DE102015015985A1 - Means and method for multifunctional marking of a roadway - Google Patents

Abstract

The invention relates to an agent and its specific composition and a method for marking surfaces of road traffic z. B. a strip of a roadway with z. As luminescent luminescent and magnetic color.

Description

It is hereby incorporated as an invention an agent and its specific composition and a method of marking adherent surface areas of road traffic which more particularly relates to a composition according to claims 1-15 and a method according to claims 16-18. The wording of all claims is hereby incorporated by reference into the content of this specification.

Lane markings are traffic signs within the meaning of the Highway Code ( §§ 39 ff StVO ) and must be clearly recognizable as such, ensure continuous visual guidance of road users and withstand the highest loads. To meet these requirements, marking systems must be highly visible, grippy and wear-resistant. As marking materials, paints (low-solvent paints and dispersions, two-component paints), high-solids dispersions, thermoplastics, reactive systems (cold plastics / spray plastics) and films can be used. A distinction is made between conventional markings (type I) and markings with increased wet night visibility (type II). The increased night visibility in the wet is achieved in that in particular the parts on the surface of the markings are designed so that they protrude from the mark and thus also from the water film, which inter alia by coarse Nachstreumittel (large reflex beads), a profiling, a Structure or by agglomerate markings. In combination with the color of the marking, a mirror is thus produced (cf. Frank, H., Reinsberg, H .: Guideline road markings, Bonn, Bad Sachsa: German Road Safety Council e. V., Deutsche Studiengesellschaft für Straßenmarkierungen e. V., 2014 ).

Road markings can be applied to the desired road surface by spraying, with a drawing shoe, in an extruder process or by gluing or rolling up (cf. Frank, H., Reinsberg, H .: Guideline road markings, Bonn, Bad Sachsa: German Road Safety Council e. V., Deutsche Studiengesellschaft für Straßenmarkierungen e. V., 2014 ). A composition for spraying must have a viscosity that is suitable on the one hand for spray application and on the other hand keeps the particles in suspension during drying after application (cf. WO 2007/056820 A1 ). As sprayable systems so apply colors and cold spray plastics. A device for dispensing a liquid, for which a liquid container and a dispensing opening with many openings are essential, is disclosed in US Pat EP 2008/1958517 A2 described.

In order to increase the night visibility of road markings, reflective markings may be used, better street lighting and / or luminescent markers or forms. At present, the increased night visibility of road markings in addition to the color contrast to the road surface is essentially determined by reflecting beads (see above) embedded in the surface and predominantly reflecting the headlight. The need for better visibility of the street lane markings at night, however, prove recent patent applications such. B. EP 2827047 A1 in which a possibility for better illumination of lanes by a lighting system is presented, which comprises a plurality of arranged along a guideline of the lane, on a support structure suspended marker lights above the lane. In EP 2827047 A1 It is stated that in particular a far-sighted recognizability of the routing of a lane marked with today's lane markings (eg a multi-lane highway) is limited by poor visibility conditions (eg at night, in wet conditions, in snow cover).

Increasing the night visibility of a road marking by a form of luminescence has advantages over merely reflective markings or better illumination of the roadway. Compared to reflective luminescent markings, significantly larger lanes become visible. Compared with the higher power requirements and the increased necessary assembly and construction work by an additional roadway lighting luminescent road marking is relatively cheap.

To DIN 67510-1: 2009-11 are photoluminescent pigments, pigments which can be excited by UV radiation or visible radiation and then luminesce without further excitation and photoluminescent products, products made using long-luminescent pigments, e.g. As coating materials, films, enamels, polymers and signs made therefrom, controls and paints. Luminescent luminescence is understood to be a phenomenon which is not to be confused with fluorescence and phosphorescence, since it is caused by energy traps (electron or hole traps) of a material which are filled after illumination and not by excited electron states. After illumination, the absorbed energy in phosphorescent materials is gradually degraded and finally emitted in the form of light. According to the mechanism Therefore, the term thermally stimulated luminescence (TSL) is more appropriate. However, in the case of the luminescence phenomenon luminescence has often been spoken of by phosphorescence (cf. Hölsä, J. Electrochem. Soc. Interface 2009, 42-45 ).

The degree of saturation of the stimulation of a persistent pigment depends on the intensity, the type of light and the duration of the illumination and the ambient temperature. To DIN 67510-1: 2009-11 , Appendix B is the complete saturation excitation of a photoluminescent product is reached when by varying the excitation time, the type of illumination and illuminance at a certain ambient temperature (22 ± 3 ° C) no further increase in luminance can occur. Relative saturation excitation is achieved when, at the point of application, there is no increase in the luminance of the photoluminescent product by prolonging the duration of application of excitation illumination.

Luminescent luminescent materials are typically solids and crystalline materials for which powdery presentations of mixing, sintering and milling are necessary (cf. WO 2012/141626 A1 ). In CH 709020 A1 For the first time, the depiction of luminescent monocrystals instead of powders is described. Corresponding US 5424006 A For example, europium and dysprosium doped aluminum strontium oxides can be used as materials with effective phosphorescence. In WO 2015/099145 A1 is a phosphor or its specific composition, which is characterized by the empirical formula hereinafter, patented with excellent long-lasting properties: A ₃ B ₂ C ₃ O ₁₂ : Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Hf, Si, Yb, Eu, Pr, Tb [A = Mg, Ca, Sr, La, Gd, Tb, Lu, Y, Ce; B = Al, Ga, Sc, In, Mg, Lu, Y; C = Si, Ge, Al, Ga]. In CN 104479676 A Also, a long-lasting luminophore is patented, which is characterized by the following composition: Ca _6-xy BaP ₄ O ₁₇ : Eu _x , R _y [0.08 ≤ x ≥ 0.005; 0.12 ≤ y ≥ 0; R = variable].

At present, a variety of luminescent products are commercialized. Photoluminescent materials are used commercially, especially for safety guidance such as escape route markings. In the following examples, various compositions and methods of execution are described. In US 2010/0291409 A1 describes a method for displaying products that glow at night. Explicitly road markings are also mentioned as an application example. By coating the products with a photoluminescent or reflective pigment, a photoluminescent or reflective ink or a plastic containing the desired photoluminescent or reflective pigment, photoluminescent or luminous products can be obtained. For the corresponding application, plastic materials of polypropylene, polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene fluoride, vinyl esters, epoxy resins, polyethylene, high molecular weight polyethylene, ethylene chlorotrifluoroethylene, ethylene tetrafluoroethylene, chlorotrifluoroethylene, fluorinated ethylene propylene, perfluoroalkoxy, acrylonitrile-butadiene-styrene, polyphenylene sulfide, polyphthalamide, glass fiber reinforced polyvinyl chloride, Polysulfone, thermoplastics and thermosets patented. The photoluminescent pigment is described by the following formulas: m Sr _1-x Eu _x O n Al ₂ O ₃ y B ₂ O ₃ ; m Sr _0.97 Eu _0.03 O · Al ₂ O ₃ · 0.01 B ₂ O ₃ [1≤m≤5, 1≤n≤8, 0.001≤x≤0.1, 0.005≤y≤0.35]; ZnS: Cu; (ZnCd) S: Cu. In WO 2012/141626 A1 describes a method for the electrochemical representation of a phosphorescent surface layer, which is characterized by the following empirical formula, of an aluminum object: AAl ₂ O ₄ : Eu _x , B _y [A = Ca, Mg, Sr, Ba; B = La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sn, Bi; 0.0001 ≤ x 10, 0.0001 ≤ y 10]

So far, some compositions and methods of luminescent roadway markings are also legally protected. Two examples are mentioned below. In WO 2007/056820 A1 a luminescent road marking paint comprising a dispersion resin (acrylic resin), a solvent of at least one coalescing solvent (2,2,4-trimethyl-1,3-pentanediol monoiso-butyrate) and a pigment of at least one luminescent (e.g. purchasable) material. Corresponding WO 2015/053632 A1 For example, a luminescent and multi-functional pavement marking may consist of a monomer having a high boiling point and a polyacrylate and a binder and other additives and luminophores and / or thermochromic liquid crystals / dyes. The luminophores to be used are: SrAl ₂ O ₄ , CaS and alkaline earth metal silicates.

Clearly visible road lane markings or their automatic detection in all light and weather conditions also form the basis for a large number of current and future so-called driver assistance systems (eg lane departure warning systems) also for use in highly autonomous driving (cf. Frank, H., Reinsberg, H .: Guideline road markings, Bonn, Bad Sachsa: German Road Safety Council e. V., Deutsche Studiengesellschaft für Straßenmarkierungen e. V., 2014 ), whose potential lies especially in avoiding accidents and increasing comfort during driving (cf. Winner, H., Hakuli, S., Lotz, F., Singer, C .: Manual Driver Assistance Systems, Basics, Components and Systems for Active Safety and Comfort, 3rd ed., Wiesbaden: Springer Vieweg, 2015, p. 56 f , ). The actuators of driver assistance systems so far comprise hydraulic passenger car brake systems, electromechanical brake systems and steering control systems (cf. Winner, H., Hakuli, S., Lotz, F., Singer, C .: Manual Driver Assistance Systems, Basics, Components and Systems for Active Safety and Comfort, 3rd ed., Wiesbaden: Springer Vieweg, 2015, p. 591 ). For an autonomous journey, however, the machine environment perception of previous driver assistance systems is still far from a complete environmental detection, so that further research and development work must take place for a more comprehensive perception of the required physical quantities (cf. Winner, H., Hakuli, S., Lotz, F., Singer, C .: Manual driver assistance systems, fundamentals, components and systems for active safety and comfort, 3rd ed., Wiesbaden: Springer Vieweg, 2015, p. 1147 f , ). For driver assistance systems, a number of automotive sensors are currently available. It is ultrasound z. B. used in ultrasonic parking assistance systems (see. Winner, H., Hakuli, S., Lotz, F., Singer, C .: Manual Driver Assistance Systems, Basics, Components and Systems for Active Safety and Comfort, 3rd ed., Wiesbaden: Springer Vieweg, 2015, p. 244- 257 ) and radar (above all the 76.5 GHz range) for Adaptive Cruise Control (ACC) with integrated start-up warning function, automatic emergency brakes and lane change assistance (cf. Winner, H., Hakuli, S., Lotz, F., Singer, C .: Manual Driver Assistance Systems, Basics, Components and Systems for Active Safety and Comfort, 3rd Ed., Wiesbaden: Springer Vieweg, 2015, p. 260 ). Furthermore, cameras for environment detection z. For example, as a reversing camera, in surround view camera systems, as mirror replacement, in automatic high beam functions and in machine vision systems as image sensors for object detection and intersection detection used (see. Winner, H., Hakuli, S., Lotz, F., Singer, C .: Manual Driver Assistance Systems, Basics, Components and Systems for Active Safety and Comfort, 3rd ed., Wiesbaden: Springer Vieweg, 2015, p. 348 + P. 391 ). Lidar (Light Detection And Ranging), which is similar in principle to the radar method, is also available to date, although UV, IR or radiation from the visible light range are used instead of microwaves (cf. Winner, H., Hakuli, S., Lotz, F., Singer, C .: Manual driver assistance systems, fundamentals, components and systems for active safety and comfort, 3rd ed., Wiesbaden: Springer Vieweg, 2015, p. 318 f , ). It should be noted in particular that in the future, laser scanners will potentially be used increasingly in the field of semi-autonomous / fully autonomous driving applications (cf. Winner, H., Hakuli, S., Lotz, F., Singer, C .: Manual Driver Assistance Systems, Basics, Components and Systems for Active Safety and Comfort, 3rd ed., Wiesbaden: Springer Vieweg, 2015, p. 333 ).

A functional road marking to be detected by microwaves by adding metal spheres or particles or other materials with a high dielectric constant to the marking composition is disclosed in US Pat EP 0881333 A1 described. In WO 2014/166693 A1 Also, a road marking is reported as an invention, which is to serve the support of the environment perception of vehicles. Comparable to EP 0881333 A1 is in WO 2014/166693 A1 an additional reflectivity of the mark for electromagnetic radiation (especially for microwave and infrared radiation) by the addition of spherical and / or cylindrical metal particles used.

With the invention described herein, the technical fundamentals of a means for multifunctional marking of a roadway and the method according to the invention for application are presented. In particular, the safety in road traffic z. B. by a luminescent material and a material to be effectively mounted by a sensor which is to be mounted in a corresponding device on a vehicle to be detected material to be improved. The optical effect of a luminophore is intended to serve especially at night for better detection of a road surface of traffic and thus exceed the usual warning effect of a well-known road lane marking. In addition, z. As a magnetically active substance as quantitatively measurable size even under the most severe weather conditions such. B. under a blanket of snow by means of z. B. to be detected by a magnetometer, which is given the possibility of evaluating the data of the control of the vehicle when leaving the lane warning signals to notify the driver and possibly initiate correction controls the vehicle.

These objects are achieved according to the invention by a means and a method having the features of the dependent claims.

und die Variablen bevorzugt wie folgt definiert sind:

• • die Reste R¹, R², R³ und R⁴ sind unabhängig voneinander,
• • der Rest R¹ ist Wasserstoff, ein Alkyl-, Cycloalky-, Alkylcycloalkyl-, Heteroalkyl-, Heterocycloalkyl-, Heteroalkylcycloalkyl-, Aryl-, Heteroaryl-, Aralkyl- oder Heteroaralkyl-Rest mit bis zu 40 C-Atomen oder ein -Si(R)_x(OR)_3-x-Rest mit R = ein Alkyl-, Cycloalky-, Alkenyl-, Cycloalkenyl-, Alkinyl-, Cycloalkinyl-, Alkylcycloalkyl-, Heteroalkyl-, Heterocycloalkyl-, Heteroalkylcycloalkyl-, Aryl-, Heteroaryl-, Aralkyl-, Heteroaralkyl-Rest mit bis zu 40 C-Atomen und x = 0, 1, 2 oder 3, und
• • der Rest R² ist Wasserstoff oder ein Alkyl- oder Heteroalkyl-Rest mit bis zu 40 C-Atomen, und
• • die Reste R³ und R⁴ sind Wasserstoffe oder Alkyl-, Cycloalky-, Alkylcycloalkyl-, Heteroalkyl-, Heterocycloalkyl-, Heteroalkylcycloalkyl-, Aryl-, Heteroaryl-, Aralkyl- oder Heteroaralkyl-Reste mit bis zu 40 C-Atomen, und
• • n ist variabel.

The road marking according to the invention is characterized in that it comprises binders which consist of monomers which can form homogeneous and / or inhomogeneous acrylic resins and mixtures of acrylic resins, the composition of the polymer units forming thereby being characterized by formula I.

and the variables are preferably defined as follows:

• • the radicals R ¹ , R ² , R ³ and R ⁴ are independent of one another,
• • the radical R ¹ is hydrogen, an alkyl, cycloalky, alkylcycloalkyl, heteroalkyl, heterocycloalkyl, heteroalkylcycloalkyl, aryl, heteroaryl, aralkyl or heteroaralkyl radical having up to 40 carbon atoms or a -Si (R) _x (OR) _3-x- radical where R = an alkyl, cycloalky, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, alkylcycloalkyl, heteroalkyl, heterocycloalkyl, heteroalkylcycloalkyl, aryl, heteroaryl -, aralkyl, heteroaralkyl radical having up to 40 carbon atoms and x = 0, 1, 2 or 3, and
• • the radical R ² is hydrogen or an alkyl or heteroalkyl radical having up to 40 carbon atoms, and
• • the radicals R ³ and R ⁴ are hydrogens or alkyl, cycloalky, alkylcycloalkyl, heteroalkyl, heterocycloalkyl, heteroalkylcycloalkyl, aryl, heteroaryl, aralkyl or heteroaralkyl radicals having up to 40 carbon atoms, and
• • n is variable.

Each of the alkyl, cycloalkyl, alkylcycloalkyl, heteroalkyl, heterocycloalkyl, heteroalkylcycloalkyl, aryl, heteroaryl, aralkyl or heteroaralkyl radicals may, in preferred embodiments, contain one or more halo, hydroxy, thiol, carbonyl, , Keto, carboxyl, cyano-sulfone, amino and / or imino functions.

The term alkyl radical having up to 40 carbon atoms refers in particular to a saturated, straight-chain or branched hydrocarbon group which has 1 to 20 C atoms, preferably 1 to 12 C atoms, particularly preferably 1 to 6 C atoms , Examples of these are the methyl, ethyl, propyl, isopropyl, isobutyl, t-butyl, n-hexyl, 2,2-dimethylbutyl or n-octyl group.

The term cycloalkyl radical having up to 40 carbon atoms refers in particular to saturated cyclic groups which have one or more rings which have in particular 3 to 14 ring C atoms, more preferably 3 to 10 ring C atoms , Examples include the cyclopropyl group.

The term heteroalkyl radical having up to 40 carbon atoms refers in particular to an alkyl group in which one or more (preferably 1, 2 or 3) carbon atoms or CH or CH ₂ groups is replaced by O, N , P and / or S are replaced. Examples of these are alkyloxy groups such as methoxy or ethoxy or tertiary amine structures.

The term heterocycloalkyl radical having up to 40 carbon atoms refers in particular to a cycloalkyl group in which one or more (preferably 1, 2 or 3) ring C atoms or ring CH or CH ₂ groups are replaced by O, N, P and / or S, and may be, for example, the piperidine or N-phenylpiperazine group.

The term aryl radical having up to 40 carbon atoms refers in particular to an aromatic group which has one or more rings which in particular have 5 or 6 to 14 ring C atoms, more preferably 5 or 6 to 10 ring C atoms Atoms, included. An example of this is a phenyl group.

The term heteroaryl radical having up to 40 carbon atoms refers in particular to an aryl group in which one or more (preferably 1, 2 or 3) ring C atoms or ring CH or CH ₂ groups are replaced by O, N, P and / or S. An example of this is the pyridyl group.

The terms aralkyl or heteroaralkyl radical having up to 40 carbon atoms refer in particular to groups which, in accordance with the above definitions, have both aryl and / or heteroaryl groups and also alkyl and / or heteroalkyl groups.

The terms alkylcycloalkyl or heteroalkylcycloalkyl radical having up to 40 carbon atoms refer to groups which according to the above definitions contain both cycloalkyl or heterocycloalkyl and also alkyl and / or heteroalkyl groups.

As examples of a group of the above-described general formula -Si (R) _x (OR) _3-x where x = 0, 1, 2 or 3, here are organosilicon compounds such as -SiMe ₃ , -SiEt ₃ , -SiPr ₃ , - Si (OMe) ₃ , -SiMe (OMe) ₂ , -SiMe ₂ (OMe), -Si (OPh) ₃ , -SiMe (OPh) ₂ , -SiMe ₂ (OPh), -Si (OEt) ₃ , -SiMe (OEt) ₂ , -SiMe ₂ (OEt), -Si (OPr) ₃ , -SiMe (OPr) ₂ , -SiMe ₂ (OPr), -SiEt (OMe) ₂ , -SiEtMe (OMe), -SiEt ₂ ( OMe), -SiPh (OMe) ₂ , -SiPhMe (OMe) or -SiPh ₂ (OMe), where the abbreviations Me for methyl, Ph for phenyl, Et for ethyl and Pr for iso- or n- Propyl.

R ² , R ³ and R ^{4 are} preferably hydrogen atoms or alkyl radicals, more preferably at least one radical of R ² , R ³ and R ^{4 is} a hydrogen atom and the others are alkyl radicals.

The road marking according to the invention is also distinguished by the fact that it has further additives. Thus, the agent pigments z. As metal oxides such as ZnO, BaSO ₄ , MgO, FeO (OH), Fe ₂ O ₃ , Fe ₃ O ₄ and TiO ₂ included.

Furthermore, the road marking according to the invention can particles of all sizes of abrasive materials having a high hardness such as SiO ₂ , Al ₂ [(F, OH) ₂ SiO ₄ ], Al ₂ SiO ₄ (F, OH) ₂ , Al ₂ Be ₃ (Si ₆ O ₁₈ ), other silicates, Al ₂ O ₃ and SiC.

In addition, in particular embodiments, the road marking according to the invention may additionally contain polymer fibers of all sizes consisting of homogeneous and / or inhomogeneous thermosets or mixtures of thermosets such as epoxy resins and highly crosslinked polyacrylates to increase the strength, thereby significantly increasing the longevity of the marking.

The road marking according to the invention is also distinguished by the fact that it can have hardeners such as dibenzoyl peroxide.

The road marking according to the invention is furthermore distinguished by the fact that it can have accelerators, binders, adhesion promoters, crosslinkers, stabilizers and inhibitors.

The road marking according to the invention is also distinguished by the fact that it can have waxes, wax-water emulsions or paraffins.

Embodiments of road markings according to the invention may be composed of commercially available road marking paints, high-solids dispersions, thermoplastic materials, reactive systems or films for producing road markings with structure or without structure.

The road marking according to the invention is characterized in particular by the fact that it can have long luminescent luminophores of rare earth doped mixed and pure alkaline earth aluminates, silicates and phosphates. Formulas II-V give examples of chemical compositions of luminophores for use in the invention. Lumineszenzdauern after resolution to 00:32 mcd / m ^2, respectively. Luminescence duration (0.32 mcd / m ² ) Formula II CaAl ₂ O ₄ : Eu ²⁺ , Nd ³⁺ > 10 h ⁽¹⁾ Formula III Sr ₂ MgSi ₂ O ₇ : Eu ²⁺ , Dy ³⁺ > 10 h ⁽²⁾ Formula IV Sr ₄ Al ₁₄ O ₂₅ : Eu ²⁺ , Dy ³⁺ > 15 h ⁽³⁾ Formula V Ca ₆ BaP ₄ O ₁₇ : Eu ²⁺ , Ho ³⁺ > 47 h ^{(4) (1)} Smet, PF; Avci, IV .; Van den Eeckhout, K .; Poelman, D. Opt. Mater. Express 2012, 2, 1306-1313 ,
⁽²⁾ Lin, Y .; Tang, Z .; Zhang, Z .; Wang, X .; Zhang, JJ Mater. Sci. Lett. 2001, 20, 1505-1506 ,
⁽³⁾ Lin, Y .; Tang. Z .; Zhang, Z. Mater. Lett. 2001, 51, 14-18 ,
⁽⁴⁾ Guo, H .; Chen, W .; Zeng, W .; Li, G .; Wang, Y .; Li, Y .; Li, Y .; Ding, XJ Mater. Chem. C 2015, 3, 5844-5850 ,

The road marking according to the invention is also characterized by the fact that it mixtures of long luminescent luminophores from z. B. rare earth doped mixed and pure alkaline earth aluminates, silicates and phosphates may have a variety of compositions which can emit according to the composition of the mixture in the sum of white light.

Furthermore, the road marking according to the invention is characterized in particular by the fact that it may comprise magnets such as magnetite, further (hard) ferrites, neodymium-iron-boron, samarium-cobalt, aluminum-nickel-cobalt, wherein the condition for an application is that For corrosion prone magnets surfaces can be treated.

In particular, a production method for a roadway marking according to the invention is characterized in that mixtures of marking additives according to the invention are particularly preferably produced by luminophores, magnets and paints / high-solids dispersions / thermoplastics / reactive systems. These mixtures are applied to the road surface. Optionally, glass beads are added during or immediately after application.

The road marking according to the invention is characterized in that it comprises a mixture of at least 0-30 wt .-% of a magnetic additive and / or 1-50 wt .-%, particularly preferably 10-30 wt .-%, a luminescent pigment and 50 -99 wt .-% of a carrier material, which may contain all other additives, is.

Depending on the latitude or climatic zone of the location of application of the agent, the composition of the mixture of road pavement marking according to the invention may vary, so that in certain embodiments, depending on the relative saturation excitation, the marker may have more or less addition of the afterglowing pigment.

By the means presented herein, the leadership of the road users by a multi-functional street lane marking is to be guaranteed and significantly improved even at night, in low light and in extreme weather conditions. The composition of the road marking according to the invention ensures an application at low temperatures, rapid drying, a large adhesion to a road surface, few formation breaks and detachments, good color fastness and a high resistance to stresses such as impact forces and thus a long life. By z. B. luminescent additives should v. a. the night visibility can be increased. Driver assistance systems should also by z. B. magnetic additives for road marking effective transmitter are given. Thus, the automatic recognition of road markings should be facilitated for driver-supported.

Further features of the invention will become apparent from the following description of a preferred embodiment. It should be emphasized at this point that all facultative aspects of the agent or the method according to the invention described in the present application can each be implemented alone or in combination with one or more of the further optional aspects described in one embodiment of the invention. The following description of a preferred embodiment is merely illustrative and for a better understanding of the invention and is in no way limiting. Both the means and methods described herein and the embodiment may be variously modified and adapted to other requirements.

embodiment

Straßenmarkierfarbe was obtained from Eagle Germany GmbH, LumiNova ^® BG-300M of Nemoto Lumi Materials Co., Ltd .. 2 × 2 × 2 mm NdFeB permanent magnet cube (1.28 T) were purchased from Conrad Electronic SE.

To determine the time course of the light intensity, a light meter PCE-170 A PCE Germany GmbH was used.

LumiNova ^® BG-300M is a blue luminescent compound with the following composition: Sr _(4-xy) Al ₁₄ O ₂₅ : Eu _y , Dy _x . According to the manufacturer, the luminescence time (until fading to 0.32 mcd / m ² ) is over 2000 minutes.

A composition was shown as follows:

A mixture of the following composition was produced:
120 ml road marking paint
40 g LumiNova ^®
0.6 g magnets

The composition was applied using a hand-held paint roller.

After 15 minutes 1000 lx universal white exposure, an emission value of 0.03 cd / m ^{2 was} determined after 60 min. The time to decay to 0.32 mcd / m ² was approximately (after linear adjustment; DIN 67510-1: 2009-11 ) 47 h.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• WO 2007/056820 A1 [0003, 0010]
• EP 2008/1958517 A2 [0003]
• EP 2827047 A1 [0004, 0004]
• WO 2012/141626 A1 [0008, 0009]
• CH 709020 A1 [0008]
• US 5424006 A [0008]
• WO 2015/099145 A1 [0008]
• CN 104479676 A [0008]
• US 2010/0291409 A1 [0009]
• WO 2015/053632 A1 [0010]
• EP 0881333 A1 [0012, 0012]
• WO 2014/166693 A1 [0012, 0012]

Cited non-patent literature

• §§ 39 ff StVO [0002]
• Frank, H., Reinsberg, H .: Guideline road markings, Bonn, Bad Sachsa: German Road Safety Council e. V., Deutsche Studiengesellschaft für Straßenmarkierungen e. V., 2014 [0002]
• Frank, H., Reinsberg, H .: Guideline road markings, Bonn, Bad Sachsa: German Road Safety Council e. V., Deutsche Studiengesellschaft für Straßenmarkierungen e. V., 2014 [0003]
• DIN 67510-1: 2009-11 [0006]
• Hölsä, J. Electrochem. Soc. Interface 2009, 42-45 [0006]
• DIN 67510-1: 2009-11 [0007]
• Frank, H., Reinsberg, H .: Guideline road markings, Bonn, Bad Sachsa: German Road Safety Council e. V., Deutsche Studiengesellschaft für Straßenmarkierungen e. V., 2014 [0011]
• Winner, H., Hakuli, S., Lotz, F., Singer, C .: Manual Driver Assistance Systems, Basics, Components and Systems for Active Safety and Comfort, 3rd ed., Wiesbaden: Springer Vieweg, 2015, p. 56 f , [0011]
• Winner, H., Hakuli, S., Lotz, F., Singer, C .: Handbook Driver Assistance Systems, Basics, Components and Systems for Active Safety and Comfort, 3rd Ed., Wiesbaden: Springer Vieweg, 2015, p. 591 [ 0011]
• Winner, H., Hakuli, S., Lotz, F., Singer, C .: Manual driver assistance systems, fundamentals, components and systems for active safety and comfort, 3rd ed., Wiesbaden: Springer Vieweg, 2015, p. 1147 f , [0011]
• Winner, H., Hakuli, S., Lotz, F., Singer, C .: Manual Driver Assistance Systems, Basics, Components and Systems for Active Safety and Comfort, 3rd ed., Wiesbaden: Springer Vieweg, 2015, p. 244- 257 [0011]
• Winner, H., Hakuli, S. Lotz, F., Singer, C .: manual driver assistance systems, principles, components and systems for active safety and comfort, 3rd edition, Wiesbaden. Springer Vieweg, 2015, p 260 [ 0011]
• Winner, H., Hakuli, S., Lotz, F., Singer, C .: Manual Driver Assistance Systems, Basics, Components and Systems for Active Safety and Comfort, 3rd ed., Wiesbaden: Springer Vieweg, 2015, p. 348 + P. 391 [0011]
• Winner, H., Hakuli, S., Lotz, F., Singer, C .: Manual driver assistance systems, fundamentals, components and systems for active safety and comfort, 3rd ed., Wiesbaden: Springer Vieweg, 2015, p. 318 f , [0011]
• Winner, H., Hakuli, S., Lotz, F., Singer, C .: Manual Driver Assistance Systems, Basics, Components and Systems for Active Safety and Comfort, 3rd Ed., Wiesbaden: Springer Vieweg, 2015, p. 333 [ 0011]
• Smet, PF; Avci, IV .; Van den Eeckhout, K .; Poelman, D. Opt. Mater. Express 2012, 2, 1306-1313 [0034]
• Lin, Y .; Tang, Z .; Zhang, Z .; Wang, X .; Zhang, JJ Mater. Sci. Lett. 2001, 20, 1505-1506 [0034]
• Lin, Y .; Tang. Z .; Zhang, Z. Mater. Lett. 2001, 51, 14-18 [0034]
• Guo, H .; Chen, W .; Zeng, W .; Li, G .; Wang, Y .; Li, Y .; Li, Y .; Ding, XJ Mater. Chem. C 2015, 3, 5844-5850 [0034]
• DIN 67510-1: 2009-11 [0047]

Claims (18)

Roadway marking means, characterized in that the means consist of luminophores described below and of a paint and / or a varnish and of other materials and thus contribute to the increased environmental perception of vehicles by better optical night visibility and effective detection of the marking even under extreme weather conditions by means of sensors, which is mounted in a corresponding device on a vehicle makes. Roadway marking material according to claim 1, characterized in that the binder of an adhesive material according to the invention consists of monomers which form homogeneous and / or inhomogeneous acrylic resins and mixtures of acrylic resins, wherein the composition of the polymer units used is characterized by formula I.

and for the symbols and indices used: n is variable; R ¹ , R ² , R ³ and R ⁴ are independently; R ¹ is selected from hydrogen, a saturated, straight-chain or branched alkyl, a saturated cycloalky, an alkylcycloalkyl, a heteroalkyl, a heterocycloalkyl, a heteroalkylcycloalkyl, an aryl, a heteroaryl, an aralkyl, a Heteroaralkyl radical having up to 40 carbon atoms or a -Si (R) _x (OR) _3-x radical with R = an alkyl, cycloalky, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, alkylcycloalkyl radical , Heteroalkyl, heterocycloalkyl, heteroalkylcycloalkyl, aryl, heteroaryl, aralkyl or a heteroaralkyl radical having up to 40 carbon atoms and x = 0, 1, 2 or 3; R ² is selected from hydrogen or a saturated, straight-chain or branched alkyl or heteroalkyl radical having up to 40 carbon atoms, and R ³ and R ⁴ are selected from hydrogen or a saturated, straight-chain or branched alkyl, a saturated cycloalky -, an alkylcycloalkyl, a heteroalkyl, a heterocycloalkyl, a Heteroalkylcycloalkyl-, an aryl, a heteroaryl, an aralkyl, a heteroaralkyl radical having up to 40 carbon atoms. Roadway marking means according to claims 1 and 2, characterized in that the means also abrasive substances such as SiO ₂ , Al ₂ [(F, OH) ₂ SiO ₄ ], Al ₂ SiO ₄ (F, OH) ₂ , Al ₂ Be ₃ (Si ₆ O ₁₈ ), further silicates, Al ₂ O ₃ and / or SiC may contain. Roadway marking means according to one or more of claims 1-3, characterized in that the agent in particular embodiments may additionally contain homogeneous and / or inhomogeneous thermosetting polymer fibers of all sizes to increase the strength of the applied marking. Roadway marking material according to one or more of claims 1-4, characterized in that the luminophore can consist of a luminescent substance, wherein the luminescent luminophore consists of rare earth doped mixed and pure alkaline earth aluminates, silicates and phosphates as flour, powder or ( Nano-) particles may be present. Roadway marking means according to one or more of claims 1-5, characterized in that the means of a mixture of long luminescent luminophores of z. B. rare earth doped, mixed and pure alkaline earth aluminates, silicates and phosphates of various composition may exist, which can emit according to the composition of the mixture in the sum of white light. Roadway marking means according to one or more of claims 1-6, characterized in that the luminescent substances must be located close to the surface of the applied marking. Roadway marking means according to one or more of claims 1-7, characterized in that the means may contain primarily magnets such as magnetite, further (hard) ferrites, neodymium-iron-boron, samarium-cobalt, aluminum-nickel-cobalt. Roadway marking means according to one or more of claims 1-8, characterized in that surfaces susceptible to corrosion can be treated surfaces. Roadway marking means according to one or more of claims 1-9, characterized in that the agent may additionally consist of further substances of the material types mentioned below: fillers, accelerators, hardeners, inhibitors, binders, adhesion promoters, crosslinkers, prepolymers, pigments, paints , Stabilizers, waxes. Roadway marking material according to one or more of claims 1-10, characterized in that the agent can be composed of mixtures of additives according to the invention and prefabricated paints, high-solids dispersions, thermoplastics or reactive systems for road marking. Roadway marking means according to one or more of claims 1-11, characterized in that the means on the surface may additionally comprise glass beads. Roadway marking means according to one or more of claims 1-12, characterized in that the agent of at least 0-30 wt .-% of a magnetic additive and / or 1-50 wt .-%, particularly preferably 10-30 wt.- %, a luminescent pigment and / or 50-99 wt .-% of a carrier material, which may contain all other additives consists. Roadway marking material according to one or more of Claims 1-13, characterized in that the composition of the composition, ie the amount of long-luminescent pigment added and the viscosity of the composition before application, in particular embodiments depending on the latitude and the climatic zone of the place Application can be. Roadway marking material according to one or more of claims 1-14, characterized in that the viscosity of the agent before application can be determined inter alia by the polymer lengths of the homogeneous and / or inhomogeneous acrylic resins. Method for marking a roadway with a means according to claims 1-15, characterized in that the magnets are introduced individually during the application of the roadway lane marking, so that it can come to no ball formation of the magnets. Method for marking a roadway with a means according to claims 1-15, characterized in that the surface of the applied marking of the means for roadway marking can be sealed with a lacquer and last glass beads can be applied. A method of marking a roadway with an agent according to claims 1-15, characterized in that the means for road pavement marking by spraying, with a draw shoe, in the extrusion process or by gluing or rolling can be applied.