DE102016003526A1 - Roadway marking with great performance and method of application - 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 a color with great performance and increased night visibility.

Description

It is hereby incorporated an agent and its specific composition, as well as a method of marking specified areas of road traffic with a paint and / or varnish as an invention, in particular a composition according to claims 1-13 and a method according to claims 14-16 concerns. The wording of all claims is hereby incorporated by reference into the content of this specification.

Important properties of a paint are the viscosity, the drying behavior and the properties of the applied agent, the coating, such as gloss, resistance to scratching, hardness, adhesion to the desired surface and surface structure. By a specific composition of the paint its macroscopic properties can be influenced. So z. B. the selected binder of crucial importance. In addition, pigments and fillers, plasticizers (plasticizers), solvents and other additives can be important factors influencing the desired properties of a paint (cf. Stoye, D., Marwald, B., Plehn, W .: Paints and Coatings, 1st Introduction, Ullmann's Encyclopaedia of Industial Chemistry, 8th edition, Weinheim: Wiley-VCH, 2015 ).

A special paint is acrylic paints (or lacquers). Polyacrylates are characterized by high chemical resistance, resistance to yellowing, high gloss and high gloss retention and stability against hydrolysis. Polyacrylates without aryl groups do not absorb above 300 nm and thus do not degrade by UV radiation. There are so-called low-solvent high-solid inks, water dispersions and solvent-free inks (cf. Funke, W., Hoppe, L., Hasselkus, J., Curtis, LG, Hoehne, K., Zech, H.-J., Heiling, P., Yamabe, M., Dören, K., Schupp, H , Küchenmeister, R., Schmitthenner, M., Kremer, W., Wieczorrek, W., Gempeler, H., Schneider, W., White, JW, Short, AG, Blank, WJ, Calbo, LJ, Plath, D., Wagner, F., Haller, W., Rödder, K.M .: Paints and Coatings, 2nd Types, Ullmann's Encyclopedia of Industial Chemistry, 8th edition, Weinheim: Wiley-VCH, 2015 ).

A particular coating method of paints, which is potentially characterized by high economy and environmental friendliness (= eco-efficiency) and is enjoying increasing popularity or increasing growth rates of application, is the radiation curing. A hallmark of her is that the resulting products are of high quality and have high scratch and abrasion resistance. In the specific case of UV curing, the photochemical formation of a reactive species that is capable of initiating spontaneous polymerization of the binder at room temperature and resulting in curing of the entire applied layer occurs by UV light. UV curing is universally applicable: For solvent-free coatings, 100% liquid lacquer, water-based UV coatings, UV powder coatings and dual-cure systems (UV and thermal curing). Solvent-free coatings can be cured in seconds, whereby the physical properties of the not yet applied coatings are adjustable from highly elastic to highly cross-linked. Problems are associated with an excessively high reactivity, ie with a polymerization reaction that proceeds too rapidly, since these cause the coating to shrink, which can lead to adhesion problems on the applied surface. Potentially, UV coatings can be used outdoors (oxygen is a polymerization inhibitor, but can be cured in the presence of UV absorbers and HALS radical scavengers). One reason why so far only a few UV-cured outdoor applications have been realized is due to the lack of through-hardening of pigmented lacquer layers (cf. Streitberger, H.-J., Urbano, E., Laible, R., Meyer, BD, Bagda, E., Waite, FA, Philips, M .: Paints and Coatings, 3. Paint Systems, Ullmann's Encyclopaedia of Industial Chemistry , 8th edition, Weinheim: Wiley-VCH, 2015 ; Schwalm, R .: UV Coatings Basics, Recent Developments and New Applications, Elsevier, 2007 ).

Components of an ordinary UV-curable acrylic paint or varnish are one or more prepolymer (s) and monomer (s) having acrylic functionality (s), one or more photoinitiator (s), and additives. The oligomer system of the prepolymer greatly affects the film forming properties of the paint. Usually, acrylated epoxy, acrylated urethane, acrylated acrylic systems, polyether and polyester acrylates are used. Acrylated epoxy resins generally provide for hard, solvent resistant coatings with fast cure and relatively low cost. On the other hand, coatings made of acrylated urethane resins are highly flexible and resistant to abrasion, while those made of acrylated acrylic resins do not yellow. Because of the low viscosity, polyether acrylates are often used as reactive diluents. Polyester acrylates, on the other hand, are real all-rounders and have a balanced range of properties. Monomers serve as reactive liquefiers (viscosity reduction) and are integrated by cross-linking directly into the network of the binder, which solvent can be completely replaced. Paints can thus be cast, rolled or sprayed without the use of solvents. In addition, the crosslinking density can be varied by the functionality of the reactive diluents. All physical and chemical properties of the coating are greatly influenced by the monomers. It has been shown that z. B. the high scratch resistance of UV clearcoats correlates relatively well with high crosslinking density. In addition, the hardness and chemical resistance. In general, network properties are characterized by physical (modulus, hardness, elasticity, scratch resistance, etc.) or chemical (swelling, solvent, chemical resistance, hydrolysis, etc.) methods (cf. Meichsner, G., Deuter, F., Gross, T., Beck, E., Menzel, K. Color & Lacquer 1997, 103 (8), 45-50 ). In addition to acrylate monomers, other monomers are used in specific embodiments, such as styrene, vinylpyrrolidone, vinylcaprolactam or vinyl ether. Pigments, fillers, antifoam agents, wetting agents, matting agents and anti-slipping agents play an important role as additives (cf. Streitberger, H.-J., Urbano, E., Laible, R., Meyer, BD, Bagda, E., Waite, FA, Philips, M .: Paints and Coatings, 3. Paint Systems, Ullmann's Encyclopaedia of Industial Chemistry , 8th edition, Weinheim: Wiley-VCH, 2015 ; Schwalm, R .: UV Coatings Basics, Recent Developments and New Applications, Elsevier, 2007 ).

Improved or further (as described in previous patent applications) possibilities of a better dispersion of a pigment Kronos has shown: Poorly dispersible pigments of 100% TiO ₂ can be subjected to a surface treatment with colorless oxides of Si, Al or Zr, whereby the dispersibility should increase significantly. A better wettability of the pigment surface by the surrounding medium can finally be ensured by a subsequent and final treatment with a polyol (cf. WO 2012/130408 A1 . DE 10 2004 037 272 A1 . DE 10 2011 113 896 A1 ).

Hybrid polymers (silicate acrylate) are enjoying increasing popularity due to their convincing properties. So z. As the chemical bonding of silicates to acrylate polymers instead of the physical involvement (ordinary mixture) a greater thermal stability and a higher flame retardancy (see. Vahabi, H., Ferry, L., Longuet, C., Otazaghine, B., Negrell-Guirao, C., David, G., Lopez-Cuesta, J.-M. Mater. Chem. Phys. 2012, 135, 762-770 ).

In general, there are two ways of realizing a chemical bonding of silicates to polymers, wherein a common step namely the silanol functionalization is necessary: first, Si-OH groups of silicates can be functionalized by reaction with functionalized chlorosilanes or functionalized alkoxysilanes and followed by subsequent reactions functional groups are incorporated with monomers or Präpolmeren in the carbon-containing polymer network. If, on the other hand, functionalized alkoxysilanes are used with monomers or prepolymers, they can polymerize themselves, so that, for. B. for alkyoxysilane acrylic monomers for the polymerization of the carbon-containing monomer, a second polymerization reaction takes place, wherein the reaction rate depends strongly on the monomer used (see. Klapdohr, S., Moszner, N., Kickelbick, G., Krüger, R.-P. Monatsh. Chem. 2006, 137, 667-679 ; Altmann, S., Pfeiffer, J. Monatsh. Chem. 2003, 134, 1081-1092 ).

With the invention described herein, the technical principles of a means for marking a roadway with high performance and the application of the method according to the invention are presented. In particular, the safety in traffic should be improved by a long-lasting material. 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.

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

und Forme II

mit Variablen, die 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, ein Si(R)_x(OR)_3-x-, oder ein Si(R)_4-x(OR)_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
• • Y ist ein Alkyl- oder Heteroalkyl-Rest mit bis zu 40 C-Atomen, und
• • n ist 1, 2 oder 3, und
• • 1 ist das unten beschriebene Luminophor.

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 polymers and mixtures of polymers, wherein the monomers are characterized by formula I and formula II and the following applies:

and Forms II

with variables that 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, an Si ( R) _x (OR) _3-x- , or a Si (R) _4-x (OR) _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
• Y is an alkyl or heteroalkyl radical with up to 40 C atoms, and
• • n is 1, 2 or 3, and
• • 1 is the luminophore described below.

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 terms alkenyl and alkynyl radical having up to 40 carbon atoms refer in particular to at least partially unsaturated, straight-chain or branched hydrocarbon groups containing 2 to 20 C atoms, preferably 2 to 12 C atoms, particularly preferably 2 to 5 C Atoms. Examples include the ethenyl, allyl, acetylenyl, propargyl, isoprenyl or hex-2-enyl group.

The terms cycloalkyl, cycloalkenyl and cycloalkynyl radical having up to 40 carbon atoms refer in particular to saturated or partially unsaturated cyclic groups which have one or more rings which in particular have 3 to 14 ring C atoms, particularly preferably 3 up to 10 ring C atoms. Examples of these are the cyclopropyl, cyclohexyl, tetralin or cyclohex-2-enyl 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, according to the above definitions, are both aryl and / or heteroaryl groups and also alkyl, alkenyl, alkynyl or heteroalkyl groups exhibit. Examples of these are arylalkyl, arylalkenyl, arylalkynyl, arylheteroalkyl, arylheteroalkenyl, arylheteroalkynyl, heteroarylheteroalkyl, heteroarylheteroalkenyl, heteroarylheteroalkynyl, arylcycloalkyl, heteroarylcycloalkyl, arylheterocycloalkyl, heteroarylheterocycloalkyl, heteroarylcycloalkenyl, arylcycloalkenyl, arylcycloalkynyl, Heteroarylheterocycloalkyl-, Heteroarylheterocycloalkenyl-, Arylcycloalkyl-, Heteroarylcycloalkyl-, Arylheterocycloalkyl-, Heteroarylheterocycloalkyl-, Heteroarylcycloalkenyl-, Arylcycloalkenyl-, Arylcycloalkinyl-, Heteroarylcycloalkinyl-, Arylheteroalkenyl-, Heteroarylheteroalkenyl-, Arylheteroalkinyl-, Heteroarylheteroalkinyl-, heteroarylalkyl, heteroalkenyl and heteroarylalkynyl- 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.

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 characterized by the fact that they inorganic pigments and fillers, such. As ZnO, BaSO ₄ , MgO, FeO (OH), Fe ₂ O ₃ , Fe ₃ O ₄ and TiO ₂ may contain. Fillers are used for reasons of cost reduction and viscosity reasons in particular embodiments.

In addition, the road marking according to the invention may comprise hardeners (eg dibenzoyl peroxide), accelerators, stabilizers and inhibitors, plasticizers, solvents, waxes, wax-water emulsions and paraffins.

In a particular embodiment, the road marking according to the invention may also co-initiators such as UV absorbers and radical scavengers and / or photoinitiators such. As hydroxyalkyl ketones, benzophenones and Acylphosphanoxide included.

The road marking of the invention is further characterized in that it may contain additives such as leveling agents, flow agents, film forming accelerators, dispersants, wetting aids, anti-foaming agents, catalysts, desiccants, anti-fogging agents, anti-skinning agents, matting agents, neutralizing agents, thickening agents and preservatives.

In a particular embodiment of the road marking according to the invention, as few additives as possible and as far as possible no solvent, but instead reactive liquefier should be used.

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 from homogeneous and / or inhomogeneous thermosets or mixtures of thermosets such as epoxy resins and highly crosslinked polyacrylates to increase the strength, thereby increasing the longevity of the marking.

The road marking according to the invention is also distinguished by the fact that the agent can be composed of mixtures of additives according to the invention and prefabricated (ie also commercially available) paints, high-solids dispersions, thermoplastics or reactive systems for road marking with structure or without structure.

The road marking according to the invention is characterized in particular by the fact that it luminescent phosphorescent ( 1 ) may contain rare earth doped mixed and pure alkaline earth aluminates, silicates and phosphates.

The road marking according to the invention is also characterized in that it comprises mixtures of luminescent luminophores ( 1 ) 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.

The luminophores ( 1 ) are also characterized by the fact that they are functionalized on the surface of their grains by formula II, whereby they themselves become a constituent of the binder and thereby, inter alia, an excellent distribution of the luminescent pigments in the paint and / or the coating during curing is possible ,

To illustrate the invention, an embodiment (n = 1, see formula II) of functionalized luminophores according to the invention ( 1 ) shown in the drawings and described in more detail below.

Show it:

1 a schematic representation of a grain of the functionalized luminophore ( 1 )

2 a schematic representation of several chemically linked (Z) and chemically bound in the surrounding resin (R ') grains of the functionalized luminophore ( 1 )

3 a chemical representation (structural formula) of the manner of linking (Z) two grains of the functionalized luminophore ( 1 ).

In the drawings, only the elements essential for the immediate understanding of the invention are shown.

1 1 shows a schematic representation of a grain of the (II) functionalized with monomers of the formula II (R) Luminophor ( 1 ). In this embodiment, the grain of the luminophore ( 1 ) was first coated with a layer of SiO ₂ and functionalized by chemical bonding to at least partially present on the surface of the SiO ₂ layer Si-OH groups by the monomer.

2 shows a schematic representation of several chemically linked and chemically bound in the surrounding resin grains of the functionalized luminophore ( 1 ), each before the link as in 1 are shown schematically. The chemical linkage of the grains (Z) is in 3 especially clear. Schematically, the chemical incorporation of the individual grains into the resin is generally represented by the R radical.

In 3 is a structural formula of the chemical linkage (Z) of two grains of the functionalized luminophore ( 1 ), each before the link as in 1 are shown schematically, and shown the connection in the resin.

The road marking according to the invention is characterized in that it comprises a mixture of at least 0-95% by weight of oligomeric binder resins (prepolymers), 20-60% by weight of monomers (of the formula I), 5-60% by weight of functionalized luminophores (of formula II), 0-10 wt .-% of photoinitiators and 0-50 wt .-% of other additives and pigments / fillers.

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

In one particular embodiment, the road marking according to the invention can be cured by UV light, in which case it must contain photoinitiators.

The means of road marking presented herein is intended to ensure and significantly improve the guidance of the road users at night and under poor lighting conditions. The composition of the road marking according to the invention ensures an application at low temperatures, fast drying, few formation breaks and detachments, good color fastness, a high resistance to stresses such as impact forces, high scratch and abrasion resistance and thus a long life. Due to the luminescent pigment v. a. the night visibility can be increased. The special functionalization of the luminophore ensures an excellent distribution of the pigment in the paint and / or the paint.

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

LumiNova ^® BG-300M was Nemoto Lumi Materials Co., Ltd. based. 2-Ethylhexyl acrylate, phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide and 3- (trimethoxysilyl) propyl methacrylate were purchased from Sigma-Aldrich Chemie GmbH.

For UV curing, a UV lamp designated UVKL 4 U was used by Aug. Hedinger GmbH & Co. KG.

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.

LumiNova ^® was functionalized as follows:
LumiNova ^® was treated with Na water glass and thereby the grains of the pigment of a silicate layer coated or surface treated with SiO ₂ (modified surface treatment US 3,591,398 ). Subsequently, the surface-treated pigment was functionalized by reaction with 3- (trimethoxysilyl) propyl methacrylate (see formula III) in toluene (cf. Van Der Voort, P., Vansant, EFJ Liq. Chromatogr. Related Technol. 1996, 19 (17 & 18), 2723-2752 ). Formula III

According to the manufacturer, phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide is a UV photoinitiator which is particularly effective for pigmented systems and can be used for the radical polymerization of unsaturated resins (cf. Kolczak, U., Rist, G., Dietliker, K., Wirz, JJ Am. Chem. Soc. 1996, 118 (27), 6477-6489 ).

• • 50 g (≙ 0.27 mol ≙ 56.50 mL) 2-Ethylhexylacrylat (M = 184.28 g/mol; ☐ = 0.885 g/mL (25°C); T_Siede (bp) = 215–219°C)
• • 49 g funktionalisiertes LumiNova^®
• • 1 g (≙ 2.39 mmol) Phenyl-bis(2,4,6-trimethylbenzoyl)phosphanoxid (M = 418.46 g/mol)

A color composition was shown as follows:
A homogeneous mixture of the following composition was produced:

• • 50 g (0.27 mol ≙ 56.50 mL) of 2-ethylhexyl acrylate (M = 184.28 g / mol; □ = 0.885 g / mL (25 ° C); T _boiling (bp) = 215-219 ° C)
• • 49 g functionalized LumiNova ^®
• 1 g (2.39 mmol) of phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide (M = 418.46 g / mol)

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

Subsequently, the mixture was cured by UV light.

LIST OF REFERENCE NUMBERS

1

Long luminescent luminophore

R

To the luminophore ( 1 ) chemically bound monomer of formula II

R '

Polymerized monomers of the formulas II and I (resin)

R ¹

Variable of the monomer of the formula I.

R ²

Variable of the monomer of formulas I and II

R ³

Variable of the monomer of formulas I and II

R ⁴

Variable of the monomer of formulas I and II

Y

Variable of the monomer of formula II

X

variable

m

Variable of 3 ; m = 0, 1, 2, ...

Z

Chemical description of the connection between 2 grains of the luminophore ( 1 )

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 2012/130408 A1 [0006]
• DE 102004037272 A1 [0006]
• DE 102011113896 A1 [0006]
• US 3591398 [0050]

Cited non-patent literature

• Stoye, D., Marwald, B., Plehn, W .: Paints and Coatings, 1st Introduction, Ullmann's Encyclopedia of Industial Chemistry, 8th edition, Weinheim: Wiley-VCH, 2015 [0002]
• Funke, W., Hoppe, L., Hasselkus, J., Curtis, LG, Hoehne, K., Zech, H.-J., Heiling, P., Yamabe, M., Dören, K., Schupp, H , Küchenmeister, R., Schmitthenner, M., Kremer, W., Wieczorrek, W., Gempeler, H., Schneider, W., White, JW, Short, AG, Blank, WJ, Calbo, LJ, Plath, D., Wagner, F., Haller, W., Rödder, K.M .: Paints and Coatings, 2nd Types, Ullmann's Encyclopedia of Industial Chemistry, 8th edition, Weinheim: Wiley-VCH, 2015 [0003]
• Streitberger, H.-J., Urbano, E., Laible, R., Meyer, BD, Bagda, E., Waite, FA, Philips, M .: Paints and Coatings, 3. Paint Systems, Ullmann's Encyclopaedia of Industial Chemistry , 8th Edition, Weinheim: Wiley-VCH, 2015 [0004]
• Schwalm, R .: UV Coatings Basics, Recent Developments and New Applications, Elsevier, 2007 [0004]
• Meichsner, G., Deuter, F., Gross, T., Beck, E., Menzel, K. Color & Lacquer 1997, 103 (8), 45-50 [0005]
• Streitberger, H.-J., Urbano, E., Laible, R., Meyer, BD, Bagda, E., Waite, FA, Philips, M .: Paints and Coatings, 3. Paint Systems, Ullmann's Encyclopaedia of Industial Chemistry , 8th edition, Weinheim: Wiley-VCH, 2015 [0005]
• Schwalm, R .: UV Coatings Basics, Recent Developments and New Applications, Elsevier, 2007 [0005]
• Vahabi, H., Ferry, L., Longuet, C., Otazaghine, B., Negrell-Guirao, C., David, G., Lopez-Cuesta, J.-M. Mater. Chem. Phys. 2012, 135, 762-770 [0007]
• Klapdohr, S., Moszner, N., Kickelbick, G., Krüger, R.-P. Monatsh. Chem. 2006, 137, 667-679 [0008]
• Altmann, S., Pfeiffer, J. Monatsh. Chem. 2003, 134, 1081-1092 [0008]
• Van Der Voort, P., Vansant, EFJ Liq. Chromatogr. Related Technol. 1996, 19 (17 & 18), 2723-2752 [0050]
• Kolczak, U., Rist, G., Dietliker, K., Wirz, JJ Am. Chem. Soc. 1996, 118 (27), 6477-6489 [0051]

Claims (16)

Roadway marking means, characterized in that the means consists of a paint and / or a varnish comprising luminophores described below, thus contributing to the enhanced environmental perception of vehicles by better optical night visibility. Roadway marking agent according to claim 1, characterized in that the binder consists of monomers characterized by formula I and formula II. Where: Formula I

and formula II

with variables which are preferably defined as follows: • the radicals R ¹ , R ² , R ³ and R ⁴ are independent of each other, • 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, a Si (R) _x (OR) _3-x -, or a Si (R) _4-x (OR _x - radical where R = an alkyl, cycloalky, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, alkylcycloalkyl, heteroalkyl, heterocycloalkyl, heteroalkylcycloalkyl, aryl, heteroaryl, aralkyl, heteroaralkyl radical with up to 40 C 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 Y is an alkyl or He teroalkyl radical having up to 40 carbon atoms, and • n is 1, 2 or 3, and • 1 is the luminophore described below. 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 means according to one or more of claims 1-4, characterized in that the luminophore can consist of a luminescent substance luminescent, wherein the luminescent luminophore may be of rare earth doped mixed and pure alkaline earth aluminates, silicates and phosphates as flour, powder or (nano) particles. 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 agent according to one or more of claims 1-6, characterized in that the luminophore is functionalized on the surface of its grains by formula II, whereby they themselves become a constituent of the binder. Roadway marking means according to one or more of claims 1-7, characterized in that the agent may additionally contain further substances of the material types mentioned below: pigments, fillers, prepolymers, photoinitiators, co-initiators, accelerators, hardeners, inhibitors, adhesion promoters, Crosslinkers, stabilizers, plasticizers, solvents, leveling agents, flow agents, film-forming accelerators, dispersants, wetting aids, anti-foaming agents, catalysts, drying agents, anti-UV agents, anti-skinning agents, matting agents, neutralizing agents, thickeners, preservatives, waxes, wax-water emulsions and paraffins. Roadway marking means according to one or more of claims 1-8, characterized in that the agent should contain as few additives and as possible no solvent, but instead Reaktiwerflüssiger. Roadway marking material according to one or more of claims 1-9, 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 agent according to one or more of Claims 1-10, characterized in that the agent comprises at least 0-95% by weight of oligomeric binder resins (prepolymers), 20-60% by weight of monomers (of the formula I), 60% by weight of functionalized luminophores (of the formula II), 0-10% by weight of photoinitiators and 0-50% by weight of further additives and pigments / fillers. Roadway marking material according to one or more of claims 1-11, characterized in that the composition of the composition, ie the amount of long-luminescent pigment added and the viscosity of the agent before application, in special embodiments depending on the latitude and the climatic zone of the place Application can be. Roadway marking agent according to one or more of claims 1-12, characterized in that the viscosity of the agent before the application can be determined inter alia by the monomers used, the polymer lengths of the prepolymers and additionally by additives such as plasticizers. A method of marking a roadway with a means according to claims 1-13, characterized in that the paint and / or the paint can be cured by UV light. Method for marking a roadway with a means according to claims 1-13, characterized in that the surface of the coating of the applied means for road lane marking can be sealed with a lacquer. A method of marking a roadway with a means according to claims 1-13, characterized in that the means for road lane marking can be applied by spraying, with a drawing shoe, in the extruder process or by gluing or rolling up.

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