METHOD FOR MANUFACTURING AN OBJECT FROM COMPOSITE MATERIAL, A FORMED OBJECT MANUFACTURED IN ACCORDAN

专利摘要:

公开号:BE1019746A5
申请号:E2010/0436
申请日:2010-07-14
公开日:2012-12-04
发明作者:Ludo Debergh
申请人:Ludo Debergh；
IPC主号:

专利说明:

Method for manufacturing an article from composite material, a shaped article made according to this method
DOMAIN OF THE INVENTION
The invention relates to a method for manufacturing an object from a composite material, and a shaped object manufactured in this way.
STATE OF THE ART
Various methods for manufacturing composite materials are known. In addition, a filler material is often used to obtain a certain volume, to which fibers are added to increase the strength, and to which a binder is added to keep the whole together.
The manual "Molding compounds", DB Miracle & SL Donaldson, "Composites", December 2001, ASM International, USA, XP002612163, ISBN: 0871707039, part 21, pages 141-14, describes some composite compositions with a resin (as a binder or matrix), fibers (as a reinforcing agent) and additives (such as dyes, flame retardants, etc.) and indicates the influence of the fiber length and the resin type on the mechanical properties, such as tensile strength, flexural strength and impact strength of a product made from such a composite material.
FR 2 235 775 A1 describes a method for manufacturing a mixture with a plastic and a filling material, wherein both the drying and the mixing of the filling materials take place at high temperature (100 ° C) and under vacuum (1 Torr). The plastic particles are in powder form. Intended products are blown hollow bodies such as containers for storing liquids or powders.
US 2006/057319 A1 describes a process for manufacturing a fiber-reinforced polymer for making fiber-reinforced polymer products, by mixing a high temperature polymer (150 - 450 ° C) with a wet fiber product (moisture content of 5-15%) ). The method is based on the principle that the fiber product does not have to be completely dry, but that it is dried during the production of the fiber-reinforced polymer. The intended products are, for example, instrument boards or door panels for cars, which require a perfect surface.
DE 10 2005 048874 A1 describes a process for the production of fiber-reinforced plastic molding or coating, wherein cut fibers are mixed with raw materials for polyurethane.
JM Henshaw: "Recycling and Disposal of Polymer-Matrix Composites", In: DB Miracle & SL Donaldson: "Composites", December 2001, ASM International, USA, XP002612183, ISBN: 0871707039, part 21, p 1006-1012, is a article about the incineration, landfilling and recycling of polymer-matrix composites. It describes processes to separate the components of a composite material.
EP0442435 describes a method for recycling waste or used articles made from cross-linked plastic, in particular polyurethane, which comprises the steps of: a) reducing residues from waste products composed of cross-linked synthetic resin, in particular polyurethane or polyurea, to flakes or granules up to a size <15 mm, in particular <= 5 mm; b) the reduced material is processed in a thermomechanical energy device, for example a kneading machine, for 5 to 30 minutes at an appliance temperature of 130-180 ° C, whereby a mechanical-thermal decomposition takes place without loss of mass; c) in a mixing device a polyfunctional isocyanate is added to this mass for renewing the cross-linking, the mass having a temperature <= 80 ° C and the mixing device having a temperature of <= 30 ° C; d) the reaction mixture is cooled within 10 minutes; e) the mixture is heated in a mold for 5 to 20 minutes to a temperature of 130 ° C-170 ° C at a pressure of at least 100 bar and is therefore cross-linked. A disadvantage of this process and the resulting product is that the product has only moderate mechanical properties.
DISCLOSURE OF THE INVENTION
It is an object of the invention to provide a method for manufacturing an article from a composite material containing thermoset plastic particles, with improved mechanical properties (e.g., a higher flexural strength).
This object is achieved by a method with the features of the first claim. To this end, the method according to the invention comprises the following steps: a) providing a dry, homogeneous mixture comprising fiber material with an average length of 2-40 mm and a granulate of thermoset plastic particles with an average particle size of 2 -15 mm, wherein the volume percentage of the fiber material is 10 - 80% of the dry homogeneous mixture, and wherein the dry homogeneous mixture has a humidity which is in equilibrium with air having a dew point of at most 25 ° C; b) adding at least one polyol and at least one isocyanate to the dry homogeneous mixture to form a viscous compound mixture, the weight percent of the at least one polyol and the at least one isocyanate together being 4.0 - 25.0% of the dry homogeneous mixture, and mixing the viscous compound mixture, thereby forming a viscous homogeneous mixture; c) forming a shaped article by curing the viscous homogeneous mixture in a mold at a temperature of 15 - 60 ° C under a curing pressure of at least 50 bar, the pressure p being maintained for at least 1 minute.
In this document, "particle diameter" or "grain size" or "particle size" of a particle or particle means the largest linear distance between two points of that particle. By "mean" is meant the mathematical mean over a group of particles.
In this document, "length of the fiber material" or "fiber length" means the largest linear distance between two points of a particle of a fibrous material, even if the particle is not pronounced elongated in shape. By "mean" is meant the mathematical mean over a group of particles.
In contrast to the method described in EP0442435 where the cohesion of the particles of the mixture is achieved by cross-linking by means of a polyisocyanate, and in which fibers and dust must be removed because they cause the cross-linking disrupting (as described in EP0442435), the inventor has surprisingly determined that it is nevertheless possible to add fibers (e.g. glass fiber or carbon fibers) to such a granulate thereby improving the mechanical properties (such as flexural strength) of the molded article. To this end, according to the invention, polyol and isocyanate are added to the dry mixture, which together will form to form polyurethane which serves as a binder for both the granulate and for the fibers. By mixing the viscous mixture such that the polyol and the isocyanate distribute substantially uniformly over the dry homogeneous mixture, this binder (polyurethane) will spread between and around all particles. By compressing this viscous homogeneous mixture before the reaction of the polyol and the isocyanate takes place, the polyol and the isocyanate will be pressed into the pores of the particles, and only then bond, whereby a very strong mechanical adhesion is obtained between the filler material (granulate) and the reinforcement material (fibers) and the binder (polyurethane). By molding in a mold, objects of very different shapes can be produced.
Tests have shown that the article thus formed has good mechanical properties (eg a manhole cover with a flexural strength that meets the load class A and / or B and / or C of standard NBN EN 124) that is comparable to that of existing cast iron articles of the same size, so that the method according to the invention can be used for the manufacture of a wide range of objects where until now mostly only concrete or cast iron were used, in particular in the construction sector.
An additional advantage of the method according to the present invention is that it allows to recycle a large number of non-thermoplastic plastic materials as well as rejected or used fiber materials, so that these materials do not have to be incinerated or dumped, which is favorable for the environment, and whereby the cost price of the objects to be formed can be drastically reduced. Furthermore, the shaped article according to the invention has the advantage over a similar concrete or steel or cast iron article that it is lighter. Another advantage is that the shaped object is very impact-resistant and temperature-resistant (over a temperature range of -40 ° C to + 70 ° C). Another advantage of the molded article according to the invention is that it has a less smooth surface, which offers particular advantages in the winter, whereby such an object is extremely suitable as street tiles or the like. An additional advantage over steel or cast iron is that the composite material of the molded article according to the invention does not rust. A further interesting advantage is that steel has become extremely scarce and expensive in recent years, so that the price of "old iron" has risen sharply, and therefore also the number of thefts of metal objects on or along public roads (eg sewer grates , manhole covers and the like). This is not only very dangerous for pedestrians or vehicles, but also costs the authorities a lot of money. When the article according to the invention is made as much as possible from recycled material, not only is the cost price of the molded articles very low, but moreover theft is avoided, since there is no (paying) outlet for stolen molded articles made from such recycled material.
The inventor has determined that the above method does not work well when thermoplastic plastic particles (such as, for example, PVC or PE or PP) or thermoplastic fiber material are used because it does not adhere well to polyurethane.
In an embodiment of the method according to the invention, providing the dry homogeneous mixture comprises the following steps: - providing a fiber material with an average length of 2 - 40 mm, and drying the fiber material until the fiber material has a humidity that is is in equilibrium with air having a dew point of at most 25 ° C, thereby forming a dried fiber material; - providing a granulate of thermoset plastic particles with an average particle size of 2-15 mm, and drying the granulate until the granulate has a humidity in equilibrium with air having a dew point of at most 25 ° C, thereby forming a dried granulate; - mixing the dried fiber material and the dried granulate into the dry, homogeneous mixture, wherein the volume percentage of the fiber material is 10 - 80% of the dry, homogeneous mixture.
If the fiber material and the thermoset plastic particles are too large, they must be reduced according to known techniques. Depending on the raw materials, this reduction can be done before or after drying. Reducing and drying can also be done in several steps. If the fiber material and the thermoset plastic particles contain too much moisture, they must be dried. In a first embodiment of the method according to the invention, the fiber material and the thermoset plastic particles are dried separately. This offers the advantage that each drying installation can be set with its own temperature and humidity, and that the drying installations can contain other mechanical provisions for the optimum drying of either fiber material or the granulate of thermoset plastic particles. Drying before mixing also offers the advantage that the mixing of the fiber material and the granulate in the desired ratio is more controllable with dry matter than with matter that contains too much moisture.
Preferably, the drying of the fiber material is carried out by contacting it with dry warm air at a temperature of 100 - 300 ° C, preferably 150 - 300 ° C, more preferably 200 - 275 ° C, most preferably almost 250 ° C, for example for a period of typically 1 to 3 hours, depending on the moisture content of the dried fiber material. Tests have shown that fibers such as glass fibers or carbon fibers can be dried at a higher temperature than the granulate of thermoset plastic particles. This offers the advantage that drying can be faster, or that a lower dew point can be achieved within a given time.
The drying of the granulate is preferably carried out by contacting it with dry warm air with a temperature of 100 - 175 ° C, preferably a temperature of 125 - 160 ° C, more preferably a temperature of substantially 150 ° C .
In an alternative embodiment of the method according to the invention, providing the dry homogeneous mixture comprises the following steps: - providing a fiber material with an average length of 2 - 40 mm; - providing a granulate of thermoset plastic particles with an average particle size of 2-15 mm; - mixing the fiber material and the granulate, wherein the volume percentage of the fiber material is 10 - 80% of the mixture, and mixing the mixture into a homogeneous mixture; - drying the homogeneous mixture until the mixture has a humidity in equilibrium with air having a dew point of at most 25 ° C, thereby forming a dry homogeneous mixture.
In an alternative embodiment, therefore, the raw materials are first mixed, and then the mixture is dried. This has the advantage that only one drying installation is needed instead of two, and if desired, that the mixing can take place during the entire drying process, so that a separate step of mixing the dry fibers and the granulate particles into a homogeneous mixture can take place. be avoided.
Preferably the dry homogeneous mixture has a temperature of at most 50 ° C, preferably at most 45 ° C, more preferably at most 40 ° C, even more preferably at most 35 ° C. If the temperature of the dry homogeneous mixture is too high, the polyol and the isocyanate will bond more quickly, which is not desirable. On the other hand, a temperature lower than the ambient temperature is not desirable because it requires active cooling and / or slows down the reaction too much.
Preferably, the dry homogeneous mixture has a humidity in equilibrium with air having a dew point of 5 ° C - 22 ° C, preferably of 10 ° C - 20 ° C, most preferably substantially 18 ° C. Experiments have shown that the moisture of the dry homogeneous mixture is crucial for good adhesion of the fibers and the granulate particles and for the mechanical properties of the molded article, and that a certain humidity is desired. If the humidity is too low and therefore the mixture too dry, the polyol and the isocyanate will not spread sufficiently through the mixture and lump formation will occur. If the humidity is too high and the mixture contains too much water, then the mechanical properties of the molded article appear to be not so good. Perhaps this is because the polyurethane will then react too quickly and / or show foaming, and / or because a portion of the water will react with the isocyanate to form CO2. The inventor has found that a method in which the moisture of the dry homogeneous mixture is reduced to a dew point of almost 18 ° C appears to give very good results.
Preferably the mixing of the viscous compound mixture takes place in a period of 10 sec -10 minutes, preferably 10 sec-5 minutes, more preferably 10 sec-2 minutes, even more preferably 10 -60 seconds, most preferably almost 20 seconds. Tests have shown that a good distribution of the polyol and the isocyanate in the dry homogeneous mixture is crucial for the mechanical properties of the end product. The longer the mixing takes place, the better the distribution, but this also depends strongly on the construction of the mixing machine. On the other hand, this time should be as short as possible, since the viscous homogeneous mixture must be introduced into the mold, and the mold must be pressurized before the reaction between the polyol and the isocyanate begins. As is known, this time can be "set" to size, for example by adding known reaction retarders. Since information about this is freely available, it requires no further explanation here. The mixing time must be large enough to get a good spread, but preferably as short as possible to achieve the highest possible productivity. For a certain dry homogeneous mixture and a certain mixing machine, the optimum time can be determined by those skilled in the art by routinely performing a number of tests. If desired, the reaction time can be extended by the addition of known reaction retarders.
Preferably, the average length of the fiber material is a length of 2 - 30 mm, preferably 3 - 20 mm, more preferably 4 - 15 mm, even more preferably 6 - 12 mm, most preferably substantially 8 mm. Tests have shown that not only the volume% of fibers, but also the average length of the fibers has an influence on the mechanical properties (such as, for example, the flexural strength) of the molded article, with a longer average length generally having better mechanical properties (such as bending strength). Good results are generally achieved for an average fiber length of at least 6 mm. A longer fiber length will improve the mechanical properties a little, but usually the aesthetic appearance will decrease somewhat. The person skilled in the art can choose an optimum average fiber length depending on the intended application.
The granulate preferably has an average particle diameter of 2-10 mm, preferably 3-7 mm, more preferably substantially 6 mm. A disadvantage of small particles (eg 2 mm) is that much remains in the mixing machine, in which the polyol and isocyanate are added and mixed with the dry homogeneous mixture, after the viscous homogeneous mixture has been removed from the mixing machine. A disadvantage of particles that are too large is that the appearance of the shaped object is not aesthetically attractive and that the object appears to be less strong. Furthermore, tests have shown that the amount of polyol and isocyanate that is added to the dry homogeneous mixture should be adjusted to the average particle diameter of the granulate. The smaller the average grain size of the granulate, the more polyol and isocyanate must be added to achieve good adhesion.
The volume percentage of the fiber material in the dry mixture is preferably 20 to 60%, preferably 30 to 50%, more preferably substantially 40%. Tests have shown that the volume percentage of the fiber material in the mixture has a major influence on the strength of the molded article. Typically, the more fiber material, the stronger the final product (e.g. in terms of flexural strength), if the amount of binder (i.e. polyol and isocyanate) is optimally matched to the average length and amount of the fibers and the average grain size of the granulate.
Preferably, the weight percent of the at least one polyol and the at least one isocyanate together amounts to 5.0 - 20.0% of the dry mixture, preferably 5.0 - 15.0%, more preferably 5.5 - 10.0 %, most preferably almost 7.0%. Polyol and isocyanate will together form polyurethane which acts as a binder between the fibers and the granulate particles of the molded article. If insufficient binder is added to the dry homogeneous mixture, e.g. less than 5.0% by weight, then there will be insufficient dispersion of the polyol and the isocyanate, and then not all particles will be bonded to each other, or only by a very thin film, which translates into reduced or even poor mechanical properties (such as flexural strength). If too much polyol and isocyanate are added, for example more than 15% by weight, the viscous compound mixture will become very liquid, and the mixing machine will be moistened too much, which increases the risk that the machine will crash. Moreover, these raw materials (polyol and isocyanate) is quite expensive, so moderate use is appropriate. Again, for a certain dry mixture, the optimum amount of binder can be determined by those skilled in the art, by performing routine tests, where a value of 7 weight percent is a good city value.
The curing of the viscous homogeneous mixture preferably takes place in the mold which has a temperature of 15 - 50 ° C, preferably 15 - 40 ° C, more preferably 15 - 30 ° C, most preferably substantially 20 ° C . The mold is not heated, which is a major advantage of the method of the present invention, inter alia because of the energy saving. At production start-up, the temperature of the mold is then equal to the ambient temperature of the plant (eg 18 ° C in winter - 30 ° C in summer), and the mold typically warms up slightly (eg +5 to 10 ° C) during production due to the compression and the exothermic reaction of the formation of polyurethane. A mold temperature of 20 ° C to 40 ° C appears to give very good results, the cure is already a little too fast at temperatures higher than 50 ° C, and too slow at temperatures lower than 15 ° C.
Curing is preferably carried out in the mold at a curing pressure of at least 100 bar, preferably at least 150 bar, more preferably at least 175 bar, most preferably at least 200 bar. The pressure with which the viscous homogeneous mixture is compressed in the mold has an influence on the final volume of the object, but also on its mechanical properties. This curing pressure must be maintained for at least 1 minute, preferably at least 2 minutes.
Preferably at least one type of rejected and / or recycled fiber material is used. And preferably, at least one type of rejected or recycled thermoset plastic particles is used. By using rejected materials or used materials, such materials no longer need to be incinerated or dumped, which is beneficial to the environment, but moreover these raw materials are available at a low price, which drastically reduces the cost of the objects to be molded. can become.
It is also an object of the invention to provide a molded article manufactured according to this method, in particular a manhole cover that meets the requirements of load class B according to the NBN EN 124 standard.
BRIEF DESCRIPTION OF THE FIGURES
The present invention will be described with reference to certain embodiments and with reference to certain drawings, but the invention is not limited thereto, but only by the claims. The drawings are only schematic and are non-limitative. The drawings are not necessarily drawn to scale, and the size of some elements may be exaggerated for illustrative purposes. The dimensions and the relative dimensions do not necessarily correspond to the actual ratios in the practice of the invention. The drawings are intended to describe the principles of the invention. Embodiments of the invention can use combinations of the various features and elements of various drawings.
Fig. 1A shows an example of a method for providing a dry, homogeneous mixture.
Fig. 1B schematically shows the steps of a preferred embodiment of the method according to the invention.
Figures 2A-2E show how a first shaped object, in particular a rectangular frame, can be formed in a first mold according to the method of the invention.
Figures 3A-3E show how a second shaped object, in particular a flat plate or a floor tile, can be formed in a second mold according to the method of the invention.
Figures 4A-4C show a manhole cover according to the present invention, in perspective, top view and side view.
Figures 5A-5C show a sewer well according to the present invention, in perspective, top view and side view.
Fig. 6 shows a vowel according to the present invention.
Fig. 7 shows a fire hydrant shield or a fire hydrant sole according to the present invention.
Fig. 8 shows a tile according to the present invention.
Fig. 9 shows a principle diagram of a mixing machine that can be used to carry out the present method.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS OF THE INVENTION
REFERENCE FIGURES: 1 thermoset plastic particles 2 granules of thermoset plastic particles with a predetermined average particle size 3 dried granules of thermosets plastic particles 4 fiber material 5 fiber material with a predetermined average length 6 dried fiber material 7 polyol 8 isocyanate 10 dry mixture 11 dry homogeneous mixture 12 viscous mixture 13 viscous homogeneous mixture 14 homogeneous mixture 20 molded object 21 well cover 22 sewer well, drain 23 clinker 24 foundation sole or frame for a fire brigade valve 25 floor tile 28 mold 29 lower part of the mold 30 upper part of the mold 31 mixing machine (f. viscous mixture) 32 motor 33 inlet 1 for the dry, homogeneous mixture 34 inlet 2 for polyol 35 inlet 3 for isocyanate 36 outlet valve 37 axis of the mixing machine 38 mixing chamber 40 reducing the granulate of thermoset plastic particles 41 drying the granulate of thermoset plastic particles 42 reducing the fiber size 43 drying the fiber material 44 mixing the granulate and the fibers 45 drying the mixture 46 adding polyol 47 adding isocyanate 48 mixing the viscous mixture 49 curing the viscous mixture in the mold 50 cooling the granulate 51 cooling the granulate the fiber material
The invention relates to a method for manufacturing a molded article from a composite material comprising thermoset plastic particles, the method comprising the steps of: a) providing a dry, homogeneous mixture 11 comprising fiber material 4 with an average length of 2 -40 mm and a granulate of thermoset plastic particles with an average particle size of 2-15 mm, wherein the volume percentage of the fiber material is 10 - 80% of the dry homogeneous mixture, and wherein the dry homogeneous mixture 11 has a moisture which is in equilibrium is with air that has a dew point of no more than 25 ° C; b) adding at least one polyol 7 and at least one isocyanate 8 to the dry homogeneous mixture 11 to form a viscous mixture 12, the weight percent of the at least one polyol 7 and the at least one isocyanate 8 together being 4.0-25, Is 0% of the dry homogeneous mixture 11, and mixing the viscous mixture 12, thereby forming a viscous homogeneous mixture 13; c) forming a shaped article 20 by curing the viscous homogeneous mixture 13 in a mold 28 at a temperature of 15 - 60 ° C under a curing pressure p of at least 50 bar, the pressure p being maintained for at least 1 minute .
The steps of this method are illustrated in Fig. 1B, where a dry homogeneous mixture 11 is introduced into a mixing machine 31. An example of such a mixing machine 31 will be further discussed in more detail with reference to Fig. 10. The mixing machine 31 also an amount of polyol 7 and isocyanate 8 is introduced, and distributed as uniformly as possible over the dry homogeneous mixture 11 so that a viscous homogeneous mixture 13 is obtained. Step 48 shows the mixing of the viscous mixture 13. This viscous homogeneous mixture 13 is introduced into a mold 28 which, for example, is placed in a hydraulic press to exert a pressure on the mold 28. After the viscous homogeneous mixture 13 in step 49 at least partially cured in the mold 28, the molded article 20 can be removed from the mold. Traditional post-processing can possibly be done on the shaped object, such as, for example, deburring, grinding or drilling. The step 45 for drying the homogeneous mixture 14 (at the top in Fig. 1B) is an optional step. If the moisture content in the homogeneous mixture 14, which contains fiber material and a granulate of thermoset plastic particles, is sufficiently low (eg in equilibrium with air having a dew point of 18 ° C), then the homogeneous mixture 14 does not need to be further dried, but it can be directly introduced into the mixing machine 31. If the moisture content of the homogeneous mixture 14 is higher than a certain value (corresponding to a dew point of air of, for example, 18 ° C), then the homogeneous mixture 14 is first dried in step 45 before to be introduced into the mixing machine 31. The polyols and isocyanate family to form polyurethane are well known substances, and are freely available commercially, eg under the Baydur20® trade name from Bayer®, but other polyols and isocyanates are suitable considered by those skilled in the art can also be used.
Fig. 1A shows a preferred embodiment of a method for producing the dry, homogeneous mixture 11. Thereby, a thermoset raw material 1, for example a granulate of recycled thermoset plastic particles with dimensions of, for example, 5 mm - 5 cm, is used. This raw material is first reduced in step 40 by known techniques (e.g. milling, cutting, etc.) to an average particle diameter (also called "grain size") of, for example, substantially 8 mm, and then dried in step 41. The shrinking step 40 can be skipped when the average particle diameter of the thermoset raw material 1 is already sufficiently small (e.g. <10 mm). The drying step 41 can be skipped if the moisture content of the thermoset raw material 1 is already sufficiently low (i.e. in equilibrium with air with a dew point of, for example, 18 ° C). The moisture content of the granulate can be measured with known devices. If the granulate is dried, it must also be cooled again (eg in the ambient air) to a temperature of, for example, a maximum of 35 ° C. The result is a dried granulate 3 with an average grain size of, for example, 8 mm. A fiber material 4 is also started, e.g. rolls of rejected glass fiber mats, which are first reduced in step 42 to fibers with an average length of, for example, substantially 6 mm, which in turn are dried in step 43. The step of reducing the size of the fiber material 42 can optionally be skipped if the fiber material 4 is already sufficiently small. The step of drying the fiber material 43 can optionally be skipped if the fiber material is already sufficiently dry. Just as with the granulate, this moisture content can be measured. If the fiber material is dried, it must also be cooled down again (eg in the ambient air) to a temperature of, for example, a maximum of 35 ° C. The result is a dried fiber material 6 with an average length of, for example, 6 mm. The dried granulate 3 and the dried fiber material 6 are then combined in a ratio of, for example, 40 volume% fiber material, and mixed in step 44 to a dry, homogeneous mixture 11. This mixing is preferably carried out at room temperature (ie 18 ° C - 30 ° C) ). Variations of the method for providing the dry homogeneous mixture 13 are possible. Thus, depending on the characteristics (eg size) of the thermoset raw material 1, step 41 for drying the granulate can possibly be carried out before step 40 for shrinking the thermoset plastic particles. The same applies to the fiber material 4, where possibly the drying of step 43 can be carried out before the reduction of step 42. Optionally, the mixing step 44 can also precede the cooling 50, 51 step. Or, as is often the case in practice, the cooling will take place partly before mixing, and partly during or after mixing. In a variant of the method for providing the dry homogeneous mixture 11, the comminuted granulate can also first be combined with the comminuted fibers in the desired ratio (e.g. 40% by volume of fibers), and then the mixture can be dried and cooled. However, other variations to obtain a dry, homogeneous mixture 11 can also be used.
Referring back to Fig. 1B, when the dry homogeneous mixture 11 of Fig. 1A is used almost immediately (eg within the hour when the ambient air is not too moist) in the mixing machine 31 of Fig. 1B, the additional step 45 of drying is of the homogeneous mixture 14 superfluous. However, if the dry homogeneous mixture 11 of Fig. 1A is first stored for several hours or even days in a non-hermetic package or container (e.g. in big bags of 3 m) before it is used in the mixing machine 31 of Fig. 1B, then the dry homogeneous mixture 11 absorbs moisture from the ambient air and transforms it into a homogeneous mixture 14, which must first be dried in step 45 before being introduced into the mixing machine 31. Since the moisture content of the dry homogeneous mixture 11 is important for quality of the molded article, in practice the humidity of the homogeneous mixture 14 is usually measured first, and if the humidity is higher than the predetermined value (e.g. in equilibrium with air with a dew point of 18 ° C), then the homogeneity becomes mixture 14 dried in step 45 by contacting it with dry warm air with a temperature of, for example, 50 ° C and a dew point of, for example, 18 ° C. A relatively low temperature of 50 ° C is preferably used here to keep the heating of the homogeneous mixture 14 limited. It is desirable to limit the temperature of the dry homogeneous mixture to about 35 ° C or at most 40 ° C.
Fig. 9 schematically shows a preferred embodiment of a mixing machine 31 for adding at least one polyol 7 and at least one isocyanate 8 to the dry homogeneous mixture 11, and distributing it as uniformly as possible, thereby forming a viscous homogeneous mixture 13. A motor 32 drives a shaft 37 that rotates in a mixing chamber 38. On this shaft 37 is a spiral (not shown) comparable to the screw of a typical injection molding machine for propelling the mixture into the mixing chamber 38 and for building a pressure (from, for example, 2 bar). However, there are also elements (not shown) on this shaft 37 for distributing the polyol 7 and the isocyanate 8 over the mixture. These elements can be, for example, flat or curved square or rectangular teeth (of, for example, 10 cm x 10 cm x 1 cm) which are fixed to the shaft 37 and are spaced apart (for example 10 cm) and are angled with each other. (eg substantially 90 °) with respect to each other and have an angle with respect to the axis (eg alternately an angle of + 45 ° and -45 ° for successive elements). But other mixing machines 31 suitable for distributing a liquid through a dry granulate can also be used. Three inlets are provided at the mixing machine 31, more specifically at the mixing chamber 38: a first inlet 33 for introducing the dry homogeneous mixture 11, a second inlet 34 for adding at least one polyol 7, a third inlet 35 for adding of at least one isocyanate 8. During the operation of the mixing machine 31, first an amount of the dry homogeneous mixture 11 will be introduced into the mixing chamber 38. This dry homogeneous mixture 11 is preferably at a temperature of at most 40 ° C, at most 35 ° C, most preferably at ambient temperature (i.e. substantially 18 ° C in winter, up to 30 ° C in summer). Temperatures in excess of 30 ° C can occur, for example, when local drying 45 of the homogeneous mixture 11 takes place as discussed in Fig. 1A and Fig. 1B. After introducing an amount of the dry homogeneous mixture 11 into the mixing chamber 38 (e.g., substantially 8 kg, depending on the dimensions of the mixing machine), an amount of polyol 7 (e.g., substantially 280 g) and an amount of isocyanate 8 (e.g., substantially 280 g), together is that 7% by weight of the dry homogeneous mixture 11 is added, and distributed as uniformly as possible for a predetermined time (e.g. about 20-30 seconds) after the application of the polyol 7 and the isocyanate 8, for forming a viscous homogeneous mixture 13. The mixing machine 31 is preferably constructed in such a way that sufficient pressure is built up in the mixing chamber 38 after this predetermined time so that the mechanical outlet valve 36 on which a mechanical back pressure is exerted (e.g. by means of a spring ), so that the viscous homogeneous mixture 13 can leave the mixing chamber 38, and can be introduced into a mold 28. This is shown in Fig. 2A or 3A. The mold 28 is preferably made of steel to withstand the high pressure of 100 - 200 bar. It has been found that about 5 kg of viscous homogeneous mixture remains in the mixing chamber 38 after opening the outlet valve 36, in particular on the walls of the mixing chamber 38 on the coil and on the teeth, which will cure on the machine 31 if that would be shut down. To prevent the mixing machine 31 from becoming clogged in the long run, the machine is "rinsed dry", as it were, before it is stopped. This can be done, for example, by filling the machine 31 again with the dry, homogeneous mixture 11, but without adding polyol 7 and isocyanate 8. Since polyurethane is a thermoset plastic material, this material can be recycled again. Rinsing with another dry mixture (eg dried granules of thermoset plastic particles without fibers) is also possible.
Fig. 2A shows an example of a mold 28 for manufacturing a rectangular frame (see Fig. 2E), but other shapes considered suitable by those skilled in the art can also be used. As the mold 28 is not actively heated or cooled, the temperature of the mold 28 is approximately the same as the ambient temperature (eg 18 ° C in winter - 30 ° C in summer), although the mold 28 will heat up slightly during production ( eg +5 to 10 ° C) due to the compression of the viscous homogeneous mixture 13 and due to the exothermic reaction of the polyol 7 and the isocyanate 8. The mold 28 shown in Fig. 2A consists of two parts, a lower part 29 with a cavity into which the viscous homogeneous mixture 13 is introduced (Fig. 2B), and an upper part 30 which is brought to the lower part 29, after which the two parts 29, 30 are compressed (Fig. 2C and Fig. 2D) under a predetermined press p, eg in a traditional press. For obtaining a shaped article 20 with desired mechanical properties (such as, for example, hardness, flexural strength, tensile strength, porosity), this pressure p is a pressure of at least 50 bar, preferably at least 100 bar, more preferably at least 150 bar, with even more preferably at least 175 bar, most preferably at least 200 bar. This pressure p can be maintained during the entire curing period (e.g. 4 - 8 minutes) or only for a part thereof (e.g. 2 minutes), but other curing periods are also possible, e.g. 1 minute or 30 seconds. After curing, the mold 28 is opened, and the molded article 20 is removed from the mold. Fig. 2E shows an example of a rectangular frame thus formed that can be used, for example, as the sole of a fire hydrant. Typical dimensions are: 11 cm high, 70 cm long, 50 cm wide, 8 cm wall thickness.
Figures 3A-3E show a second example of a mold 28 with a different cavity, and a second shaped object 20, in this case a floor tile or a street tile or a cover or a flat plate with predetermined dimensions (length, width and thickness) . The mechanical properties of this cover are determined both by the raw materials used: - the choice of the fiber material, for example glass fiber, carbon fiber or fibers of thermoset plastics, whereby carbon fibers will generally provide greater strength than, for example, glass fibers; - the average length of the fibers, eg 8 mm; - the choice of granulate made of thermoset plastic particles, for example from recycled polyurethane or recycled bakelite or other thermoset plastics; - the average particle size (also called "grain size") of the granulate, for example 6 mm; - the volume percentage of the dry fiber material and the dry granulate, for example a ratio of 20/80 or 30/70 or 40/60 or 50/50; - the amount of polyol 7 and the amount of isocyanate 8 that are added to the dry homogeneous mixture 11, for example substantially 290 g of isocyanate and approximately 270 g of polyol that is added to approximately 8 kg of dry mixture; and also by the process parameters: - the temperature, the humidity and the uniformity of the dry homogeneous mixture 11, the time during which the viscous mixture is mixed in the mixing machine 31, the temperature, humidity and the uniformity of the viscous mixture 13, the temperature of the mold 28, the pressure p exerted on the mold 28 during curing, the time during which this pressure p is exerted (e.g. 2 minutes), as well as by external factors such as the ambient temperature, the humidity of the environment, which, although so much possibly be excluded.
The person skilled in the art can measure the mechanical properties of an article thus formed, and if desired can adjust the choice of materials, and / or the mixing ratio and / or the process parameters, if necessary. The inventor has determined that metal fibers or metal chips also work well as a filler and adhere well with the binder (polyurethane), but has also determined that they give rise to rust and form sharp protruding particles on the surface of the molded product 20, which is undesirable . The incorporation of, for example, an aluminum handle or an aluminum plate with an inscription (eg coordinates) is very interesting.
Figures 4A-4C show resp. in perspective view, top view and side view an example of a manhole cover 21 (also called "sewer cover") that can be manufactured according to the method described above. This manhole cover 21 has a thickness of, for example, 50 mm and a diameter of, for example, 160, 250, 315, 400 or 630 mm, but manhole covers 21 with other dimensions can also be manufactured. Such manhole covers 21 are today mostly made of concrete or steel or cast iron, and the mechanical requirements that they must meet are specified in the NBN EN 124 standard. In summary, it means that three load classes are defined for manhole covers, load class A (15 kN) for traffic areas that can only be used by pedestrians or cyclists, load class B (125 kN) for footpaths, parking places or parking levels for passenger cars, and load class C (250 kN) for zones between roadway and footpath, as well as parking places accessible for heavy traffic. The test consists of pressing the manhole cover 21 with a certain force (15 kN, 125 kN, 250 kN) by means of a pressure stamp with a diameter of 25 cm, whereby certain criteria must be met with regard to static load, dynamic load and fracture load, as described in the NBN EN 124 standard. A manhole cover 21 that meets load class B also meets load class A. A manhole cover 21 that meets load class C also meets load class A and B.
The inventor has determined experimentally that a manhole cover 21 of 50 mm thick and, for example, 315 mm diameter that meets the load class B according to the NBN EN 124 standard, and a manhole cover 21 of 60 mm thick and, for example, 315 mm diameter that meets the load class C according to the standard standard NBN EN 124 can be manufactured by a method as described above, in which: - the fibrous material mainly comprises recycled glass fibers; - the fiber material is reduced until the average length of the fiber material is almost 6 mm; - drying the fiber material is carried out by contacting dry hot air at a temperature of 250 ° C, and drying this air until the air has reached a dew point of at most 5 ° C. (This can be done eg in known dry air installation such as eg commercially available from Mann + Hummel® under the brand name Somos®); - the granulate of thermoset plastic particles comprises mainly recycled polyurethane particles; the granulate is reduced until the average particle diameter of the granulate is almost 6 mm; - drying the granulate of thermoset plastic particles is carried out by contacting dry hot air with a temperature of 150 ° C, and drying this air in a second dry air installation, until this air has reached a dew point of too high. highest 18 ° C; - the volume percentage of the fiber material in the dry homogeneous mixture 11 is substantially 40%, and the volume percentage of the granulate in the dry homogeneous mixture 11 is approximately 60%; - this dry, homogeneous mixture 11 may be stored for several hours or a few days in bags (or containers or "big bags"), exposed to the ambient air, until it can be processed in the mixing machine 31; - just prior to processing in the mixing machine 31, re-drying the homogeneous mixture 11 by bringing it into contact with dry warm air of 50 ° C in a third dry air installation until the air has reached a dew point of at most 18 ° C ; - the weight percent of the polyol 7 and the isocyanate 8 that is added to the dry homogeneous mixture 11 at ambient temperature (typically 18 ° C in winter - 30 ° C in summer) together amounts to almost 7 weight percent of the dry homogeneous mixture 11; - the amount of the viscous homogeneous mixture 13 that is introduced into the mold 28 is almost 2.0 times the volume of the space in the mold 28; the curing takes place in a mold 28 which has a temperature of substantially 18 ° C - 30 ° C, wherein the curing takes place under a pressure of almost 200 bar, the pressure being maintained for a period of almost 4 minutes.
Comparative tests for the manufacture of such well lids, in which an equal amount of viscous homogeneous mixture 13 was introduced into the mold 28, but where the curing pressure p was maintained for only 2 minutes instead of 4 minutes, have shown that the thickness of the well lid is approximately 5.2 - 5.3 cm instead of 5.0 cm. Although the mechanical properties of this lid were not precisely determined, it is expected that it may be at least 10% less strong (eg in terms of deflection).
The factor of approximately 2.0 volume compression was observed in the manufacture of well covers with a thickness of 5 cm and a diameter of 25 cm, 30 cm and 40 cm. (other diameters were not tested).
Drop tests in which this manhole cover 21 from a height of 3 and 7 meters is thrown onto a hard surface (vowels) without breaking, show that this manhole cover 21 has a high impact resistance. Concrete manhole covers are much brittle. Temperature tests have shown that the well covers 21 according to the invention are suitable for use in a temperature range of -40 ° C to + 70 ° C, and that the thermal expansion is negligibly small.
The inventor has also surprisingly determined that the material of this manhole cover 21 adheres particularly well to cement or concrete. Other advantages of this manhole cover are that drilling, grinding, milling, sawing, etc. can be done easily in this material, which is not possible or much more difficult with a cast-iron cover. Moreover, the surface of the manhole cover also appears to exhibit very good anti-slip properties, so that the traditional protruding blocks present on classic cast iron manhole covers to increase grip on shoes and / or tires in the winter can be omitted. These blocks are very annoying for pedestrians and cyclists. Finally, the weight of the manhole cover 21 according to the invention (typically 4 kg) is much lighter than a comparable cast iron manhole cover (typically 8 kg), making it easier to open or place. Moreover, it does not rust, but retains its aesthetic appearance. Furthermore, it cannot rust firmly, which is a major advantage over cast-iron sewer covers, where people are often confronted with this problem.
These improved mechanical properties will of course also apply to other shaped articles manufactured according to this method and with the same composition, regardless of the specific shape.
From tests where the same viscous homogeneous mixture 13 was used to manufacture a base sole for a fire hydrant 24 (as shown in Fig 3E or Fig 8) but where a curing pressure of 130 bar was used, and where the curing pressure was only maintained for 2 minutes It was found that the amount of the viscous homogeneous mixture 13 to be introduced into the mold 28 is only about 1.5 times the volume of the space in the mold 28.
To produce manhole covers 21 that comply with load class A of standard NBN EN 124, a pressure of 100 bar is probably sufficient, and / or the volume% of fiber material can probably be reduced, and / or a shorter average fiber length is sufficient. Those skilled in the art can easily determine the influence of any of the aforementioned parameters, or one or more combinations thereof, on the flexural strength of the well cover 21 by performing routine tests.
Figures 5A-5C show, in perspective view, top view and side view, respectively, an example of a sewer well 22 that can be manufactured according to the method as described above. Typical external dimensions are, for example, 40 cm x 40 cm x 20 cm, but the invention is not limited thereto, and sewer pits 22 with other dimensions or shapes are also possible.
Figures 6 to 9 show examples of other typical shaped articles 20 that can be manufactured according to the method of the present invention, but the invention is not limited thereto, and other shapes are also possible, such as, for example, flower boxes, garden pots or other garden objects, but also other objects are possible.
Fig. 6 shows a vowel 23 as can be used on an entrance or parking space. Typical dimensions of such a vowel are 10 cm x 10 cm x 20 cm. The low weight, the mechanical workability (grinding, sawing, milling, drilling, etc.), the frost resistance, the anti-slip and the shock resistance are very favorable properties of this product for this application. Moreover, the cost price will be very low if rejected or recycled material is used for at least a part of the raw materials.
Fig. 8 shows a hollow tube 24 that can be used as a frame for a fire hydrant. Typical dimensions for this tube 24 are: W1 = 60 cm, H = 20 cm, L = 40 cm, W2 = 4 cm. The weight of a tube according to the invention is almost 24 kg. Such sleeves, for example, offer protection to fire hydrants against damage caused by, for example, flail mowers, when they come to mow the crop on the side of the street, and accidentally collide with such a tube 24. The impact resistance of the material of the sleeve 24 as obtained by the method of the invention is particularly suitable for absorbing shocks of such flail mowers.
Fig. 9 shows a floor tile or street tile 25. Typical dimensions are, for example, 20 cm x 20 cm x 4 cm thick, or 30 cm x 30 cm x 4 cm thick. The same favorable properties as for the vowel also apply here.
But the invention is not limited to the shapes shown in the figures. The method can thus also be used for the production of round frames, flat rectangular or round panels, round or rectangular covers, hollow cylindrical or beam-shaped pits, etc.
Preferably at least one type of recycled fiber material and / or at least one type of recycled thermoset plastic particles is used.
Preferably, the recycled thermoset plastic particles come at least partially from one or more kayaks, one or more plastic windows, billiard balls, or combinations thereof. But the invention is not limited thereto, and other thermoset plastic materials can also be used.
In one embodiment, the volume amount of the viscous homogeneous mixture 13 that is introduced into the mold 28 is 1.3-2.3 times the volume of the molded article 20, preferably 1.8-2.2 times the volume of the shaped article 20.
Preferably, the recycled fiber material is at least partially from the group of used or rejected glass fibers, glass fiber mats, drive belts, shoes, or combinations thereof. For example, leather items can also be used.
In one embodiment, the object is a grid, in particular a cattle shed grid. The following properties are especially advantageous for this application: the material is not affected by urine (as opposed to iron or cast iron), the material is a good heat insulator (so that the use of straw as a ground cover can be avoided), the anti-slip as a result of which an animal will not stumble and injure itself so easily.
If desired or required, the person skilled in the art can add other substances to the dry mixture or viscous mixture 12, such as, for example, pigments, or reaction retardants, UV-stabilizer, fire retardants, colorant or the like.
Although the present invention has been described with reference to specific embodiments, it will be appreciated that various modifications may be made to these embodiments without departing from the broader scope of the invention as set forth in the claims. Consequently, the description and drawings are to be considered in an illustrative sense rather than a restrictive sense.

权利要求:
Claims (22)
[1]
A method for manufacturing a shaped article (20) from a composite material comprising thermoset plastic particles, characterized in that the method comprises the following steps: a) providing a dry, homogeneous mixture (11) comprising fiber material (4) with a average length of 2 - 40 mm and a granulate of thermoset plastic particles with an average particle size of 2-15 mm, wherein the volume percentage of the fiber material is 10 - 80% of the dry homogeneous mixture (11), and wherein the dry homogeneous mixture (11) has a humidity in equilibrium with air that has a dew point of no more than 25 ° C; b) adding at least one polyol (7) and at least one isocyanate (8) to the dry homogeneous mixture (11) to form a viscous mixture (12), the weight percent of the at least one polyol (7) and the at least one one isocyanate (8) together is 4.0 - 25.0% of the dry homogeneous mixture (11), and mixing the viscous mixture (12), thereby forming a viscous homogeneous mixture (13); c) forming a shaped article (20) by curing the viscous homogeneous mixture (13) in a mold (28) at a temperature of 15 - 60 ° C and under a curing pressure (p) of at least 50 bar, wherein the pressure (p) is maintained for at least 1 minute.
[2]
Method according to claim 1, wherein providing the dry homogeneous mixture (11) comprises the following steps: - providing a fiber material with an average length of 2 - 40 mm, and drying the fiber material (4) until the fiber material has a humidity in equilibrium with air having a dew point of at most 25 ° C, thereby forming a dried fiber material (6); - providing a granulate of thermoset plastic particles with an average particle size of 2-15 mm, and drying the granulate until the granulate has a humidity in equilibrium with air having a dew point of at most 25 ° C, thereby forming a dried granulate (3); - mixing the dried fiber material (6) and the dried granulate (3) into the dry homogeneous mixture (11), wherein the volume percentage of the dried fiber material (6) is 10 - 80% of the dry homogeneous mixture (11).
[3]
Method according to claim 2, wherein the drying of the fiber material (4) is carried out by contacting it with hot air at a temperature of 100 - 300 ° C, preferably 150 - 300 ° C, more preferably 200 - 275 ° C, most preferably substantially 250 ° C.
[4]
Method according to claim 2 or 3, wherein the drying of the granulate (2) is carried out by contacting it with hot air at a temperature of 100 - 175 ° C, preferably a temperature of 125 - 160 ° C, more preferably a temperature of substantially 150 ° C.
[5]
The method of claim 1, wherein providing the dry homogeneous mixture (11) comprises the steps of: - providing a fiber material (5) with an average length of 2 - 40 mm; - providing a granulate of thermoset plastic particles (2) with an average particle size of 2-15 mm; - mixing the fiber material (5) and the granulate (2), wherein the volume percentage of the fiber material (5) is 10 - 80% of the mixture, and mixing the mixture into a homogeneous mixture; - drying the homogeneous mixture until the mixture has a humidity in equilibrium with air having a dew point of at most 25 ° C, thereby forming a dry homogeneous mixture (11).
[6]
A method according to any one of the preceding claims, wherein the dry homogeneous mixture (11) has a temperature of at most 50 ° C, preferably at most 45 ° C, more preferably at most 40 ° C, even more preferably at most 35 ° C.
[7]
A method according to any one of the preceding claims, wherein the dry homogeneous mixture (11) has a humidity that is in equilibrium with air having a dew point of 5 ° C - 22 ° C, preferably of 10 ° C - 20 ° C, most preferably substantially 18 ° C.
[8]
A method according to any one of the preceding claims, wherein the mixing of the viscous mixture (12) takes place in a period of 10 seconds -10 minutes, preferably 10 seconds-5 minutes, more preferably 10 seconds -2 minutes, even more preferably 10-60 seconds, most preferably substantially 20 seconds.
[9]
A method according to any one of the preceding claims, wherein the average length of the fiber material (4) is a length of 2 - 30 mm, preferably 3 - 20 mm, more preferably 4 - 15 mm, even more preferably 6 - 12 mm , most preferably substantially 8 mm.
[10]
A method according to any one of the preceding claims, wherein the granulate (2) has an average particle diameter of 2-10 mm, preferably 3 - 7 mm, more preferably substantially 6 mm.
[11]
A method according to any one of the preceding claims, wherein the volume percentage of the fiber material (4) in the dry mixture is 20 - 60%, preferably 30 - 50%, more preferably substantially 40%.
[12]
A method according to any one of the preceding claims, wherein the weight percent of the at least one polyol (7) and the at least one isocyanate (8) together amounts to 5.0 - 20.0% of the dry homogeneous mixture (11), preferably 5 , 0-15.0%, more preferably 5.5-10.0%, most preferably substantially 7.0%.
[13]
A method according to any one of the preceding claims, wherein curing takes place in the mold (28) at a temperature of 15 - 50 ° C, preferably 15 - 40 ° C, more preferably 15 - 30 ° C, most preferably almost 20 ° C.
[14]
A method according to any one of the preceding claims, wherein curing in the mold (30) takes place at a curing pressure (p) of at least 100 bar, preferably at least 150 bar, more preferably at least 175 bar, most preferably at least 200 bar .
[15]
A method according to any one of the preceding claims, wherein the fiber material (4) comprises glass fibers or carbon fibers, or fibers of thermoset plastics.
[16]
A method according to any one of the preceding claims, wherein the granulate of thermoset plastic particles (2) comprises bakelite and / or polyester particles and / or polyurethane particles and / or cellulose particles.
[17]
A method according to any one of the claims, wherein at least one kind of recycled fiber material and / or at least one kind of recycled thermoset plastic particles are used.
[18]
The method of claim 17, wherein the recycled thermoset plastic particles come at least in part from one or more kayaks, one or more plastic windows, billiard balls, or combinations thereof.
[19]
A method according to claim 17 or 18, wherein a volume amount of the viscous homogeneous mixture (23) that is introduced into the mold (28) is 1.3 to 2.3 times the volume of the molded article (20), preferably 1.8 - 2.2 times.
[20]
The method of any one of claims 17-19, wherein the recycled fiber material is at least partially from the group of used or rejected glass fibers, glass fiber mats, drive belts, shoes, or combinations thereof.
[21]
A method according to any one of the preceding claims for producing a composite manhole cover (21) that meets the requirements of load class A and / or B and / or C according to the NBN EN 124 standard, wherein preferably: - the fibrous material is recycled glass fiber; - the average length of the dried fiber material (6) is 4-10 mm; - the granulate of thermoset plastic particles comprises recycled polyurethane; - the average particle diameter of the dried granulate (2) is 4-8 mm; - the volume percentage of the dried fiber material (6) in the dry homogeneous mixture (11) is 30% - 60%; - the weight percent of the polyol (7) and the isocyanate (8) added to the dry homogeneous mixture (11) amounts to 5-10% of the dry homogeneous mixture (11); - the dry homogeneous mixture (11) has a humidity that is in equilibrium with air that has a dew point of 10 - 20 ° C; - the amount of the viscous mixture (12) that is introduced into the mold (28) is 1.8 - 2.2 times the volume of the space in the mold (28); - the curing takes place in a mold (20) at a temperature of 18 - 35 ° C that is subjected to a pressure of at least 50 bar, for a period of at least 2 minutes.
[22]
A method according to any one of the preceding claims, wherein the article (20) is selected from the group of: a manhole cover (25), a manhole cover (25) that meets the requirements of load class A and / or load class B and / or load class C according to the NBN EN 124 standard, a grid, a cowshed grid, a clinker (23), a floor tile (25), a roof tile, a foundation sole for a fire hydrant and a frame for a fire hydrant (24).

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EP2454062A2|2012-05-23|

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US20120112386A1|2012-05-10|

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法律状态:
2018-07-25| PD| Change of ownership|Owner name: ETABLISSEMENTS SIMONIS S.; BE Free format text: DETAILS ASSIGNMENT: CHANGE OF OWNER(S), CESSION; FORMER OWNER NAME: DEBERGH LUDO Effective date: 20180523 |

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2018-07-25| RC| Pledge established (pawning)|Free format text: DETAILS PLEDGE: RIGHT OF PLEDGE, ETABLI Effective date: 20140819 |

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2018-07-25| RF| Seizure terminated|Free format text: DETAILS PLEDGE: RIGHT OF PLEDGE, SUPPRIME Name of requester: VERMEC NV Effective date: 20180523 |

优先权:

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申请号 | 申请日 | 专利标题

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BE200900430|2009-07-15|

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BE200900430|2009-07-15|

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