has a density (at 20 ° C) of about 1.3 g / mL. The pH (100 g / L at 20 ° C) is about 11. K-WG2 is a potash water glass which, in addition to the above viscosity, has a density (at 20 ° C) of about 1.3 g / mL having. The pH (100 g / L at 20 ° C) is about 11.

Definition of the other ingredients used in the experiments

The component "Al (OH) ₃ -Mixture" is a mixture of Al (OH) ₃ with various other oxides, such as sodium oxide, iron oxide and silicon dioxide. Al (OH) ₃ is the main constituent with over 99%.

The component "expanded granules A" are (surface-treated) glass hollow spheres whose material consists to> 95% of silicon dioxide and which begin to soften at about 1300 ° C (in the cluster). Expanded granules A has a pH of 5 to 8. The component "expanded aggregate 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 ³ , grain density of 700 (± 80) kg / m ³ , wherein the examination of the grain density in accordance with DIN V 18004 and the calculation according to EN 1097-6 was carried out, average grain strength of 2.6 N / mm ² , wherein the determination of the grain strength according to DIN EN 13055-1 was carried out. The expanded granules B consist (based on a dried at 105 ° C sample) of about 70 to 75% Si0 ₂ , 10 to 15% Na ₂ 0, 7 to 1 1% CaO, 0.5 to 5% Al ₂ 0 ₃ , 0 to 5% MgO and 0 to 4% K ₂ 0. The "Bläh granulat B" begins to soften at about 700 ° C. It has a pH of 8 to 11.

The component "microcapsule A" is dry, unexpanded, propellant-filled microcapsules. 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 mean particle size is 10 to 16 pm and the density is <12 kg / m ³ . The propellant gas release takes place in a temperature range of 80 to 95 ° C.

The component "microcapsule B" is dry, unexpanded, propellant-filled microcapsules. They comprise about 13% of a propellant, about 0 to 20% amorphous silica and about 60 to 90% of a copolymer. The mean particle size is 10 to 16 pm and the density is <17 kg / m ³ . The propellant gas release takes place in a temperature range of 94 to 99 ° C.

The component "microcapsule C" are dry, unexpanded, propellant-filled microcapsules. They comprise about 15 to 20% of the propellant isopentane and about 75% of a copolymer. The mean particle size is 10 to 16 pm and the density is <17 kg / m ³ . The propellant gas release takes place in a temperature range of 123 to 133 ° C.

The component "microcapsule D" is dry, unexpanded, propellant-filled microcapsules. They comprise about 15 to 20% of the propellant isopentane, about 60% of a copolymer and about 0 to 20% of magnesium hydroxide. The average Parti kelgröße is 28 to 38 pm and the density is <14 kg / m ³ . The propellant gas release takes place in a temperature range of 122 to 132 ° C.

The component "copolymer dispersion A" is an aqueous copolymer dispersion based on vinyl acetate / vinyl ester. Stabilizers of the dispersion are emulsifiers and cellulose derivatives.

Polyethylene fiber A is a fiber made from HDPE.

The component "dispersant A" is the solution of a high molecular weight anionic copolymer in water.

The component "surfactant mixture A" is a medium-viscosity 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) about 120 mPas and the pH (2% in distilled water ) is about 6.5. The component "marble powder A" is a marble powder with an average particle diameter of 2.5 μm.

The component "marble flour B" is a marble powder with an average particle diameter of 5 μm.

The constituent "marble powder C" is a marble powder with an average particle diameter in a value range which comprises 12 μm to 15 μm.

The ingredient vermiculite is expanded vermiculite. Main constituents of this aluminum-magnesium iron silicate are (approx.) 43% to 46% SiO ₂ , 9% to 12% Al ₂ O ₃ , 7% to 9% Fe ₂ O ₃ , 1% to 3% CaO, 24 % to 27% MgO and 4% to 6% K ₂ 0. The particle size distribution is (in each case 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 remainder has larger particle sizes, wherein, the proportion of product with particle sizes greater than 1 mm at most (about) 1%.

The component vermiculite powder is a corresponding vermiculite powder. The grain size is less than 50 microns and the specific surface area is about 2.6 m ² / g.

The constituent glass fiber is a glass fiber which has the following chemical composition (in each case approx.): 62-68% Si0 ₂ , 26-32% CaO + MgO, less than 1% other constituents.

The component "polyurethane dispersion" is a non-ionic polyurethane system in water, wherein the ratio of polyurethane to water is about 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 25,000 mPas (according to DIN EN ISO 3219) and the pH (2% in distilled water) is about 6.5.

experiments

The following experiments illustrate the advantage of the method according to the invention.

1 component system

The following experiments deal with processes in which the swelling of the microcapsules takes place by the action of temperature.

Experimental group Wasserfestiqkeit

The increase in water resistance in the addition of potassium silicate to soda waterglass or in the exclusive use of potash water is illustrated by the following experiments (Tables 2A and 2B):

Table 2A: Water resistance of water glasses ( ^* = tests not according to the invention).

Table 2B: Water resistance of water glasses ( ^* = experiments not according to the invention).

The composition of the respective experiments was provided in accordance with the proportions by mass of the constituents given in the table, and process step (2 ') was carried out thermally at an oven temperature of 86 ° C.

The resulting molded articles were examined for their water resistance. The rating was on a scale from 1 (very good) to 6 (insufficient). The ratios of the individual components were identical in the experiments, or when using several glasses of water (1-WF-3 and 1-WF-5 to 1-WF-13), the sum of the sum of water glasses used was identical to the respective water glass of the other Tries. Therefore, a direct comparison of the resulting fire protection materials is possible.

The ratio of potassium silicate to soda water glass in this test series was graded from 0%, i. no potassium water glass present (in experiments 1 -WF-1 and 1-WF-2), up to 100%, i. no soda water glass present (in experiment 1-WF-4) increased.

The water resistance improved (in comparison to the pure soda water glass in 1-WF-1 and 1-WF-2) with a poor water resistance with an increase of the potash water glass content. This improvement can be divided into three groups:

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

Group 2: When using 60% to 75% potassium silicate, a further improvement in water resistance was observed. The water resistance is in the range between satisfactory and sufficient.

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

These experiments clearly demonstrate the increased water resistance of the molded bodies increasing the potassium silicate content in the composition. In this case, a use of at least 50% potassium silicate glass (based on the sum of the water glasses) is preferred, more preferably a use of at least 60% potassium silicate, more preferably a use of more than 75% potassium silicate.

Experimental group temperature

The experiments in the following tables (Tables 3, 4, 5a, 5b and 6) show the influence of microcapsules, waterglass and temperature on the resulting shaped article. In the experiments summarized in these tables, the respective composition (as listed) was provided (method step (T)) and the consistency was assessed. The compositions were then cured in a ring (0 4.5 cm) at the stated temperatures (process step (2 ')).

The temperature of the experiments in Table 3 is according to the invention and is 85 ° C, the temperature in the tables (4, 5a and 5b) is not according to the invention (temperatures greater than or equal to 90 ° C). Table 6 contains comparative experiments of a composition at different temperatures. After process step (2 '), the evaluation of the shaped bodies obtained takes place. The evaluation included the evaluation of the structure of the bottom area, the remaining structure, the color, the swelling behavior (which was carried out over the foam height, with a foam height of more than about 2 cm being considered to be "strongly inflated") and the consistency. The consistency was divided into powdery, brittle, crumbly and soft.

Table 3: Process at 85 ° C and characterization of the resulting molded articles ( ^* = experiments not according to the invention).

Table 4: Comparative experiments ( ^* = experiments not according to the invention) at 97 ° C and characterization of the resulting molded articles.

Table 5a: Comparative experiments ( ^* = experiments not according to the invention) at 125 ° C and characterization of the resulting molded articles.

Table 5b: Comparative experiments ( ^* = tests not according to the invention) at 125 ° C. and characterization of the resulting shaped articles. Ideally, there is a strongly puffed product that has a smooth bottom area and a residual structure that is good and uniform. More preferably, the molded body is not powdery or at most slightly pulverulent. In the normal case, a creamy white color of the molding is preferred.

While the experiment 1-Temp-1 (Table 3) according to the invention results in a product with ideal characteristics, molded articles from the comparative experiments (Tables 3, 4, 5a and 5b) are not ideal and have various defects in one or more of the dots soil structure , remaining structure, swelling behavior, as well as consistency. The two experiments in Table 3 differ only in the type of glass used and show that the use of a potash water glass results in a better consistency of the shaped body compared to a sodium water glass.

The importance of the temperature is further clarified by the following experiments. In these experiments, the experiment with the same composition used in the experiment "1-Temp-1" was carried out at different temperatures:

Table 6: Experiments with identical composition at different temperatures and characterization of the resulting molded articles ( ^* = experiments not according to the invention).

These comparative experiments clearly show that the shaped body obtained by the process according to the invention (1-temp-1) has ideal properties. An increase in the temperature in process step (2 ') to non-inventive temperatures of 90 ° C (1-Temp-1A), 100-106 ° C (1-Temp-1 B) or 1 10 ° C (1- Temp-1 C) results in a deterioration in the properties of the molded articles obtained.

2-Component Systems The following experiments cover processes in which the breaking up of the polymeric material of the shell of the microcapsules occurs by the addition of an agent.

Preliminary experiments have shown that microcapsules can be broken up with various solvents and release gas. First, good combinations were identified. For this purpose, various microcapsules with different solvents (in each case in the same mass ratio) were associated with each other and evaluated the reaction or noted the absence of a reaction (see the table below).

Table 7: Reaction between microcapsules and solvents.

In the above table, an "X" indicates the presence of the corresponding component and "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 the case of the excellent reactions, the beginning of the reaction (after the components have been added) was also noted.

Experiments 2-M-1 and 2-M-2 resulted in an excellent reaction. On the basis of these preliminary experiments, the follow-up experiments focused on a means of breaking up the Use microcapsules for combinations between microcapsule A and propylene carbonate.

Examples according to the invention are listed in the following table.

Table 8: Experiments to break up the microcapsules with an agent. The components of component 1 were presented in the ratios listed above and the density was determined. The constituents of component 2 were used in another presented and determined the density, and judged the consistency. Subsequently, 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 beginning of the reaction - ie the beginning of the gas release - determined. In all cases, a good miscibility of the components is present and the reaction begins after about 1 min. (Mixture A),> 1 min (mixture B) or> 2 min (mixture C).

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

Table 9a: Inventive experiments for the production of fire protection materials.

Table 9b: Inventive experiments for the production of fire protection materials. In each case a mixture of two different soda water glasses with microcapsules was used as component 1. In addition, component 1 contained, depending on the mixture, different additives. The density of component 1 was determined in each case and is listed.

The components of component 2 are identical in these experiments. Component 2 contained inter alia propylene carbonate, which serves to break up the shell material of the microcapsules. The density of component 2 was determined and is listed in the table.

Subsequently, 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 taken until the start of the reaction, and the expansion time (reaction time) were measured. Subsequently, the obtained structure was evaluated.

The consistency of the mixture was liquid in all cases, with the mixture 2-4 slightly thick. The start of the reaction was for all mixtures between about 2 to about 3 minutes after the addition of the two components and the reaction time was about 10 to 12 minutes. In all cases, the structure of the obtained molded article was evaluated as very good and uniform.

In another series of tests, four of the mixtures defined above were scaled up by a mold having the dimensions 10 cm ^* 10 cm ^* 2.5 cm (= 250 cm ³⁾ and to fill the erhalte- NEN fire protection panels were then evaluated. The components of components 1 and 2, as well as the associated densities are listed in the above tables.

Table 10: Inventive experiments for the production of fire protection materials.

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

After combining the two components, the consistency of the mixture was evaluated, the time taken until the start of the reaction and the expansion time (reaction time) were measured. Subsequently, the obtained structure was evaluated. The consistency of the mixture was liquid in all cases. While Mixture 2-4 was judged to be slightly viscous, the analogous mixture 2-4-G was judged to be well liquid. The start of the reaction was between about 2 and about 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 former mixtures are upscalings of the latter mixtures. Accordingly, it is easier to detect a reaction in the upscaled mixtures; This means that in the reactions on a small scale, the reaction is visually simply no longer noticeable according to the approx. 12 minutes listed there.

In all cases, a very good and uniform structure was obtained.

The four moldings were then stored at room temperature and the structure evaluated. After storage for one night, there is still a very good, uniform structure and the volume is virtually unchanged. After storage at room temperature for several days, a slight decrease in volume of the moldings was observed. The molded article obtained from mixture 2-2-G was also stored in the oven after storage for three days at room temperature still at 96 ° C, with a considerable decrease in volume was observed.

Claims

claims:

1. A process for producing a solid fire protection material, in particular in

Shape of a fire protection board, characterized by the following

Process steps (1) and (2):

(1) providing a composition containing at least one

Waterglass and propellant gas microcapsules having a propellant gas core and a polymeric material as a shell, said microcapsules having at least 20% by weight propellant based on dry weight;

(2) inflating the microcapsules and / or rupturing the polymer material of the shell of the microcapsules by the addition of propylene carbonate; or by the following method steps (T) and (2 '):

(T) providing a composition containing at least one

Potassium waterglass and propellant gas microcapsules having a propellant gas core and a polymeric material as a shell;

2. The method according to claim 1, characterized in that the mass ratio between the at least one water glass and the at least one provided with propellant microcapsules is from 5.0 to 30.0.

3. The method according to claim 1 or 2, characterized in that the composition comprises at least one Kaliwasserglas.

4. The method according to any one of claims 1 to 3, characterized in that the gas release of the composition takes place after addition of a shell-breaking agent in a period of 20 seconds to 20 minutes.

5. The method according to any one of claims 1 to 4, characterized in that the composition comprises at least one further constituent selected from the group consisting of at least one component which promotes ceramization of the composition at elevated temperatures; and / or at least one organic fiber.

6. The method according to claim 5, characterized in that the at least one ceramization at elevated temperatures supportive constituent of the composition is selected from the group consisting of mineral additives, aluminum hydroxide, filter dust, fly ash, ceramic hollow spheres, glass hollow spheres, foam glass granules, slate, quartz powder , Mica, wollastonite, calcium carbonate, kaolin, vermiculite and Ettingritt.

7. The method according to any one of claims 1 to 6, characterized in that the composition comprises the following components: (1) at least one further ingredient which results in curing and / or setting of the composition; and or

(2) at least one further ingredient having a moisture-retaining and / or hygroscopic property; and or

(3) at least one silica.

8. The method according to any one of claims 1 to 7, characterized in that the resulting fire protection material has a density of less than 0.6 g / cm ³ .

A composite material comprising a fire protection material obtained by a process according to any one of claims 1 to 8 and at least one support material.

10. Composite material according to claim 9, characterized in that the carrier material is selected from the group consisting of nonwoven materials; Paper materials and cardboard materials, such as paper honeycomb; Plastic materials; Metal materials, such as metal foils, in particular aluminum foils; Glass materials such as glass foils and glass wool; Cotton fabrics; Wood materials; Mineral wool; Extruded polystyrene foam, polyurethane foam, polyethylene foam and polypropylene foam materials; Jute, flax, hemp and cellulose fiber materials; and textile materials.

1 1. A composite material according to claim 10, characterized in that at least one further layer, which is formed by an aluminum foil, a glass fleece or a paper or cardboard material and which is applied to the carrier material is present.

12. Composite material according to claim 9, characterized by the following structure:

(1) a first layer of an aluminum foil, a glass fleece, a

Paper or cardboard material or a composite thereof;

(2) a second layer of nonwoven materials; Paper materials and

Cardboard materials, such as paper honeycomb; Plastic materials; Metal materials, such as metal foils, in particular aluminum foils; Glass materials such as glass foils and glass wool; Cotton fabrics; Wood materials; Mineral wool; Materials of extruded polystyrene foam, polyurethane foam, polyethylene foam and polypropylene foam; Jute, flax, hemp and cellulose fiber materials; and textile materials;

(3) a third layer of an aluminum foil, a glass fleece, a

Paper or cardboard material or a composite thereof; wherein the composite material is constructed such that the first layer is provided on one side of the second layer and the third layer on the other side the second layer is provided and the fire protection material, which was obtained by a method according to any one of claims 1 to 8, is located on one side or on both sides.

13. Fire protection material, in particular in the form of plates, rectangular bodies such as bricks, concave or convex bodies or tubular bodies, obtainable by a process according to one of claims 1 to 8.

14. Use of fire protection materials according to claim 13 in the construction industry, such as in the lining and / or lining of doors, walls, floors, ceilings, openings, ducts and other openings and tunnels and pipes, also in ship and vehicle construction, such as For example, in wagons, in transportation, such as containers, for the protection of cables and other electronics, as well as in personal protective clothing, also in the insulation of stoves and other thermal insulation, such as in building construction.