JPH0528721B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method of forming a polymer matrix comprising a filler material, which together contain a filler material, a polymerizable material, and a catalyst for polymerizing the polymerizable material to form a polymer matrix. The invention extends to vitreous filler materials for incorporation into polymer matrices, including filled polymer matrices formed by the method of the invention. Many polymerizable materials are known and their applications are increasingly being extended to various fields. One significant advantage of such materials is that they can be used in fluid form or even in a viscoelastic state and that they can be extruded, injected or otherwise shaped at controlled temperatures. Many polymerizable materials that can be formed by such methods at ambient temperatures or heat formed at moderate temperatures require the presence of a polymerization catalyst to initiate the chain reaction that provides a useful cured, formed article. In order to allow the polymerization reaction to proceed appropriately and produce a homogeneous polymeric substance,
It goes without saying that the catalyst must be well dispersed in the polymerizable material. It is also well known to incorporate filler materials into polymer matrices. This is done to modify the mechanical, electrical or thermal properties of the polymer, or simply to reduce the cost of articles formed from the polymer. It is well known to incorporate glass fibers into polymer matrices, either as individual glass fibers or as glass fiber mats (which can be woven or non-woven). A filler material that is finding increasing use is vitreous beads. The term "vitreous" is used herein to refer to glass or glass-crystalline materials, the latter materials being made by heat treating glass to introduce a crystalline phase therein. . In particular, the use of hollow glass beads as filler material allows the production of articles with low density. Difficulties are encountered in achieving good distribution of filler material and catalyst in the polymerizable material for the formation of high quality polymer matrices, especially when the polymerization reaction is one that proceeds fairly rapidly. An example of this difficulty is in the case of road markings, where the paint is coated with a glass bead-filling material mixed in to give it retroreflectivity so that the marking is easily visible at night. One known method is shown in U.S. Pat. No. 2,897,732, which involves applying a polymerizable paint to form a polyester-vinylidene copolymer, spraying the surface of the paint mark with a powdered polymerization catalyst, and then It consists of scattering glass beads on the paint, thus allowing at least some of them to settle into the mark before polymerization is complete. This method suffers from several drawbacks. Firstly, it requires fairly complex equipment with three separate material ejection heads. The second most expensive component, the catalyst, is easily blown away during discharge and is wasted. Third, the catalyst is deposited on the surface of the paint mark, which causes differential polymerization of the paint leading to surface crack formation and a lack of catalyst deep within the paint. Fourth, while rapid polymerization of the paint is obviously desirable, the more rapidly such polymerization occurs, the less easy it is to achieve the desired distribution of filler material beads deep into the paint mark. The present invention facilitates good distribution of catalyst within the polymerizable material, allows for rapid catalysis, and proportionally reduces the amount of catalyst required for complete polymerization of the polymerizable material to form a polymer matrix. It is an object of the present invention to provide a method for forming a polymer matrix containing filler material that can be reduced. According to the present invention, a polymer matrix containing an inorganic filler material is formed by polymerizing a filler material, a polymerizable material, and a polymerizable material to form a polymer matrix containing an inorganic filler material, including bringing together a filler material, a polymerizable material, and a catalyst to form said polymer matrix. A method is provided, characterized in that the catalyst is immobilized on the surface of the filler material prior to contact with the polymerizable material. Such a method is very simple to implement. Compared to mixing catalyst and polymerizable material, it is generally much easier to ensure that the filler material and polymerizable material have the desired relative texture. Since according to the invention the catalyst is fixed in the filling material, a good relative distribution of the polymerizable material and the filling material ensures a good distribution of the catalyst and the polymerizable material. As a result, catalytic polymerization can occur rapidly, efficiently and uniformly within the polymerizable material/polymer matrix. Also, the amount of catalyst applied to the packing material can be easily adjusted, thus greatly reducing the amount of wasted catalyst. It has been observed that it is sometimes possible to use less catalyst in the process of the invention than when using filler material and catalyst separately. Rather, it is surprising that the method of the present invention provides more efficient catalysis, as one would expect a reduction in efficiency by immobilizing the catalyst on a material other than the material to be catalyzed. I understand. Advantageously, the catalyst is adsorbed on a layer of fixing agent that adheres to the surface of the filling material. This is done in such a way that the catalyst can be stored and handled prior to contact with the polymerizable material without reducing the reactivity of the catalyst with respect to the polymerizable material being polymerized and without loss of catalyst. Allows it to be fixed to the material. It has been discovered that many materials can form tight chemical bonds with filler materials commonly used to fill polymer matrices and can be used as fixatives for catalysts. Preferably, the organometallic compound is adhered to the filling material to act as a fixing agent. Many such compounds can readily be chemically bonded to inorganic filler materials in the form of monolayers or multilayers, and they can immobilize the catalyst to the filler material. It is particularly preferred that the organometallic compound is selected from the group consisting of silanes, chromium complexes, titanium derivatives and polymers containing methoxysilyl groups. Such compounds are particularly effective as fixatives; they also have the advantage of being able to facilitate coupling between many common polymeric materials such as polyesters and polyacrylates and filler materials. This facilitates the production of composite materials with high fracture strength under bending. It also promotes strong resistance to pull-out of the filler material due to abrasion, which is particularly important when the polymer matrix is to be used as a road marking. Examples of such materials include: vinylsilane (A151 from Union Carbide), methacryloxysilane (from Union Carbide).
A174), styrylsilane, Warner type chromium complexes (Volans trademark from DuPont), including complexes with fumaric acid, isopropyl titanates (TSM2-7, TSA2- from Kenrich)
11, TTM33, TTAC-39) and special polymers with methoxysilyl groups (Polyvest 25, trademark from Huels). The fixative coating can be applied in various ways, for example by immersion or contact with other liquid reagents, followed by drying, or by depositing from vaporized reagents in the form of a fluidized bed, e.g. in the case of granular packed materials. Therefore, it can be applied to the filling material. Formation of such a coating can be followed by impregnating the coating with catalyst by contacting the coating with a liquid or dissolved catalyst. In a preferred embodiment of the invention,
The filling material is brought into contact with a solution containing the catalyst and a fixing agent in order to fix the catalyst on the surface of the filling material, and then the filling material is dried. In this method, the fixative and catalyst are applied to the filler material in a single step. This method is therefore very simple and quick. In another preferred embodiment of the invention, the packing material is brought into contact with a suspension containing the catalyst and the fixing agent in order to fix the catalyst on the surface of the packing material. This is even simpler and faster since the drying step can sometimes be omitted. For example, the silane fixative may be mixed with Interotux BP-40-S™ from Peroxide Chemie GmbH, Munich, West Germany, which is a 40% suspension of dibenzoyl peroxide in phthalate as a catalyst. An embodiment of the invention is preferred in which the filler material is mixed with an unsaturated polyester for carrying out the polymerization. The present invention can be used to make articles of such materials, such as acrylic or urethane/acrylic resins, at room temperature in the presence of catalysts, optionally using promoters. This process consists of unsaturated polyesters dissolved in copolymerizable monomers, such as polyester resins mixed with vinyl, acrylic or allyl monomers, or oligourethane methacrylate resins in methyl methacrylate as the solvent monomer. Can be used to make goods. There are various polymerization catalysts that allow polymerizable materials to be cured more quickly and/or at lower temperatures. Particularly for unsaturated polyester resins and copolymers thereof, the use of peroxides as catalysts is often recommended. The present invention includes a method of immobilizing peroxide, such as benzoyl peroxide, which is available as a powder which is easy to handle, on the surface of the filler material as said catalyst. In the most preferred embodiment of the invention, said filler material comprises vitreous beads. Vitreous beads are particularly easy to mix into fluids or viscoelastic polymeric materials because of their very high degree of spherical symmetry;
The beads and therefore the catalyst are also well dispersed therein, and their use is particularly useful as it gives good flowability in any molding operation and allows uniform distribution of stress within the formed polymer matrix. It is. Hollow vitreous beads may be used when it is desired to make articles of low density. However, when it is intended that good mechanical resistance in the product is more important than low density, the vitreous beads preferably comprise solid vitreous beads. For best mechanical properties in the product, it may be desirable to use glass crystalline beads rather than glass beads, although they are generally more expensive. The size of the beads used as filler material can have an important effect on the ease with which a filled polymer matrix can be formed and/or the final properties of that matrix. For molded plastic materials, it is generally preferred for the beads to have a median diameter of 20 to 50 μm, such as about 44 μm.
This is because the presence of beads has an effect on the fluidity of the polymerizable material during molding. On the other hand, the beads to be used in the paint generally have a median diameter of 50 to 650 μm, since it is found to be advantageous for a good reflectivity of the filled paint. Here and throughout the specification, median bead diameter refers to the median diameter by number of beads, in other words many diameters have diameters smaller than the median and also have diameters larger than the median. . Therefore, in a preferred embodiment of the invention, said vitreous beads are
Select to have a median diameter of 20-650 μm. It will be appreciated that the smaller the specific surface area of the beads, the less area is available for catalyst immobilization. In the case of casting or molding resins, where small beads are usually used, it may be sufficient to select the bead size depending on the amount of catalyst to be delivered to the polymerizable material with which the beads are mixed. However, in the case of paints or other resins where the beads are applied to the polymeric material after being applied to the surface as a layer, it may be desirable to use relatively large beads, e.g. having a diameter of 150-650 μm, thus Beads can be more easily settled into the layer of polymerizable material, and even if such large beads have a small specific surface area, they can entrain the catalyst deep into the layer and thus carry relatively less catalyst. Advantageously, at least some of the vitreous beads have a rough surface. Such roughening can be obtained by mechanical frosting methods, but in view of the preferred size of the beads it is necessarily easier to frost them chemically. It is therefore particularly preferred to treat at least some of the vitreous beads with an etching medium before coating. Beads so etched have a rough surface and therefore they have a larger specific surface area than smooth beads of the same size. Such roughened beads can therefore immobilize more catalyst for the same median diameter; the use of such an etching method results in a three-fold increase in the amount of catalyst that can be supported by the beads. bring. This is especially true when working with fairly large beads and/or when rapid polymerization is required and/or when it is desired to carry out such polymerization at low ambient temperatures, for example when making pavement markings in winter. Particularly advantageous. It can be seen that beads with rough surfaces partially lose their reflectivity when they are used for pavement marking formation. This does not present any practical drawbacks as such beads can be mixed with unetched catalyst-supported beads to ensure the desired degree of reflectivity from the marks, or with other unetched beads as discussed below. In fact, in some cases, such etched beads are a positive advantage as they can be used to replace filler materials that act as white pigments, such as titanium dioxide or titanium dioxide, which can be quite costly. I can do it. Such etching methods are very simply carried out using etching media containing fluorine ions, for example ammonium hydrogen fluoride solutions. However, such treatments should only be used to treat solid beads, since hollow beads may have walls that are too thin to withstand the treatment. The invention also concerns the possibility of mixing catalyst-supported vitreous beads with other beads. In one preferred embodiment of the invention, vitreous beads are coated with a material that gives them hydrophilic and hydrophobic properties and are incorporated into the packing material together with the catalyst-loaded vitreous beads. Such mixtures are particularly well suited for use in pavement marking, since the catalyst-supported beads can be prepared using hydrophilic and This is because it can be sprayed onto the wet paint in the form of a mixture with hydrophobic beads. The catalyst-supported beads sink and mix within the layer of paint while the hydrophobic and hydrophilic beads remain exposed on top of the paint surface, allowing them to reflect light until they are eroded by traffic movement. The erosion then exposes some of the catalyst-loaded beads, allowing them to then reflect light. Advantageously, the catalyst-supported beads are incorporated into the packing material in a proportion of 70 to 90% by weight of the total packing material. Employing this feature has been found to be particularly advantageous for the rapid formation of retro-reflective coatings of polymerized paints. The method according to the invention is particularly suitable for the formation of pavement markings and in a most preferred embodiment comprises:
A polymerizable material is applied to a pavement, and catalyst-supported vitreous beads are applied to the polymerizable material to cause its polymerization in situ to form the pavement markings. The expression "paved road" is used here in a broad sense, including roadways, sidewalks, aircraft runways and toll roads;
Includes parking areas and other paved areas. One very simple and effective method of marking pavement is to deposit a coating of polymeric paint onto the pavement and then, while the paint is still wet, to cure the paint on the surface. Vitreous beads with fixed polymerization catalysts are sprinkled onto the paint. Catalyst-loaded beads may be the only beads used, or they may be mixed with other vitreous beads. This method makes it possible to form lines, patterns, letters or other symbols, for example on concrete or tarmac surfaces, and the marks are perfectly clean and visible even at night in the presence of light from the vehicle's headlights. I can do it.
Marks can be applied in a very short time and therefore with a very short disruption of normal traffic flow. It has been found that by using such a method, the amount of catalyst that must be used can be saved when compared to conventional pavement marking methods that apply a powdered catalyst to the surface of the paint. Furthermore, such a method requires only fairly simple equipment comprising a paint spray gun and a bead ejection device. Such equipment can be used to form marks with polymeric paints as well as with conventional emulsion paints. In another preferred embodiment of the invention, the polymerizable material is mixed with the catalyst-supported filler material and the mixture is shaped before its hardening by polymerization. Such a method allows for truly precise dosing of the amount of catalyst required to carry out the polymerization of the polymerizable material. The present invention includes a filled polymer matrix formed by the method of the present invention. The vitreous packing material supporting the catalyst is itself a new and useful product, and the present invention provides a vitreous packing material for incorporating into a polymer matrix, characterized in that a polymerization catalyst is fixed on the surface of such a packing material. This also applies to filling materials. Such products are particularly useful because it is much easier to mix the catalyst-supported filler material into the polymerizable material with good distribution than to mix the filler material and another catalyst into the polymerizable material. . It is therefore easy to obtain a rapid and efficient polymerization of polymerizable materials. The use of vitreous filler materials has many advantages, in particular that vitreous filler materials are inexpensive and widely available, and such materials can also be used in a variety of forms to impart particularly desired properties to the filled polymeric material. It can also be made in different sizes. Advantageously, the catalyst is adsorbed on a layer of fixing agent that adheres to the surface of the filling material. This allows the material of interest to be stored and handled prior to contact with the polymerizable material without reducing the reactivity of the catalyst with respect to the material to be polymerized and without loss of catalyst. As previously mentioned, many materials can be used as fixatives for the catalyst. Preference is given to using organometallic compounds as fixatives. Many such compounds can readily be caused to be chemically bound to the inorganic filler material in monomolecular or multilayer form, and they can immobilize the catalyst on the filler material. Particularly preferably, the organometallic compound is selected from the group consisting of silanes, chromium complexes, titanium derivatives and polymers containing methoxysilyl groups. Such compounds are particularly effective as fixatives; they also have the advantage of being able to facilitate coupling between many common polymeric materials such as polyesters and polyacrylates and filler materials. There are various polymerization catalysts that allow polymerizable materials to be cured more rapidly and/or at lower temperatures.
The use of peroxides as catalysts is often recommended, especially for unsaturated polyesters and their copolymers. The present invention comprises said filler material in which a peroxide, for example benzoyl peroxide available as a powder which is easy to handle, is immobilized on the surface of the filler material as said catalyst. In the most preferred embodiment of the invention, said filler material comprises vitreous beads. Vitreous beads are particularly useful because their very high degree of spherical symmetry allows them to be particularly easily mixed into fluid or viscoelastic polymerizable materials, thus providing a good distribution of the beads and catalyst therein. This is because their use provides good fluidity to the molding operation and allows uniform distribution of stress within the polymer matrix formed. When it is desired to make articles of low density,
It is recommended to use hollow vitreous beads. However, when it is intended that good mechanical resistance for the product is more important than low density, the vitreous beads preferably comprise solid vitreous beads. For the best mechanical properties in the product, use glass crystalline beads rather than glass beads.
They may generally be desirable despite their high cost. The size of the beads used as filler material can have a significant effect on the ease with which a filled polymer matrix can be formed and/or the ultimate properties of that matrix. In the case of molded plastic materials, generally 20 to
It is desirable to have a median diameter of 50 μm, for example about 44 μm. This is because the presence of beads has an effect on the flowability of the polymerizable material during the molding process. On the other hand, the beads that should be used for painting are
Generally having a median diameter of 50 to 650 μm, as this has been found to be advantageous for good reflectivity of the filled pane. Therefore, in a preferred embodiment of the invention,
The vitreous beads have a median diameter of 20-650 μm. Advantageously, at least some of the vitreous beads have a rough surface that supports the catalyst. Such rough beads have a larger specific surface area than smooth beads of the same size. Such coarse beads can therefore immobilize more catalysts for the same median diameter, whereas they can
Can support up to twice as much catalyst. This is particularly advantageous when working with fairly large beads and/or when rapid polymerization is required and/or when it is desired to carry out such polymerization at low ambient temperatures. It can be seen that beads with a rough surface partially lose their reflective properties for which they are primarily used for pavement markings. This does not present any real disadvantages, as such beads can be mixed with smooth catalyst-supported beads to ensure the desired degree of reflection from the mark, or with other smooth beads as described below. . In fact, under certain circumstances, it is a positive advantage that such roughened beads can be used to replace filler materials that act as white pigments, such as titanium dioxide or titanium dioxide, which can be quite expensive. In a preferred embodiment of the invention, the filling material further comprises a vitreous material coated with a material making it both hydrophilic and hydrophobic. Such mixtures are particularly suitable for use in pavement markings, since the catalyst-supported beads can be prepared using hydrophilic and hydrophobic beads using a simple device with a paint spray gun and a single bead and a catalyst discharge head. This is because it can be sprayed onto wet paint in the form of a mixture with. The catalyst-supported beads settle and mix within the layer of paint while the hydrophilic and hydrophobic beads remain exposed on top of the paint surface, where they reflect light until they are eroded by traffic movement. The erosion then exposes the catalyst-loaded beads to light, thus allowing them to in turn reflect light. Advantageously said catalyst-supported beads account for 70% of the total packing material.
Mixed into the filling material in a proportion of ~90% by weight. Employing this feature has been found to be particularly advantageous for the rapid formation of retroreflective coatings of polymerized paints. The present invention will be explained in more detail by the following examples. Example 1 Beads were made for inclusion in road marking paint. The beads have a diameter of 150-250μm and
It had a median diameter (depending on the number of particles) of 180 μm. The paint was Rohm's acrylic resin Plexilith SE663 (trademark). Benzoyl peroxide was dissolved in toluene at a rate of 200 g/mt. After a few minutes Union Carbide Silane A174 (gamma-methacryloxypropyl-trimethoxysilane) was added. A solution containing peroxide catalyst and silane was poured onto the beads while continuously stirring the mixture. After stirring for 15 minutes, the beads were dried at room temperature for 24 hours. Beads contain 0.075g/Kg of silane and 8g/Kg of peroxide.
It was carried at a rate of Kg. This mixture was stored prior to road marking. The paint was sprayed onto the road, and the beads prepared as described above were scattered on the paint at a ratio of 1 part by weight of beads to 1 part by weight of paint. After 15 minutes the paint was completely polymerized. The light retroreflectivity exhibited by this paint was not different from that of similar paints except for the separate incorporation of tactile and bare glass beads. When using the conventional method,
That is, when using the method of supplying the catalyst separately, 15
Two to three times more peroxide was required to cure the paint in minutes. In a modification of this example, 20% of the beads carrying the catalyst were replaced with beads treated with a fluorocarbon agent of type FC129 from Three M Company to impart hydrophobic and hydrophilic properties. Although curing of the paint took several minutes longer, the retroreflectivity of the paint was improved due to the presence of hydrophilic and hydrophobic beads on the surface of the cured coating. Example 2 Example 1 using a mixture of beads of different particle sizes
repeated. 1/3 beads with a diameter of 40-80 μm, 1/3 beads with a diameter of 75-150 μm,
A mixture was then used consisting of beads, one third of which had a diameter of 150-250 μm. Different amounts of peroxide were attached to the beads, in this example silane A174 was replaced with an equal amount of Polyvest 25™ from Huels, a binder with methoxysilyl groups. Table 1 below shows the curing time of acrylic paint in the presence of this mixture of beads for a 1:1 bead to resin ratio (by weight).

Table: Example 3 Solid glass beads with a median diameter of 44 μm were treated with an aqueous solution of ammonium hydrogen fluoride. Beads subjected to this treatment had an opaque white appearance. Their surfaces were rough. These beads were prepared using silane A174 in toluene.
and a solution of benzoyl peroxide. 2 g of silane and 8 g of peroxide were deposited on the surface of the beads per 1 kg of beads. ICI methyl acrylic resin type MDR824 containing dimethyl-p-toluidine as accelerator was added to beads per kg of resin at 20°C.
Mixed with 1.25Kg. The filled resin was injection molded. Hardening of the molded article was observed after 50 seconds at 70°C. Example 4 Glass beads with a median diameter of 44 μm were treated in the same manner as in Example 3 using a glass etching agent and then a mixture of silane and peroxide. In this example, the peroxide with which the beads were impregnated was methyl ethyl ketone peroxide. 100 parts by weight of these beads were mixed with Epocryl 322 acrylic resin from Ciel Chemical Co.
100 parts by weight and 0.4 parts by weight of cobalt naphthanate (6% cobalt) as promoter. The mixture was poured into a molder at 25°C. The gelation time of the mixture was approximately 10 minutes, and curing was obtained after 20 minutes. In a modification of this example, beads treated as described above and carrying a polymerization catalyst were coated with a first substance (which, when used alone, renders the beads hydrophobic;
add glass beads carrying a coating containing a second substance (which, when used alone, makes the beads hydrophobic and hydrophilic) (these beads are covered by a Belgian patent) No.
904453),
A good distribution of these beads in the resin was obtained to provide reflective properties. The above mixture was used to mold reflectors. Example 5 Solid glass beads having a median diameter of about 400 μm were treated with a mixture of Silane A174 and Intelotx BP-40-s™ from Peroxide Chemie. Interotux BP-40-s is a 40% suspension of dibenzoyl peroxide in phthalate. This mixture adheres well to beads and
No active drying of the beads after treatment was necessary. The phthalate acted as a plasticizer in the resin. In this method, 0.3g silane and 2.5g per 1Kg of beads.
catalyst was immobilized on the beads. The retroreflective properties of the treated beads were useful for incorporation into acrylic paints. Example 6 Solid glass beads having a median diameter of approximately 20 μm were coated with vinyltriethoxysilane A151 (Union Carbide) and Interotx BP-40.
-s (trademark). This gave immobilization of 0.5 g of silane and 2 g of perbenzoate per Kg of beads. The beads were mixed with liquid polyester resin and the mixture was immediately applied to a mat of woven glass fibers in a molder, and curing was observed at room temperature. Example 7 In a modification of Example 3, the beads are approximately 40 μm.
, and they did not etch. Silane in toluene with these beads
0.77 g of silane and 2 g of peroxide per Kg of beads were deposited on the surface of the beads by mixing with a solution of A174 and benzoyl peroxide. In another example, glass crystalline beads of the same particle size were used.

Claims (1)

[Claims] 1. A method of forming a polymer matrix containing an inorganic filler material by polymerizing the polymerizable material and combining a filler material, a polymerizable material, and a catalyst to form a polymer matrix, comprising: the filler material contains vitreous beads, the catalyst is
A method characterized by adsorption into a layer of fixative that adheres to the surface of the vitreous beads before contact with the polymerizable material. 2. The method of claim 1, wherein the organometallic compound acts as a fixative to adhere to the filler material. 3. The method of claim 2, wherein the organometallic compound is selected from the group consisting of silanes, chromium complexes, titanium derivatives and polymers having methoxysilyl groups. 4. The method according to any one of claims 1 to 3, wherein the filling material is brought into contact with a solution containing the catalyst and a fixing agent for fixing the catalyst on the surface of the filling material, and then the filling material is dried. 5. The method according to any one of claims 1 to 3, wherein the packing material is brought into contact with a suspension containing the catalyst and a fixing agent for fixing the catalyst on the surface of the packing material. 6. A method according to any one of claims 1 to 5, in which the filler material is mixed with an unsaturated polyester and polymerized. 7. The method according to claim 6, wherein peroxide is immobilized as the catalyst on the surface of the filling material. 8. The method according to any one of claims 1 to 7, wherein the vitreous beads contain solid beads. 9. The glass beads are 20 to 650μ in size.
Claim 1 selected to have a median diameter of m.
8. The method according to any one of 8. 10. Claims 1-9 wherein at least some of the vitreous beads are treated with an etching medium prior to coating.
The method described in any of the above. 11. The method according to any one of claims 8 to 10, wherein the etching medium used contains fluorine ions. 12. The vitreous beads are coated with a material that makes them both hydrophilic and hydrophobic and are incorporated into the packing material together with the catalyst-supported vitreous beads.
The method described in any of the above. 13. Claim 1, wherein the catalyst-supported beads are mixed in the filling material at a proportion of 70 to 90% by weight of the total filling material.
The method described in 2. 14. Any one of claims 1 to 13, wherein a polymerizable material is applied to a paved road, and catalyst-supported vitreous beads are applied to the polymerizable material to cause polymerization in situ to form markings on the paved road. Method described. 15. Mixing the polymerizable material with the catalyst-supported packing material;
14. A method according to claim 1, wherein the mixture is shaped before being cured by polymerization. 16. A filled polymer matrix formed by the method of any one of claims 1 to 15. 17. A vitreous filling material for mixing into a polymer matrix, characterized in that a polymerization catalyst is adsorbed and fixed in a layer of a fixing agent that adheres to the surface of vitreous beads. 18. Filling material according to claim 17, characterized in that an organometallic compound is used as fixative. 19. The filling material of claim 18, wherein the organometallic compound is selected from the group consisting of silanes, chromium complexes, titanium derivatives and polymers having methoxysilyl groups. 20. The filling material according to any one of claims 17 to 19, wherein peroxide is fixed on the surface of the filling material as the catalyst. 21. The filling material according to any one of claims 17 to 20, wherein the vitreous beads contain solid beads. 22. The filler material of claim 21, wherein the vitreous beads have a median diameter of 20 to 650 μm. 23. Claims 17 to 23, wherein at least some of the vitreous beads have a rough surface that supports the catalyst.
23. The filling material according to any one of 22. 24. A filling material according to any of claims 17 to 23, wherein the filling material further contains vitreous beads coated with a material making them both hydrophilic and hydrophobic. 25 the catalyst-supported beads in the packing material;
Filler material according to claim 24, which is incorporated in a proportion of 70 to 90% by weight of the total filler material.