EP0430957A1

EP0430957A1 - Poorly-flammable structural elements, in particular panels, and process for producing them

Info

Publication number: EP0430957A1
Application number: EP89907742A
Authority: EP
Inventors: Robert Graf; Dieter Annemaier
Original assignee: Chemische Fabrik Gruenau AG
Current assignee: Gruenau Illertissen GmbH
Priority date: 1988-07-16
Filing date: 1989-07-07
Publication date: 1991-06-12
Also published as: DE3824149A1; EP0351670B1; EP0351670A3; WO1990000576A1; US5126076A; DE58903213D1; EP0351670A2

Abstract

Lesdits éléments de construction sont fabriqués à partir de déchets synthétiques combustibles. Ils comprennent en outre des éléments additionnels inorganiques non inflammables et un mélange d'agents ignifuges. Lesdits composants sont liés à l'aide d'au moins une colle durcie. Cette composition rend lesdits éléments de construction difficilement inflammables en dépit de leurs constituants combustibles.Said construction elements are produced from combustible synthetic waste. They also include additional non-flammable inorganic elements and a mixture of flame retardants. Said components are linked using at least one hardened adhesive. This composition makes said building elements difficult to ignite despite their combustible constituents.

Description

description

Flame retardant components, in particular panels, and processes for their production

The invention relates to flame-retardant components, in particular elattas, and a method for their production.

In the industrialized countries, large quantities of waste products, such as plastic parts, plastic films, pieces of tissue, synthetic fibers and, fall in many technical processes

Synthetic fleece. For a long time, these unwanted waste products were stored in landfills, occasionally causing great problems due to their lightness

(Space requirement, wind blown away) or cause ecological difficulties because they are either not microbially degradable or because when they are broken down, chemical substances are released that can damage the air, soil and water. For this reason, attempts are continually being made to use these old materials as raw materials for new articles. For example, DE-OS 34 16 473 describes a process for producing molded parts from fibrous waste materials and adhesives. The parts manufactured in this way are comparable in terms of their mechanical and insulation properties to lightweight construction and insulation panels made of foamed plastics and have the advantage of being environmentally friendly. In terms of fire protection, however, they are clearly inferior. When using the fire pit method in accordance with DIN 4102, part 1, such a violent fire phenomenon, combined with rapid fire spreading, shows that panels according to DE-OS 34 16 473 are only flammable building materials (building material class B 2) or even highly flammable building materials ( Building material class B 3) can be classified.

Building regulations, however, increasingly require flame-retardant building materials (building material class B1)

DIN 4102, part 1).

Experiments by the applicant have shown that the addition of classic flame retardants, such as Korab in ati onen from antimony tri oxide and halogenated substances or aluminum hydroxide in the production of plates from waste polyester fiber material even at relatively high dosages (up to 20 wt .-% %) cannot achieve the desired fire protection. Even higher doses of these flame retardants are not possible, since only molded parts with absolutely inadequate mechanical properties are then obtained. Surprisingly, the effect of the flame retardants described is so low that no better molded parts are obtained in terms of fire protection than if the amount of the classic fire retardant is merely replaced by inorganic inert material, such as calcium carbonate powder. A further known method would be surface coating and / or lamination with flame retardants. This can be done, for example, by lamination with anor ganic fabrics happen, which may be additionally treated with fire protection coatings. But even this path does not lead to the desired success.

The invention has for its object to provide components utilizing waste materials, which have the desired mechanical properties and, moreover, are more difficult.

It has now been found that components which, in addition to the waste material and the adhesive, additionally contain a combination of non-combustible inorganic additives and a flame retardant mixture, have the desired flame retardancy and still have good mechanical properties.

The invention relates to flame-retardant components, in particular panels, made from a pressed mixture

5 to 50% by weight of combustible organic waste material, 75 to 20% by weight of non-combustible inorganic additives,

4 to 40 wt .-% of a flame retardant mixture and

3 to 25% by weight of at least one hardened adhesive that holds the components together.

Sheets or other molded parts, such as pipe shells, which consist of such a mixture, meet the criteria for "flame-resistant building materials" with a considerable safety margin. In addition to protecting the environment, they also have technical advantages over a variety of commercially available panels, molded parts or cladding materials. So they are of commercial quality compared to chipboard much lighter, cheaper in fire behavior and more water resistant. The latter property is particularly evident in the fact that the water absorption can be significantly reduced and in addition no dimensional changes (sources) are found. Compared to foam plastic panels, there are not only fire protection-related advantages, but also acoustic and building-physical advantages (open porosity). The components also have good sound and thermal insulation properties.

The individual components, at least the plastic waste material and at least some of the inorganic additives, are preferably present in the components in a heterogeneous mixture, in particular in a coarsely heterogeneous mixture. Surprisingly, this brings considerable advantages for that

Fire behavior. The waste material is preferably present in the component in the form of parts or pieces, preferably in a size of 1 to 20 mm, in particular 2 to 15 mm. Flat parts in which the thickness is 0.01 to 4 mm, in particular 0.5 to 2 mm, are particularly advantageous. The heterogeneous structure of the component means that the parts of the waste material in the component can be arranged spatially separated from one another, non-combustible additives and / or flame retardants being located between the parts of the waste material. If the components come into contact with fire, individual parts of the waste material can burn off on the surface, but the fire cannot continue because of the subsequent inert filler material or the fire protection agents.

The waste materials are advantageously in the form of small pieces of nonwoven fabric. Ball of fiber, shredded foil and / or foam pieces. The invention is of particular importance for the recycling of polyester fibers, in particular in the form of irregularly large area pieces of nonwoven fabrics as waste pro large quantities of products and pose a significant disposal problem. In addition to plastic fibers, waste from natural fibers can also be used, which in turn is preferably not in the form of individual fibers, but rather in the form of pieces or particles. For example, cellulose can be in the form of shredded paper, cotton in the form of pieces of tissue or balls of fiber. Other plastics, which can be in the form of fibers, pieces of film or in other lumpy form, can also be used. For example, waste materials can also consist of polyacrylonitrile, polystyrene, nylon, polypropylene or polyethylene. Furthermore, the waste material need not necessarily consist of real waste. Similar to chipboard, which was originally made from waste chips, the combustible organic material can be specifically produced and processed for the components according to the invention.

The flame retardant mixture is advantageously free of aliphatic and aromatic halogen compounds and in particular also free of antimony salts and other heavy metal compounds, so that no harmful substances are released in the event of fire, as is the case with these classic fire retardants. The entire component is preferably free of such substances. The component is advantageously stiff and has high strength. This is particularly high if the waste materials are in fiber form. The component can be machined and can be sawn, nailed, drilled and glued, for example. Due to its heterogeneous and relatively coarse-grained primary structure, the component is permeable to air and also has low thermal conductivity. In addition, the primary particles themselves are advantageously permeable to air, such as the fleece particles or balls of fiber, for example. The surface of the component can be designed so that the individual components can be clearly distinguished, in particular the waste pieces and the inorganic additives are clearly recognizable and can be distinguished from one another. The density of the components depends on the density of the individual components and the degree of compression of the mixture. As a rule, the density is between 300 and 1000 kg / m ³ , in particular between 350 and 800 kg / m ³ . Densities in the range between 450 and

650 kg / m ³ have proven particularly useful in practice. The compressive strength is preferably at least 2 N / mm ² , in particular at least 3 N / mm ² . These are average values since the heterogeneity is normally in the range between 1 mm ² and 100 mm ² .

The adhesive is at least partially a two-component adhesive or thermoset. A hot melt adhesive can also be used. In contrast to the other components, the adhesive is preferably evenly distributed in the component in order to obtain a homogeneous solidification of the different components. The adhesive can also be an elastomer adhesive which, if desired, imparts elastic properties to the component, for example when a certain flexibility or elastic flexibility is desired.

The inorganic fillers are preferably inert with respect to heat and / or chemically. On the one hand, they can be used to spatially separate the combustible waste materials. On the other hand, they can also be used to correct strength values, density and other mechanical properties. A combined application is preferred. Thus, the inorganic fillers are preferably at least in part, in particular at least for the most part, in the form of inorganic fibers. The fiber length is preferably in the range of 0.5 up to 20 mm. The fibers can also be considerably longer if the fibers are wound into fiber balls, the size of which is on the order of the particles of the waste material. Such fibrous additives are particularly advantageous where the waste materials themselves do not provide sufficient strength for the component. Furthermore, fillers in the form of light fillers are particularly advantageous where a low-density component is desired. Such light fillers are particularly mineral in origin. Examples of such light fillers are hollow glass spheres, hollow aluminum silicate spheres, expanded clay, expanded vermiculite or pearlite, and gas concrete. The size of these light fillers is usually in the range between 0.01 and 2 mm. The inorganic fiber materials can be glass fiber, mineral fiber, slag fiber and ceramic fiber. In particular, if the waste materials do not give the component any particular strength, the fibrous fillers are present in larger quantities than non-fibrous fillers. The ratio of fibrous fillers to non-fibrous fillers is normally 2: 1 to 4: 1, in particular approximately 3: 1.

The flame retardant mixture preferably has an ablative effect (energy and / or substance-consuming) and acts in particular in two directions, and for this purpose preferably contains components that have a carbonizing effect on the one hand and gas components that split off on the other. The carbonizing components quickly lead to charring of combustible components. There are no additional carbon dispensers for the carbonizing components, since in the event of a fire the carbonization should take place on the combustible waste materials. The carbon formation largely removes the carbon from the one combustion process, at least initially. On the other hand, the flame retardant mixture preferably also contains gas-releasing components, which are non-combustible gases or vapors delt. The carbonizing constituents and / or the gas-releasing constituents are advantageously water-insoluble or water-resistant, so that they can develop their effect even after being moistened several times. In addition, glazing additives, such as borates, can also be present in the mixture. The entire component is particularly advantageously composed of water-resistant materials, so that it is not damaged or destroyed by the action of moisture or water.

As a carbonizing component or components, the flame retardant mixture preferably contains at least one phosphate, in particular a condensed phosphate. An advantageous example of this is ammonium polyphosphate. The phosphates develop already at temperatures from approx.

200 ° C their charring effect, ie before flames can reach the appropriate places. Suitable gas-releasing components are hydroxides, such as aluminum hydroxide, magnesium hydroxide, which release water, and carbonates, such as calcium carbonate, which release carbon dioxide. Basic carbonates can split off both water and CO ₂ . A combination of constituents which begin with the elimination of gas at different temperatures is preferred. For example, the elimination of water with aluminum hydroxide begins at approximately 200 °, whereas the elimination of water with magnesium hydroxide begins at approximately 350 °, so that the elimination of gas takes place over a larger temperature range.

The method for producing the components according to the invention is that the individual mixture components are gently mixed with one another and pressed to the desired density, the pressure being maintained until the adhesive has hardened to a sufficient extent. If hot melt adhesives are used or thermoset adhesives only set at higher temperatures, then pressing takes place at elevated temperatures, but still below the temperature at which charring components start to work. Therefore, the pressing temperature is normally at max. kept at approx. 200 ° C. The individual components are mixed in the amounts specified above. Flammable materials are preferably used in an amount of 10 to 40% by weight. In the case of non-combustible inorganic fillers, such as fibers and light fillers, the preferred amount is 70 to 25% by weight. The amount of the flame retardant mixture essentially depends on the amount of combustible materials. The preferred range is 7.5 to 30% by weight. The preferred range of binders or adhesives is 5 to 15% by weight.

The waste parts are preferably already added in small pieces, the mixing being carried out in such a way that the waste parts are essentially not further crushed. The same also applies to the inorganic fibers or fiber structures.

Mixing is preferably carried out in the absence of water, especially in the dry state. If desired, the adhesive can be added in liquid or dissolved form. The inorganic fillers, especially the

Light fillers can be added in the size in which they are commercially available. The inorganic fibers can be shortened to a length of 1 to 2 cm or, if they are in a longer form, wound into balls. The added balls are preferably obtained in their ball form when carefully mixed.

In contrast, the adhesive is added in as fine a distribution as possible in order to be distributed evenly in the mixture. For this purpose, the adhesive is preferably added in powder form. It is also possible to add adhesive components in the liquid state, for example by spraying. In addition to epoxy resins formaldehyde condensates and other thermoset adhesives are also suitable. The usual hot melt adhesives can also be used.

Further features of the invention result from the following examples, which have preferred embodiments of the invention as the subject. Both in the examples and in the subclaims, the individual features can be implemented individually or in combinations with one another! Not be and are not bound by the examples.

example 1

15% by weight of a chopped polyester fleece are placed in a ploughshare mixer. For this purpose, with mixing 15% by weight of a binder / flame retardant mixture consisting of 30% by weight of urea-formaldehyde resin, 18% by weight of ammonium polyphosphate, 20% by weight of dimel amine diphosphate,

T0% by weight of magnesium hydroxide powder and 22% by weight of water and auxiliaries sprayed on. After the water has been completely dried by this mixture, 15% by weight of microglass balls, 49% by weight of mineral fibers and 6% by weight of a phenolic resin are added and mixed intensively. The mixture is then pressed in a press at 200 to 220 ° C within 5 minutes to a plate with a density of 600 kg / m ² . In a fire shaft test carried out with such panels in accordance with DIN 4102, Part 1, an average remaining length of more than 15 cm and a maximum flue gas temperature of 155 ° C. are measured Be pi el 2

In a ploughshare mixer, 20% by weight of a chopped polyester fleece with 9% by weight ammonium polyphosphate, 3% by weight aluminum hydroxide, 5% by weight calcium borate,

7.5% by weight of calcium carbonate, 7% by weight of a powdered epoxy resin hardener mixture, 16% by weight of aluminum silicate hollow spheres, 29% by weight of glass fibers and 3.5% by weight of phenolic resin. The resulting mixture is then pressed in a press at 200 ° C within 5 minutes to a plate with a density of 750 kg / m ² . In a fire shaft test carried out with such panels in accordance with DIN 4102, Part 1, an average remaining length of more than 15 cm and a maximum flue gas temperature of 170 ° C. are measured.

Example 3

In a ploughshare mixer, 10.0% by weight of cut polyethylene film (carrier bags) with 45% by weight of ceramic fibers, 21% by weight of hollow aluminum silicate balls and 24% by weight of a binder / flame retardant mixture consisting of

56.9% by weight of phenolic resin, 14.4% by weight of ammonium polyphosphate, 16.2% by weight of aluminum hydroxide and 12.5% by weight of magnesium hydroxide mixed intensively. The mixture obtained is then pressed in a press at 180 ° C. within 10 minutes to give a tube half-shell with a density of 600 kg / m ³ . In a fire shaft test carried out with such half-shells according to DIN 4102, Part 1, an average remaining length of more than 15 cm and a maximum flue gas temperature of 135 ° C are measured. Example 4

22.0% by weight of chopped polyacrylonitrile fiber waste with 39% by weight of slag fibers, 10% by weight of perlite and 29% by weight of a binder / flame retardant mixture consisting of 36.2% by weight are mixed in a ploughshare arm .-% of a polyvinyl acetate / ethylene / copolymer, 19.7 wt .-% ammonium polyphosphate, 28.3 wt .-% aluminum hydroxide and 15.8 wt .-% magnesium hydroxide mixed intensely. The heterogeneous mixture obtained is then pressed in a press at 190 ° C. within 8 minutes to give a plate with a density of 550 kg / m ³ . In a fire shaft test carried out with such panels in accordance with DIN 4102, Part 1, an average remaining length of more than 15 cm and a maximum flue gas temperature of 165 ° C. are measured.

Example 5

In a ploughshare mixer, 32.0% by weight of papi are shredded with 30.0% by weight of glass fibers, 12.5% by weight of perlite and 25.5% by weight of a binder / flame retardant mixture consisting of 23.5 % By weight of melamine-formaldehyde resin,

11.8% by weight of phenolic resin, 27.5% by weight of ammonium polyphosphate, 25.1% by weight of aluminum hydroxide and 12.1% by weight of magnesium hydroxide were mixed intensively. The mixture obtained is pressed at 200 ° C. within 5 minutes to give a plate with a density of 600 kg / m ³ . In a fire shaft test carried out with such panels in accordance with DIN 4102, Part 1, an average remaining length of more than 15 cm and a maximum flue gas temperature of 140 ° C. are measured.

Claims

Flame-retardant components, inssonsosndner plates, and methods for their manufacture

1. Flame retardant components, in particular panels, made from a pressed mixture

5 to 50% by weight of combustible plastic waste material,

75 to 20% by weight of non-combustible inorganic additives,

4 to 40 wt .-% of a flame retardant mixture and

2. Components according to claim 1, characterized in that at least the plastic waste material and at least some of the inorganic additives are present in a heterogeneous, preferably coarse heterogeneous mixture.

3. Components according to claim 1 or 2, characterized in that the waste material is in the form of particles with an areal expansion of 1 to 20 mm, in particular 2 to 15 mm, the thickness preferably being 0.01 to 4 mm, in particular 0 , 5 to 2 mm.

4. Components according to one of the preceding claims, characterized in that the parts of the waste material are spatially separated from one another, with non-combustible additives and / or flame retardants in between.

5. Components according to one of the preceding claims, characterized in that the waste materials are present in the form of small pieces of non-woven fabrics, fiber balls, film chips and / or foam pieces.

6. Components according to one of the preceding claims, characterized in that the flame retardant mixture and preferably the entire mixture of the components are free from al i ph ati sc hen and aromatic i al compounds, antimony salts and other heavy metal compounds.

7. Components according to one of the preceding claims, characterized in that they are rigid.

8. Components according to one of the preceding claims, characterized in that they have a compressive strength of over 2 N / mm ² , in particular at least about 3 N / mm ² .

9. Components according to one of the preceding claims, characterized in that the fillers consist at least in part, preferably for the most part, of inorganic fibers.

10. Components according to one of the preceding claims, characterized in that the fillers are at least partially light fillers, in particular mineral origin.

11. Components according to claim 9 or 10, characterized in that the weight ratio is from fibrous fillers to non-fillers at 2: 1 to 4: 1, in particular approx 3: 1 lies.

12. Components according to one of the preceding claims, characterized in that the flame retardant mixture contains ablative, in particular carbonizing and / or gas-releasing components.

13. Components according to one of the preceding claims, characterized in that the components of the flame retardant mixture, in particular the entire mixture, are water-insoluble.

14. Components according to claim 12 or 13, characterized in that the carbonizing component of the flame retardant mixture is at least one phosphate, in particular a condensed phosphate.

15. Components according to one of the preceding claims, characterized in that the flame retardant mixture contains at least two gas-releasing components which are effective at different temperatures.

16. Components according to one of the preceding claims, characterized in that the flame retardant mixture contains hydroxides, such as aluminum hydroxide and magnesium hydroxide and / or carbonates and / or basic carbonates.

17. A method for producing the components according to any one of the preceding claims, characterized in that the components are gently mixed together and pressed to the desired density, the pressure being maintained until the adhesive has hardened to a sufficient extent.

18. The method according to claim 17, characterized in that the waste parts are added in small pieces and the mixing is carried out in such a way that the waste parts are essentially not further crushed.

19. The method according to claim 17 or 18, characterized in that the mixing is carried out essentially in the dry state.

20. The method according to any one of claims 17 to 19, characterized in that the adhesive or its components are added in finely divided form.

21. The method according to any one of claims 17 to 21, characterized in that the inorganic fibers are added in the form of balls or flakes and that the

The size of the balls or flakes corresponds approximately to the particle size of the waste particles.