DE102017006843A1 - Multifunctional roadway marking with high performance and method of application - Google Patents

Abstract

The invention relates to an agent and its specific composition, as well as to a method for multifunctional marking of road surfaces, e.g. a strip of roadway with a plastic with great performance and increased visual visibility and night visibility.

Description

Herewith, an agent and its specific composition as well as a method for multifunctional marking of fixed areas of road traffic with a plastic as invention are reported, which relates in particular 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.

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. For example, the chosen binder is 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 ).

Improved or further (as described in previous patent applications) possibilities of 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 are enjoying increasing popularity due to their compelling properties. For example, the chemical attachment of silicates to acrylate polymers instead of physical incorporation (ordinary mixture) shows greater thermal stability and higher flame retardancy (cf. 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 themselves polymerize, which means that a second polymerization reaction takes place, for example, for alkyoxysilane-acrylic monomers for the polymerization of the carbon-containing monomer, the reaction rate thereby being highly dependent on the monomer used (cf. 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 invention are presented. In particular, the safety in traffic should be improved by a photoluminescent material. The optical effect of the luminophore is intended to better identify a lane of the road traffic and thus exceed the usual warning effect of a well-known street pavement marking.

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

und

mit Variablen, die bevorzugt wie folgt definiert sind:

• • die Reste R¹-R¹⁷ sind unabhängig voneinander,
• • der Rest R¹ ist Wasserstoff, ein Alkyl-, Cycloalky-, Alkylcycloalkyl-, Heteroalkyl-, Heterocycloalkyl-, Heteroalkylcycloalkyl-, Aryl-, Heteroaryl-, Aralkyl- oder Heteroaralkyl-Rest, 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 und x = 0, 1, 2 oder 3, und
• • der Rest R² ist Wasserstoff oder ein Alkyl- oder Heteroalkyl-Rest, und
• • die Reste R³-R¹³ sind Wasserstoffe oder Alkyl-, Cycloalky-, Alkylcycloalkyl-, Heteroalkyl-, Heterocycloalkyl-, Heteroalkylcycloalkyl-, Aryl-, Heteroaryl-, Aralkyl-, Heteroaralkyl-Reste, und
• • die Reste R¹⁴-R¹⁷ sind Wasserstoffe oder Alkyl-Reste, und
• • Y ist ein Alkyl- oder Heteroalkyl-Rest, und
• • X ist ein Alkyl-, Cycloalky-, Alkylcycloalkyl-, Heteroalkyl-, Heterocycloalkyl-, Heteroalkylcycloalkyl-, Aryl-, Heteroaryl-, Aralkyl- oder Heteroaralkyl-Rest, 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 und x = 0, 1, 2 oder 3, und
• • n ist 1, 2 oder 3, und
• • p 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 different types of polymers, the monomers being represented by the formulas in Table 1 (Formulas I-VI) and Table 2 (Formulas VII-X) be characterized and the following applies:

and

with variables that are preferably defined as follows:

• • the radicals R ¹ -R ¹⁷ are independent of one another,
• The radical R ¹ is hydrogen, an alkyl, cycloalky, alkylcycloalkyl, heteroalkyl, heterocycloalkyl, heteroalkylcycloalkyl, aryl, heteroaryl, aralkyl or heteroaralkyl radical, 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 and x = 0, 1, 2 or 3, and
• • the radical R ² is hydrogen or an alkyl or heteroalkyl radical, and
• The R ³ -R ¹³ radicals are hydrogens or alkyl, cycloalkyl, alkylcycloalkyl, heteroalkyl, heterocycloalkyl, heteroalkylcycloalkyl, aryl, heteroaryl, aralkyl, heteroaralkyl radicals, and
• • the radicals R ¹⁴ -R ¹⁷ are hydrogens or alkyl radicals, and
• Y is an alkyl or heteroalkyl radical, and
• X is an alkyl, cycloalky, alkylcycloalkyl, heteroalkyl, heterocycloalkyl, heteroalkylcycloalkyl, aryl, heteroaryl, aralkyl or heteroaralkyl radical, a Si (R) _x (OR) _3-x radical with R = an alkyl, cycloalky, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, alkylcycloalkyl, heteroalkyl, heterocycloalkyl, heteroalkylcycloalkyl, aryl, heteroaryl, aralkyl, heteroaralkyl radical and x = 0, 1, 2 or 3, and
• • n is 1, 2 or 3, and
• • p is 1, 2 or 3, and
• • 1 is the luminophore described below.

The term alkyl radical 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 relate in particular to at least partially unsaturated, straight-chain or branched hydrocarbon groups which have 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 radicals refer in particular to saturated or partially unsaturated cyclic groups which have one or more rings, in particular 3 to 14 ring C atoms, particularly preferably 3 to 10 ring C atoms , exhibit. Examples of these are the cyclopropyl, cyclohexyl, tetralin or cyclohex-2-enyl group.

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

The term heterocycloalkyl radical 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 is represented by O, N, P and / or S, and may be, for example, the piperidine or N-phenylpiperazine group.

The term aryl radical refers in particular to an aromatic group which has one or more rings which contain in particular 5 or 6 to 14 ring C atoms, particularly preferably 5 or 6 to 10 ring C atoms. An example of this is a phenyl group.

The term heteroaryl radical 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 denoted by O, N, P and / or S are replaced. An example of this is the pyridyl group.

The terms aralkyl or heteroaralkyl radical relate in particular to groups which, in accordance with the above definitions, have both aryl and / or heteroaryl groups and also alkyl, alkenyl, alkynyl or heteroalkyl groups. Examples arylalkyl, arylalkenyl, arylalkynyl, Arylheteroalkyl-, Arylheteroalkenyl-, Arylheteroalkinyl-, Heteroärylheteroalkyl-, Heteroarylheteroalkenyl-, Heteroarylheteroalkinyl-, Arylcycloalkyl-, Heteroarylcycloalkyl-, Arylheterocycloalkyl, Heteroarylheterocycloalkyl-, Heteroarylcycloalkenyl-, Arylcycloalkenyl-, Arylcycloalkinyl-, 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 refer to groups which contain both cycloalkyl or heterocycloalkyl and also alkyl and / or heteroalkyl groups in accordance with the above definitions.

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 characterized in that it must in any case consist of monomers which can be described by a formula from Table 4 (formula VII-X). The further mixture of the monomers is not prescribed, i. to the monomers of Table 4, monomers may be added to the road marking agent which are described by formulas listed in Table 3 (Formulas I-VI). In addition, the marker mixture may contain several (several) monomers as described in Table 4.

The road marking according to the invention is additionally distinguished by the fact that it may contain inorganic pigments and fillers such as ZnO, BaSO ₄ , MgO, FeO (OH), Fe ₂ O ₃ , Fe ₃ O ₄ and TiO ₂ . Fillers are used for reasons of cost reduction and viscosity reasons in particular embodiments.

In addition, the road marking of the present invention may include curing agents (e.g., 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 can also co-initiators such as UV absorbers and radical scavengers and / or photoinitiators such. Hydroxyalkylketone, 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 characterized in that the agent can be composed of mixtures of additives according to the invention and prefabricated (i.e. also commercially available) paints, high solids dispersions, thermoplastics or road marking reactive systems with structure or without structure.

The road marking according to the invention is characterized in particular by the fact that it uses luminescent luminophores ( 1 ) of rare earth metal and / or of elements of main groups and / or subgroups doped, mixed and pure metal and / or element oxides, silicates, aluminates, gallates, phosphates, germanates, stannates, nitriles, sulphates, fluorides, chlorides, niobates, titanates, zirconates, tungstates, borates as flour, powders or (nano) particles which emit UV, VIS and / or NIR light.

The road marking according to the invention is also characterized in that it comprises mixtures of luminescent luminophores ( 1 ) of rare earth metal and / or of elements of main groups and / or subgroups doped, mixed and pure metal and / or element oxides, silicates, aluminates, gallates, phosphates, germanates, stannates, nitriles, sulphates, fluorides, chlorides, niobates, titanates, zirconates, tungstates, borates of various composition as flour, powder or (nano) particles, which according to the composition of the mixture can emit in total white light ,

The luminophores ( 1 ) are also characterized by being functionalized on the surface of their grains by the formulas VII-X, 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 paint during the Hardening becomes possible.

To illustrate the invention, an embodiment (n = 1, see formula VII-X, p = 3, see formula III-V) of functionalized luminophores according to the invention ( 1 ) shown in the drawings and described in more detail below.

• 1a)-d) eine schematische Darstellung eines Kornes des funktionalisierten Luminophors (1),
• 2 eine schematische Darstellung mehrerer chemisch verknüpfter (Z) und chemisch in das umgebende Harz eingebundener (R') Körner des funktionalisierten Luminophors (1),
• 3 a)-d) eine chemische Darstellung (Strukturformel) der Art und Weise der Verknüpfung (Z) zweier Körner des funktionalisierten Luminophors (1).

Show it:

• 1a) -d ) is 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) -d ) a chemical representation (structural formula) of the way of linking ( Z ) of two grains of the functionalized luminophore ( 1 ).

• 1 a)-d) zeigen schematische Darstellungen eines Kornes des mit Monomeren der Formeln VII-X funktionalisierten (R) Luminophors (1). In diesem Ausführungsbeispiel ist das Korn des Luminophors (1) dabei zuerst mit einer Schicht SiO₂ beschichtet und mittels chemischer Anbindung an zumindest teilweise auf der Oberfläche der SiO₂-Schicht vorhandenen Si-OH-Gruppen durch das Monomer funktionalisiert worden.
• 2 zeigt eine schematische Darstellung mehrerer chemisch verknüpfter und chemisch in das umgebende Harz eingebundener Körner des funktionalisierten Luminophors (1), die jeweils vor der Verknüpfung wie in 1 schematisch dargestellt aufgebaut sind. Die chemische Verknüpfung der Körner (Z) wird dabei in
• 3 besonders verdeutlicht. Schematisch wird die chemische Einbindung der einzelnen Körner in das Harz allgemein durch den Rest R' dargestellt.

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

• 1 a) -d ) are schematic representations of a grain of the functionalized with monomers of formulas VII-X ( R ) Luminophors ( 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 doing in
• 3 especially clear. Schematically, the chemical incorporation of the individual grains into the resin is generally governed by the remainder R ' shown.

In 3 a) -d ) structural formulas 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-VI), 5-100% by weight. functionalized luminophores (of formulas VII-X), 0-10% by weight of photoinitiators and 0-50% by weight 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.

By the road marking means presented herein, the guidance of the road users during the day and at night, and in poor lighting, guaranteed and significantly improved. The composition of the road marking according to the invention thereby ensures application at low temperatures, rapid 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. The photoluminescent pigment is intended to increase night-time visibility. Long-luminescent pigments that emit special wavelengths (UV, VIS, IR) should also increase the detectability (during the day, at night and in bad conditions such as rain and potentially fog and snow) for sensors of special driver assistance systems. The special one Functionalization of the luminophore is intended to ensure 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

Y ₃ Al ₂ Ga ₃ O ₁₂ : Nd ³⁺ , Ce ³⁺ , Cr ³⁺ was ^prepared according to literature specifications (cf. Xu, S. Tanabe, AD Sontakke, J. Ueda, Appl. Phys. Lett. 2015, 107, 081903-1-081903-4 ) produced. 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.

When Y ₃ Al ₂ Ga ₃ O _12: Nd ^3+, Ce ^3+, Cr ³⁺ is a turquoise and an NIR-light-emitting photoluminescent compound.

• Y₃Al₂Ga₃O₁₂:Nd³⁺,Ce³⁺,Cr³⁺ wurde mit Na-Wasserglas behandelt und dadurch die Körner des Pigments von einer Silikat-Schicht umzogen bzw. mit SiO₂ oberflächenbehandelt (abgewandelte Oberflächenbehandlung nach US 3,591,398 ). Anschließend wurde das oberflächenbehandelte Pigment durch Reaktion mit 3-(Trimethoxysilyl)propylmethacrylat in Toluol funktionalisiert (vgl. Van Der Voort, P., Vansant, E. F. J. Liq. Chromatogr. Related Technol. 1996, 19(17&18), 2723-2752 ).

Y ₃ Al ₂ Ga ₃ O ₁₂ : Nd ³⁺ , Ce ³⁺ , Cr ³⁺ was functionalized as follows:

• Y ₃ Al ₂ Ga ₃ O ₁₂ : Nd ³⁺ , Ce ³⁺ , Cr ³⁺ 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 after US 3,591,398 ). Subsequently, the surface-treated pigment was functionalized by reaction with 3- (trimethoxysilyl) propyl methacrylate in toluene (cf. Van Der Voort, P., Vansant, EFJ Liq. Chromatogr. Related Technol. 1996, 19 (17 & 18), 2723-2752 ).

A composition was shown as follows:

• • 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 Y₃Al₂Ga₃O₁₂:Nd³⁺, Ce³⁺, Cr³⁺
• • 1 g (≙ 2.39 mmol) Phenyl-bis(2,4,6-trimethylbenzoyl)phosphanoxid (M = 418.46 g/mol)

A homogeneous mixture of the following composition was produced:

• • 50 g (0.27 mol ≙ 56.50 mL) 2-ethylhexyl acrylate (M = 184.28 g / mol, □ = 0.885 g / mL (25 ° C); T _brew (bp) = 215-219 ° C)
• • 49 g of functionalized Y ₃ Al ₂ Ga ₃ O ₁₂ : Nd ³⁺ , Ce ³⁺ , Cr ³⁺
• 1 g (2.39 mmol) of phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide (M = 418.46 g / mol)

The composition was applied to asphalt 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 bonded monomer of the formulas VII-X

R ':

Polymerized monomers of formulas I-X (resin)

R ¹ :

Variable of the monomer of the formula I.

R ² -R ⁴ :

Variables of the monomer of formulas I and VII

R ^5:

Variable of the monomer of formula II

R ⁶ -R ⁸ :

Variables of the monomer of formulas II and VIII

R ⁹ :

Variable of the monomer of formula III

R ¹⁰ -R ¹³ :

Variables of the monomer of formulas V and X

R ¹⁴ -R ¹⁷ :

Variables of the monomer of Formulas VI

Y:

Variable of the monomer of formulas IV and VII-X

X:

Variable of the monomer of formula IV

x:

variable

m:

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

Z:

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

Quoted non-patent literature

1. 1. Stoye, D., Marwald, B., Plehn, W .: Paints and Coatings, 1st Introduction, Ullmann's Encyclopaedia of Industial Chemistry, 8th edition, Weinheim: Wiley-VCH, 2015 ,
2. Second Vahabi, H., Ferry, L., Longuet, C., Otazaghine, B., Negrell-Guirao, C., David, G., Lopez-Cuesta, J.-M. Mater. Chem. Phys. 2012, 135, 762-770 ,
3. Third 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 :
4. 4th Xu, S. Tanabe, AD Sontakke, J. Ueda, Appl. Phys. Lett. 2015, 107, 081903-1-081903-4 ,
5. 5th Van Der Voort, P., Vansant, EFJ Liq. Chromatogr. Related Technol. 1996, 19 (17 & 18), 2723-2752 ,

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 [0003]
• DE 102004037272 A1 [0003]
• DE 102011113896 A1 [0003]
• US 3591398 [0043]

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, 0047]
• Vahabi, H., Ferry, L., Longuet, C., Otazaghine, B., Negrell-Guirao, C., David, G., Lopez-Cuesta, J.-M. Mater. Chem. Phys. 2012, 135, 762-770 [0004, 0047]
• 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 [0005, 0047]
• Xu, S. Tanabe, A.D. Sontakke, J. Ueda, Appl. Phys. Lett. 2015, 107, 081903-1-081903-4 [0040, 0047]
• Van der Voort, P., Vansant, E.F. J. Liq. Chromatogr. Related Technol. 1996, 19 (17 & 18), 2723-2752 [0043, 0047]

Claims (18)

Roadway marking means, characterized in that the means consists of luminophores described below, thus contributing to enhanced environment perception of vehicles by better visual visibility and visual night visibility. Road marking means according to Claim 1 , characterized in that the binder consists of monomers characterized by the formulas in Table 3 (Formulas I-VI) and Table 4 (Formulas VII-X). Where:

and

with variables which are preferably defined as follows: • the radicals R ¹ -R ¹⁷ are independent of one another, • the radical R ¹ is hydrogen, an alkyl, cycloalky, alkylcycloalkyl, heteroalkyl, heterocycloalkyl, heteroalkylcycloalkyl, aryl , Heteroaryl, aralkyl or heteroaralkyl radical, an Si (R) _x (OR) _3-x radical with R = an alkyl, cycloalky, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, alkylcycloalkyl radical , Heteroalkyl, heterocycloalkyl, heteroalkylcycloalkyl, aryl, heteroaryl, aralkyl, heteroaralkyl radical and x = 0, 1, 2 or 3, and • the radical R ² is hydrogen or an alkyl or heteroalkyl radical, and • the radicals R ³ -R ¹³ are hydrogens or alkyl, cycloalky, alkylcycloalkyl, heteroalkyl, heterocycloalkyl, heteroalkylcycloalkyl, aryl, heteroaryl, aralkyl, heteroaralkyl radicals, and • the radicals R ¹⁴ - R ¹⁷ are hydrogens or alkyl radicals, and Y is an alkyl or heteroalkyl radical, and X is an alkyl, cycloalky, alkylcycloalkyl, heteroalkyl, heterocycloalkyl, heteroalkylcycloalkyl, aryl, heteroaryl, aralkyl or heteroaralkyl radical, an Si ( R) _x (OR) _3-x- radical where R = an alkyl, cycloalky, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, alkylcycloalkyl, heteroalkyl, heterocycloalkyl, heteroalkylcycloalkyl, aryl, heteroaryl , Aralkyl, heteroaralkyl, and x = 0, 1, 2 or 3, and • n is 1, 2 or 3, and • p is 1, 2 or 3, and • 1 is the luminophore described below. Road marking means according to Claims 1 and 2 characterized in that the agent can consist of various compositions of the monomers described by the formulas in Table 3 (Formulas I-VI) and Table 4 (Formulas VII-X), in each case a monomer in the agent must be present, which is described with a formula from Table 4 (formulas VII-X). Road marking means according to one or more of Claims 1 - 3 , characterized in that the agent 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 ), others May contain silicates, Al ₂ O ₃ and / or SiC. Road marking means according to one or more of Claims 1 - 4 , 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 label. Road marking means according to one or more of Claims 1 - 5 , characterized in that the luminophore may consist of a luminescent luminescent substance, wherein the luminescent luminophore of rare earth metal and / or elements of the main and / or subgroups doped, mixed and pure metal and / or element oxides, - silicates, - aluminates, gallates, phosphates, germanates, stannates, nitrides, - sulphides, fluorides, chlorides, niobium, titanates, zirconates, tungstates, - borates, as flour, as powder or as (nano) particles may be present. Road marking means according to one or more of Claims 1 - 6 , characterized in that the luminophore of a UV, VIS and / or NIR light emitting, persistent luminescent or not luminescent luminescent substance can exist. Road marking means according to one or more of Claims 1 - 7 , characterized in that the agent consists of a mixture of photoluminescent luminophores of rare earth metal and / or elements of the main groups and / or subgroups doped, mixed and pure metal and / or element oxides, silicates, aluminates, gallates, phosphates , - germanates, - stannates, -nitrides, -sulfides, -fluorides, -chlorides, -nobium, -titanates, - zirconates, tungstates, -borates may consist of flour, powder or (nano) particles of various composition, which accordingly the composition of the mixture in the sum can emit white light. Road marking means according to one or more of Claims 1 - 8th , characterized in that the luminophore on the surface of its grains is functionalized by Formulas VIII-X (see Table 4), thereby becoming itself a constituent of the binder. Road marking means according to one or more of Claims 1 - 9 , 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, dispersing agents, wetting aids, antifoaming agents, catalysts, drying agents, anti-fogging agents, anti-skinning agents, matting agents, neutralizing agents, thickening agents, preservatives, waxes, wax-water emulsions and paraffins. Road marking means according to one or more of Claims 1 - 10 , characterized in that the agent should contain as few additives and as possible no solvent, but instead reactive liquefier. Road marking means according to one or more of Claims 1 - 11 , characterized in that the agent consists of mixtures of additives according to the invention and ready-made colors, High solids dispersions, thermoplastics or reactive systems may be composed of road marking. Road marking means according to one or more of Claims 1 - 12 , 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-VI), 5-100% by weight of functionalized luminophores (of the formulas VII-X), 0-10 wt .-% of photoinitiators and 0-50 wt .-% of other additives and pigments / fillers. Road marking means 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 agent before application, in special embodiments depending on the latitude and the climatic zone of the place of application can be. Road marking means according to one or more of Claims 1 - 14 , characterized in that the viscosity of the agent before the application, inter alia, by the monomers used, the polymer lengths of the prepolymers and additionally by additives such as plasticizers can be determined. Method of marking a roadway with a means according to Claims 1 - 15 , characterized in that the paint and / or the paint can be cured by UV light. Method of marking a roadway with a means according to Claims 1 - 15 , characterized in that the surface of the coating of the applied agent for road lane marking can be sealed with a paint and, if necessary, a primer to be applied before the agent on the street. Method of marking a roadway with a means according to Claims 1 - 15 , 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.

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