WO2019016274A1 - SURFACE-FUNCTIONALIZED LUMINOPHORUS, COMPOSITION AND CURED COMPOSITION COMPRISING THE SIMILAR AND USE OF THE SAME AND METHOD FOR PRODUCING LUMINESCENCE-MARKED ARTICLE - Google Patents

Abstract

The invention relates to an agent for coating articles and products for safety in road traffic, methods for producing same, and applications of same, and the specific composition of said agent. The invention further relates to a method for coding traffic devices, traffic signs and other road traffic equipment by means of a luminescent material and for the multi-functional marking of road traffic surfaces, such as a strip of a roadway by means of a plastic. The invention achieves good performance and increased optical visibility, in particular night visibility. For this purpose, the invention provides a surface-functionalized luminophore having improved dispersibility.

Description

 SURFACE-FUNCTIONALIZED LUMINOPHORUS, COMPOSITION AND CURED COMPOSITION COMPRISING THE SIMILAR AND USE OF THE SAME AND METHOD FOR PRODUCING LUMINESCENCE-MARKED ARTICLE

Technical field of the invention

 [01] The present invention relates to a surface-functionalized luminophore, a composition and a cured composition comprising the same, the use of the surface-functionalized luminophore and a method for producing a luminescence-labeled article.

[02] Further, the present invention describes a composition and its specific composition, as well as a method for multi-functional marking of paved areas of road traffic with a plastic or for coding of traffic facilities, traffic signs and other street equipment with a luminescent material, which in particular is a composition according to the corresponding points i) to xvi) below and a method according to the corresponding points xvii) to xxii). Furthermore, the present invention relates to articles and products as well as methods for their production and use for road safety, which in particular articles and products according to the following points i) to xvi) and methods for their preparation and use according to the following points xvii ) to xxii).

[03] The language of all appended claims is hereby incorporated by reference.

State of the art

Within the meaning of the Road Traffic Act (§ 43 StVO) are traffic facilities barriers, barrier posts, shut-off devices and guidance devices, which are striped red-white except for delineators, thresholds and guardrails. Thresholds and guardrails have the function of a temporary valid mark and are yellow. Transport facilities are also barriers, parking meters, parking ticket machines, flashing lights and traffic lights and traffic control systems. Shutters for work, damage, accident and other places are without claim to completeness beacons (warning beacons), traffic cones and mobile barriers. Guiding devices are guide posts and directional panels in curves. Guard rails / safety barriers do not count as actual ones However, traffic facilities (or traffic signs) within the meaning of the Highway Code, as a protective device on roads, they should be a field of application according to the invention.

[05] Traffic signs in the sense of the road traffic regulations are (§ 39 StVO) danger signs, regulation signs, directional signs and auxiliary signs. Also (road) markings and Radverkehrsführungsmarkierungen are traffic signs according to the Highway Code. Traffic signs may be attached to a vehicle (they also apply while the vehicle is moving, and then follow the directions of the stationary traffic signs).

[06] A method for the encryption of information or for information storage and information coding is the so-called fluorescence or luminescence coding or marking. This optical coding was first applied in biomedical diagnostics of (bio-) molecules, in microarrays and for high-throughput screening. Some of the earliest and, from our point of view, interesting publications here are:

 - Based on Quantum Dots: M. Han, X. Gao, J.Z. Su, S. Nie, Nat. Biotechnol. 2001, 19, 631-635; Y. Zhu, H. Xu, K. Chen, J. Fu, H. Gu, Chem. Commun. 2014, 50, 14041-14044; Y.-C. Cao, Z. Wang, H.-Q. Wang, J.-H. Wang, X.-F. Hua, X. Jin, L. Yang, Z.-L. Huang, M.-X. Liu, Y.-D. Zhao, J. Nanosci. Nanotechnol. 2009, 9, 1778-1784 and X. Gong, H. Yan, J. Yang, Y. Wu, J. Zhang, Y. Yao, P. Liu, H. Wang, Z. Hu, J. Chang, Anal. Chim. Acta 2016, 939, 84-92.

 Based on organic and organometallic dyes: Z. Zhang, Y. Long, J. Pan, X. Yan, J. Mater. Chem. 2010, 20, 1179-1185; Wang, C. Yang, W. Tan, Nano Lett. 2005, 5, 37-43.

[07] In 2014, new developments in coding by NIR emitters were described (see S. Cho, SC Hong, S. Kim, J. Mater. Chem. C 2014, 2, 450-457 and C. Chen, P. Zhang, G. Gao, D. Gao, Y. Yang, H. Liu, Y. Wang, P. Gong, L. Cai, Adv. Mater. 2014, 26, 6313-6317). Potentially, NIR-emitting quantum dots can be used for NIR encodings for military purposes, for security purposes (eg for identification codes or forgery-proof markings) and for optical data storage (see P. Zijlstra, JWM Chon, M. Gu, Nature 2009, 459, 410-413). be used. Since there are some NIR-transparent materials - eg many pigments are transparent in the range 800-2500 nm (see M. Gargano, F. Cavaliere, D. Viganö, A. Galli, N. Ludwig, Infrared Phys. 81, 128-136.) -, NIR encodings can be safely installed behind them. To the NIR Encoding can also be used optical filters to increase the variety of possible emission coding.

[08] According to DIN 67510-1: 2009-1 1, photoluminescent pigments are pigments which can be excited by UV radiation or visible radiation and then luminesce without further excitation and photoluminescent products, products which are produced using long-luminescent pigments be like Coating materials, films, enamels, polymers and signs, operating elements and paints produced therefrom.

[09] Photoluminescent materials that emit in the NIR or SWIR range are, for example:

1 . )

 (see J. Xu, S. Tanabe, A.D. Sontakke, J. Ueda, Appl. Phys. Lett. 2015, 107, 081903).

2.)

 (See J. Xu, D. Murata, J. Ueda, S. Tanabe, J. Mater Chem C 2016, 4, 1096-1 1 103).

Third

(Z. Pan, Y.-Y. Lu, F. Liu, Nat. Mater. 2012, 11, 58.).

 4.)

 (See, F. Liu, W. Yan, Y.-J. Chuang, Z. Zhen, J. Xie, Z. Pan, Sei Rep., 2013, 3, 1.554; YJ Chuang, Z. Zhen, F. Zhang, F. Liu, JP Mishra, W. Tang, H. Chen, X. Huang, L. Wang, X. Chen, J. Xie, Z. Pan, Theranostics 2014, 4, 11, 12-1, 122).

5.) MAI0 ₃ : Mn ⁴⁺ (M = La, Gd) (λ emission, ca. 730 nm)

 (See Y. Li, Y.Y.Y. Li, K. Sharafudeen, G.P. Dong, S.F. Zhou, Z.J. Ma, M.Y.Peng, J.-R Qiu, J. Mater Chem C 2014, 2, 2019-2027).

 Where the SWIR (i.e. "short-wave infrared light") range is from 0.9 to 1.7 μιτι. The NIR (near infrared light) region is defined in a wavelength range of 700 to 900 nm.

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, solvents and other additives can be important factors influencing the desired properties of a paint (compare Stoye, D., Marwald, B. Plehn, W .: Paints and Coatings, 1st Introduction, Ullmann's Encyclopaedia of Industial Chemistry, 8th edition, Weinheim: Wiley-VCH, 2015).

[11] Kronos has shown improved or further possibilities of better dispersing a pigment: poorly dispersible pigments of 100% ΤiΟ ₂ can be subjected to a surface treatment with colorless oxides of Si, Al or Zr, which should considerably increase the dispersibility ( see WO 2012/130408 A1, DE 10 2004 037 272 A1, DE 10 2011 113 896 A1).

[12] Hybrid polymers are enjoying increasing popularity due to their compelling properties. Thus, e.g. the chemical attachment of silicates to acrylate polymers instead of the physical incorporation (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).

[13] In general, there are two ways of achieving a chemical attachment of silicates to polymers, with a common step, namely the silanol functionalization, is necessary. On the one hand, Si-OH groups of silicates can be functionalized by reaction with functionalized chlorosilanes or functionalized alkoxysilanes and integrated into the carbon-containing polymer network by subsequent subsequent reactions of the functional groups with monomers or prepolymers. If, on the other hand, functionalized alkoxysilanes are used with monomers or prepolymers, these can self-polymerize, thus resulting in e.g. for alkyoxysilane acrylic monomers, a second polymerization reaction takes place 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).

[14] Despite the prior art, there remains a need for improved luminophores for multifunctional marking of paved areas of road traffic or coding of traffic facilities, as well as articles and products for improving road safety. Description of the invention

 [15] The object of the present invention is therefore to provide a surface-functionalized luminophore, a composition, a cured composition and a road marking, each comprising the surface-functionalized luminophore, and the use thereof and methods for producing luminescence-labeled articles ,

 The invention improves road safety by a photoluminescent material. The optical effect of the luminophore is used to better identify a road surface of the road and thus exceeds the usual warning effect of a well-known street pavement marking.

[17] The invention thus likewise provides luminescence coding from photoluminescent luminophores for road traffic and the method according to the invention for application. In particular, road safety is enhanced by the luminescence coding. The optical effect of the luminophore is optically detectable during the day and / or at night. Either the luminescence coding acts as a transmitter for a special driver assistance system or is perceived by the human eye. In the first case, after evaluation of the data of the special driver assistance system, the control of the vehicle can emit warning signals for the driver's knowledge and, if appropriate, also initiate correction controls of the vehicle.

[18] Furthermore, the present invention relates to a means for coating and marking of articles and products for road traffic with high performance and the method according to the invention for application. In particular, the safety in traffic is improved by a photoluminescent material. The optical effect of the luminophore serves both during the day and at night for better recognition of equipment in traffic and thus exceeds the usual warning effect.

[19] The invention provides the following solutions:

 1. Surface-functionalized luminophore, wherein the surface-functionalized luminophore

a luminophore particle (1), a silicate layer (2) on the surface of the luminophore particle (1), and a polymerizable organic radical (R) bonded to the silicate layer (2),

 includes.

 Through the silicate layer (2) and the polymerizable organic radical (R), the surface-functionalized luminophore has excellent dispersibility, especially in paints and varnishes, as well as crosslinkability with other polymerizable substances compared to nonfunctionalized luminophore.

The surface-functionalized luminophore of claim 1, wherein the luminophore particle (1) comprises a luminescent luminophore, preferably a luminophore selected from rare earth metal and / or elements of the main and / or subgroups doped, mixed and pure metal and / or Elemental oxides, silicates, aluminates, gallates, phosphates, germanates, stannates, nitriles, sulfides, fluorides, chlorides, niobdate, titanates, zirconates, tungstates, borates.

Surface functionalized luminophore according to claim 1 or 2, wherein the luminophore particle (1) emits UV, VIS and / or IR light, preferably NIR and / or SWIR light.

The surface-functionalized luminophore according to any one of claims 1 to 3, wherein the luminophore particle (1) is a particle having one of the following molecular formulas:

The surface-functionalized luminophore according to any one of claims 1 to 4, wherein the luminophore particle (1) is a particle having the following molecular formula:

The surface-functionalized luminophore according to any one of claims 1 to 5, wherein the silicate layer (2) is prepared by treating the luminophore particle (1) with Na water glass, preferably with the molecular formula Na 2 SiO 3, or a sol-gel process precursor, preferably Si (OEt) ₄ , so that the luminophore particle is coated / coated with the silicate layer. The surface-functionalized luminophore according to any one of claims 1 to 6, wherein the polymerizable organic group (R) is bonded to the Si-OH group present on the surface of the silicate layer (2).

The surface-functionalized luminophore according to any one of claims 1 to 7, wherein the surface functionalization of the luminophore has a structure selected from the following Formulas VII to X, (wherein in formulas VII to X, the (4-n) -type Si bond -O- silicate layer (2) luminophore particles (1), which represents bonding to the same luminophore particle (1) with silicate layer (2)), preferably from formulas VIII to X.

 wherein in the formulas VII to X

R ² to R ⁴ , R ⁶ to R ⁸ and R ¹¹ to R ¹³ are independent of one another,

R ^{2 is} a hydrogen atom or an alkyl or heteroalkyl radical,

R ³ , R ⁴ , R ⁶ to R ⁸ and R ¹¹ to R ^{13 represent} a hydrogen atom or an alkyl, cycloalkyl,

Alkylcycloalkyl, heteroalkyl, heterocycloalkyl, heteroalkylcycloalkyl, aryl, heteroaryl,

Aralkyl or heteroaralkyl radical,

 Y is an alkylidene or heteroalkylidene group,

 n is 1, 2 or 3, and

 (1) represents the luminophore particle with silicate layer (2).

The surface functionalized luminophore of claim 8, wherein the surface functionalization of the luminophore has more of the structures shown in formulas VII to X.

10. Surface-functionalized luminophore according to claim 8 or 9, wherein in the formulas VII to X n = 1.

The surface-functionalized luminophore according to any one of claims 8 to 10, wherein the surface functionalization of the luminophore has the structure in formula VII wherein n = 1, Y represents a propylene group, R ³ and R ⁴ each represent a hydrogen atom, and R ^{2 represents} a methyl group.

12. Composition, wherein the composition

 0-95% by weight of oligomeric binder resin (s),

 20-60% by weight of monomer (s), in particular represented by one or more of the formulas I to VI,

 5-100% by weight, preferably 5-80% by weight, surface-functionalized luminophore according to one of Claims 1 to 11,

0-10 wt .-% of photoinitiators, and 0-50% by weight of further additives and pigments / fillers;

 where in the formulas I to VI

the radicals R ¹ to R ⁸ and R ¹¹ to R ^{17 are} independent of one another,

R ^{1 represents} a hydrogen atom, an alkyl, cycloalkyl, alkylcycloalkyl, heteroalkyl,

Heterocycloalkyl, heteroalkylcycloalkyl, aryl, heteroaryl, aralkyl or heteroaralkyl radical, or a Si (R) _x (OR) _3-x radical with R = one

 Alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl,

Alkylcycloalkyl, heteroalkyl, heterocycloalkyl, heteroalkylcycloalkyl, aryl, heteroaryl, aralkyl, heteroaralkyl radical, where x = 0, 1, 2 or 3, R ^{2 is} a hydrogen atom or an alkyl or heteroalkyl radical,

R ³ to R ⁸ and R ¹¹ to R ¹³ each represent a hydrogen atom or alkyl, cycloalkyl,

Alkylcycloalkyl, heteroalkyl, heterocycloalkyl, heteroalkylcycloalkyl, aryl, heteroaryl,

Aralkyl or heteroaralkyl radicals are,

R ¹⁴ to R ^{17 are} each a hydrogen atom or alkyl radical,

 Y is an alkylidene or heteroalkylidene group if p = 3,

 Y is a group derived from an alkylidene or heteroalkylidene group by removal of the corresponding number of hydrogen atoms if p = 1 or 2,

X is an alkylene (or alkylidene), cycloalkylene, alkylcycloalkylene, heteroalkylene, heterocycloalkylene, heteroalkylcycloalkylene, arylene, heteroarylene, aralkylene or heteroaralkylene group, a Si (R) _x (OR) 2- _x - R 'is an alkyl, cycloalky, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, alkylcycloalkyl, heteroalkyl, heterocycloalkyl, heteroalkylcycloalkyl, aryl, heteroaryl, aralkyl or heteroaralkyl radical and x = 0, 1 or 2, and

 p is 1, 2 or 3.

13. The composition according to claim 12 or surface-functionalized luminophore according to claim 8, wherein the alkyl radical is a saturated, straight-chain or branched hydrocarbon group containing 1 to 20 C atoms, preferably 1 to 12 C atoms, particularly preferably 1 to 6 C Atoms, is.

14. A composition according to claim 12 or a surface-functionalized luminophore according to claim 8, wherein the alkyl radical is a methyl, ethyl, propyl, isopropyl, isobutyl, t-butyl, n-hexyl, 2,2- Dimethylbutyl or n-octyl group.

15. A composition according to claim 12 or a surface-functionalized luminophore according to claim 8, wherein the alkenyl or alkynyl radical is an at least partially unsaturated, straight-chain or branched hydrocarbon group containing 2 to 20 C atoms, preferably 2 to 12 C atoms, particularly preferably 2 to 5 C atoms, is.

16. The composition of claim 12 or surface functionalized luminophore of claim 8, wherein the alkenyl radical is an ethenyl, allyl, isoprenyl or hex-2-enyl group, and wherein the alkynyl radical is an acetylenyl or propargyl Group is. The composition of claim 12 or the surface-functionalized luminophore of claim 8, wherein the cycloalkyl, cycloalkenyl or cycloalkynyl moiety is a cyclic group having one or more rings, especially 3 to 14 ring C atoms, especially preferably 3 to 10 ring C atoms.

The composition of claim 12 or the surface functionalized luminophore of claim 8, wherein the cycloalkyl radical is a cyclopropyl or cyclohexyl group, and wherein the cycloalkenyl radical is a cyclohex-2-enyl group.

19. A composition according to claim 12 or a surface-functionalized luminophore according to claim 8, wherein the heteroalkyl radical is selected from an alkyl group in which one or more (preferably 1, 2 or 3) C atoms or CH- or CH ₂ - Groups are replaced by O, N, P and / or S is substituted, in particular alkyloxy groups, such as a methoxy or ethoxy group, tertiary amine structures or carbamate groups.

20. The composition of claim 12 or surface-functionalized luminophore of claim 8, wherein the heterocycloalkyl radical is 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, preferably a piperidine or N-phenylpiperazine group.

The composition of claim 12 or the surface functionalized luminophore of claim 8, wherein the aryl moiety is an aromatic group having one or more rings, especially 5 or 6 to 14 ring C atoms, more preferably 5 or 6 to 10 ring C atoms, and in particular a phenyl group.

22. The composition of claim 12 or surface-functionalized luminophore of claim 8, wherein the heteroaryl radical is 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, more preferably a pyridyl group.

23. The composition according to claim 12 or surface-functionalized luminophore according to claim 8, wherein R ² , R ³ and R ^{4 are} 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 other alkyl radicals are. The composition of claim 12, wherein the monomer is 2-ethylhexyl acrylate and the photoinitiator is phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide.

The composition of claim 12, wherein the pigments / fillers are selected from ZnO, BaSO ₄ , MgO, FeO (OH), Fe 2 O 3, Fe 3 O _4, and 2.

26. The composition of claim 12, wherein the composition contains photoinitiators.

27. The composition of claim 12, wherein the composition further comprises one or more of hardeners, preferably dibenzoyl peroxide, accelerators, stabilizers, inhibitors, plasticizers, solvents, waxes, wax-water emulsions and paraffins.

The composition of claim 12, wherein the composition further comprises one or more additives selected from 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.

29. The composition of claim 12, wherein the composition contains a reactive plasticizer and no solvent.

30. A composition according to claim 12, wherein the composition contains no more than a single additive, preferably contains no additive.

31. The composition according to claim 12, wherein the composition contains particles of abrasive materials, preferably selected from SiO ₂ , Al ₂ [(F, OH) 2 SiO ₄ ], Al ₂ SiO ₄ (F, OH) 2, Al 2 Be ₃ (Si ₆ O 8), Al 2 O ₃ and SiC.

32. The composition of claim 12, wherein the composition further comprises polymer fibers.

The composition of claim 12, wherein the composition further comprises paints, high solids dispersions or road marking thermoplastics. 34. The composition of claim 12, wherein the composition co-initiators, preferably UV absorbers and radical scavengers and / or photoinitiators, such as. As hydroxyalkyl ketones, benzophenones and Acylphosphanoxide contains.

35. The composition of claim 12, wherein the composition emits white light.

36. Hardened composition, wherein the cured composition

 a resin and

 a surface-functionalized luminophore comprising

 a luminophore particle (1),

a silicate layer (2) on the surface of the luminophore particle (1), a group (R ^' ) representing a linking group between the silicate layer (2) and the resin, and

 a group (Z), which is a link between the silicate layer (2) of a

Luminophorteilchens (1) and another silicate layer (2) another

Represents luminophore particle (1),

 contains.

37. A cured composition according to claim 36, wherein the linking group (Z) is represented by one of the following formulas (in which the linkage to the resin and the luminophore particle (1) with silicate layer (2) do not belong to the linking group (Z))

wherein in the above formulas R ¹ to R ⁴ , R ⁵ to R ⁸ and R ¹¹ to R ¹³ are independent of one another,

 Y as defined in claim 8

R ¹ to R ⁴ , R ⁵ to R ⁸ and R ¹¹ to R ^{13 are} as defined above, preferably according to claim 8 or 12, defined

 X as defined in claim 12, and

 m is 0 or an integer.

38. The cured composition of claim 36 or 37, wherein R 'is obtained by polymerizing one or more monomers of the above formulas I to VI with the surface-functionalized luminophore.

39. The cured composition of any one of claims 36 to 38, wherein the composition is cured using UV light. 40. Road marking containing the cured composition according to any one of claims 36 to 39.

41. Use of the surface-functionalized luminophore, as defined above, or the composition, also as defined above, for marking, in particular for coating, or for luminescence coding of articles for road use, in particular a roadway.

42. Use according to claim 41 for guiding the road users in poor lighting, preferably at night.

43. Use according to claim 41 or 42, wherein the article for road transport an article selected from a shut-off device for work, damage, accident and other bodies, in particular Leitbacke, traffic cones, mobile bollards, mobile Abperrafeln with flashing arrow, baffles on roads , in particular guide posts, directional boards in curves, protective devices on roads, especially guardrails / crash barriers, is.

44. Use according to one of claims 41 to 43 for the luminescence marking of traffic facilities, traffic signs and other equipment of road traffic; preferably from special construction site markings or to luminescent marking as indicating a desired direction of travel (i.e. to prevent ghost rides).

45. Use according to claim 41 for marking a roadway.

46. Use according to claim 41 for road safety.

47. Use according to claim 41, wherein the composition serves as a signal generator for a driver assistance system.

48. Use according to claim 41, wherein, after evaluation of the data of the driver assistance system, the control of the vehicle emits warning signals for the driver's knowledge and / or initiates correction controls of the vehicle. 49. A method for producing a luminescence-marked article or a road lane marking, comprising applying the composition as defined above, by means of a spray device, by dipping, gluing or rolling on an article on road safety equipment, in particular on a guardrail, or on a roadway ,

50. The method of claim 49, wherein using the sprayer specific patterns are performed.

[20] Furthermore, the invention provides the following further solutions:

 i) means or luminescence coding for road lane marking or for the coating and marking of articles and products for road traffic, characterized in that the means consists of luminophores described below and thus contributes to increased environment perception of vehicles by better optical visibility and optical night visibility guaranteed.

 ii) means or luminescence coding according to i), characterized in that the binder consists of monomers which are represented by the formulas I-VI, and / or of luminophore-bound monomers which are represented by the formulas VII-X. Where:

 with variables that are preferably defined as follows:

• the radicals R ¹ -R ⁸ and R ¹¹ to 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 with R = an alkyl, cycloalky, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, alkylcycloalkyl, heteroalkyl, heterocycloalkyl, heteroalkylcycloalkyl, aryl, heteroaryl, aralkyl or 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 ⁸ and R ¹¹ to R ¹³ are hydrogens or alkyl, cycloalky, alkylcycloalkyl, heteroalkyl, heterocycloalkyl, heteroalkylcycloalkyl, aryl, heteroaryl, aralkyl or heteroaralkyl radicals, and

• the radicals R ¹⁴ -R ¹⁷ are hydrogens or alkyl radicals, and

 Y in the formulas VII to X is an alkylene or heteroalkylene radical and in the formulas III to V as defined in claim 12, and

X is an alkylene, cycloalkylene, alkylcycloalkylene, heteroalkylene, heterocycloalkylene, heteroalkylcycloalkylene, arylene, heteroarylene, aralkylene or heteroaralkylene radical, an Si (R) _x (OR) _3-x radical with R = an alkyl, cycloalky, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, alkylcycloalkyl, heteroalkyl, heterocycloalkyl, heteroalkylcycloalkyl, aryl, heteroaryl, aralkyl or heteroaralkyl radical and x = 0 , 1 or 2, and

 • n is 1, 2 or 3, and

 • p is 1, 2 or 3, and

 (1) The below-described luminophore particle with silicate layer (2).

iii) means or luminescence coding according to i) or ii), characterized in that the agent is constituted by different compositions of the monomers described by the formulas I-VI and / or the luminophore-bound monomers obtained by the In each case, a luminophore-bound monomer must be present in the agent which is described by a formula from formulas VII-X.

iv) Means according to one of i) to iii), characterized in that the agent also abrasive substances such as SiO ₂ , Al ₂ [(F, OH) 2SiO ₄ ], Al ₂ SiO ₄ (F, OH) ₂ , AI ₂ Be ₃ (Si ₆ O ₁₈ ), further silicates, Al ₂ O ₃ and / or SiC may contain.

v) agent according to one of i) to iv), 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. vi) means or luminescence coding according to one of i) to v), 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 groups, and / or subgroups doped , mixed and pure metal and / or elemental oxides, silicates, aluminates, gallates, phosphates, germanates, stannates, nitriles, sulfides, fluorides, chlorides, niobates, titanates, zirconates, tungstenate, borate may be present as flour, powder or (nano) particles.

vii) means according to any one of i) to vi), characterized in that the luminophore of a UV, VIS and / or NIR light emitting, persistent luminescent or not luminescent luminescent substance can exist; Preferably, the composition comprises a mixture of luminophores containing UV emitters, which excites other luminophores, preferably VIS or IR emitters, to emit light; wherein the IR emitters may be useful as transmitters for night vision devices.

viii) means according to one of i) to vii), characterized in that the agent consists of a mixture of luminescent luminophore of rare earth metal and / or elements of the main and / or subordinate groups of doped, mixed and pure metal and / or elemental oxides, Silicates, aluminates, gallates, phosphates, germanates, stannates, nitrides, sulfides, fluorides, chlorides, niobates, titanates, zirconates, tungstates, borates as flour, powder or (nano -) particles of various composition may exist, which according to the composition of the mixture in the sum can emit white light.

ix) means or luminescence coding according to one of i) to viii), characterized in that the luminophore is functionalized on the surface of its grains (or particles) as shown in the formulas VII-X, whereby itself a constituent of the binder become. x) agent according to one of i) to ix), 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-fogging agents, anti-skinning agents, matting agents, neutralizing agents, thickeners, preservatives, waxes, wax-water emulsions and paraffins.

xi) means according to one of i) to x), characterized in that the agent should contain as few additives and as possible no solvent, but instead Reaktiwerflüssiger. xii) agents according to one of i) to xi), characterized in that the agent may be composed of mixtures of additives according to the invention and prefabricated colors, high-solids dispersions, thermoplastics or reactive systems for road marking.

xiii) compositions according to one of i) to xii), characterized in that the agent of at least 0-95 wt .-% oligomeric binder resins (prepolymers), 20-60 wt .-% of monomers (of the formula I-VI), 5 -100 wt .-% of functionalized luminophores (the formulas VII-X), 0-10 wt .-% of photoinitiators and 0-50 wt .-% of other additives and pigments / fillers. xiv) Means according to one of i) to xiii), characterized in that the composition of the agent, i. the amount of photoluminescent 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.

xv) Means according to one of i) to xiv), characterized in that the viscosity of the agent before administration u.a. can be determined by the monomers used, the polymer lengths of the prepolymers and additionally by additives such as plasticizers.

xvi) Means according to one of i) to xv), characterized by the areas of application mentioned below: Shutters for work, damage, accident and other places (beacon, traffic cones, mobile shut-off board, mobile shut-off board with flashing arrow), Leiteinrichtungen on roads (Guide post, directional sign in curves), Road protection (guardrail / guardrail).

xvii) A method for marking a roadway with a means according to i) to xv), characterized in that the paint and / or the paint can be cured by UV light. xviii) A method for marking a roadway with a means according to i) to xv), characterized in that the surface of the coating of the applied means for road lane marking can be sealed with a paint and, if necessary, a primer to be applied before the agent on the street ,

 ixx) A method for marking a roadway with a means according to i) to xv), characterized in that the means for marking road lane can be applied by spraying with a drawing shoe in the extruder process or by gluing or rolling up. xx) A process for coating and marking articles and products for road traffic or for luminescence coding with an agent according to i) to xvi), characterized in that the paint and / or the paint can be cured by UV light. xxi) A method for coating and marking of articles and products for road traffic or for luminescence coding with a means according to i) to xvi), characterized in that the surface of the coating of the applied agent can be sealed with a lacquer and possibly a Primer before the agent according to the invention should be applied to the article or the product of road traffic.

 xxii) A process for coating and marking of articles and products for road traffic or for luminescence coding with a means according to i) to xvi), characterized in that the agent can be applied by spraying, dipping, gluing by rolling or by extruder method.

 The road marking according to the invention or the means as well as the luminescence coding 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 IX are. Where:

 with variables that are preferably defined as follows:

• the radicals R ¹ -R ⁸ and R ¹¹ to 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, or heteroaralkyl radical Remainder 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 ⁸ and R ¹¹ to R ¹³ are hydrogens or alkyl, cycloalky, alkylcycloalkyl, heteroalkyl, heterocycloalkyl, heteroalkylcycloalkyl, aryl, heteroaryl, aralkyl or heteroaralkyl radicals, and

• the radicals R ¹⁴ -R ¹⁷ are hydrogens or alkyl radicals, and

 Y in the formulas VII to X is an alkylidene or heteroalkylidene radical and in the formulas III to V as defined in claim 12, and

X is an alkylene (or alkylidene), cycloalkylene, alkylcycloalkylene, heteroalkylene, heterocycloalkylene, heteroalkylcycloalkylene, arylene, heteroarylene, aralkylene or heteroaralkylene 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 or

2, and

 • n is 1, 2 or 3, and

 • p is 1, 2 or 3, and

(1) The below-described luminophore particle with silicate layer (2). [22] 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.

[23] The terms alkenyl and alkynyl radical refer 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.

[24] The terms cycloalkyl, cycloalkenyl and cycloalkynyl radicals refer in particular to saturated or partially unsaturated cyclic groups which contain one or more rings which in particular have 3 to 14 ring C atoms, more preferably 3 to 10 ring rings. C atoms, have. Examples of these are the cyclopropyl, cyclohexyl, tetralin or cyclohex-2-enyl group.

[25] 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 are represented by O, N, P and / or S are replaced. Examples of these are alkyloxy groups such as methoxy or ethoxy or tertiary amine structures and carbamate groups.

[26] 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 replaced by O, N , P and / or S are replaced, and may be, for example, the piperidine or N-phenylpiperazine group.

[27] 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, more preferably 5 or 6 to 10 ring C atoms , An example of this is a phenyl group. [28] 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 refer in particular to groups which, according to the above definitions, have both aryl and / or heteroaryl groups and also alkyl, alkenyl, alkynyl or heteroalkyl groups. 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, arylcycloalkynyl, heteroarylcycloalkynyl, arylheteroalkenyl, heteroarylheteroalkenyl, arylheteroalkynyl,

Heteroaryl heteroalkynyl, heteroarylalkyl, heteroalkenyl and heteroarylalkynyl groups.

[30] The terms alkylcycloalkyl or heteroalkylcycloalkyl radicals refer to groups which contain both cycloalkyl or heterocycloalkyl and also alkyl and / or heteroalkyl groups in accordance with the above definitions.

[31] 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 or the coating or marking of articles and products as well as the luminescence coding according to the invention are characterized in that they must in any case consist of monomers which can be described by a formula of formulas VII-X. The further mixture of the monomers is not prescribed, ie to the Monomers of formulas VII-X may be added to the road marking agent monomers described by formulas as listed in Formulas I-VI. In addition, the labeling mixture may contain several (several) monomers as described in Formulas VII-X.

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 ΤiΟ ₂ . Fillers are used for reasons of cost reduction and viscosity reasons in particular embodiments.

[34] In addition, the road marking according to the invention or the coating and / or marking of articles and products according to the invention for road traffic may comprise hardeners (eg dibenzoyl peroxide), accelerators, stabilizers and inhibitors, plasticizers, solvents, waxes, wax-water emulsions and paraffins ,

[35] In a particular embodiment, the road marking according to the invention or the coating and / or marking of articles and products according to the invention for road traffic may also contain co-initiators such as UV absorbers and free-radical scavengers and / or photoinitiators such as e.g. Hydroxyalkylketone, benzophenones and Acylphosphanoxide included.

The road marking according to the invention or the coating and / or marking of articles and products according to the invention are additionally distinguished by additives such as leveling agents, flow agents, film-forming accelerators, dispersants, wetting aids, antifoams, catalysts, dryers, antisurface agents , Anti-skinning, matting, neutralizing, thickening and preservative agents.

[37] In a particular embodiment of the road marking according to the invention or the coating and / or marking of articles and products for road traffic according to the invention, as few additives as possible should be used and preferably no solvent, but instead reactive liquefier can be used.

[38] Furthermore, the road marking according to the invention or the coating and / or marking of articles and products according to the invention for road traffic can have particles of all sizes of abrasive materials with a high hardness such as SiO ₂ , Al ₂ [(F, OH) ₂ SiO 4], Al2Si04 (F, OH) 2, Al2Be3 (Si60i8), other silicates, Al2O3 and SiC.

In addition, the road marking according to the invention or the coating and / or marking of articles and products according to the invention for road use in special embodiments additionally polymer fibers of all sizes from homogeneous and / or inhomogeneous thermosets or mixtures of thermosets such as epoxy resins and highly crosslinked polyacrylates Increase in strength, which is to increase the longevity of the mark.

[40] 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., commercially available) paints, high solids dispersions, thermoplastics or road marking reactive systems of structure or structure.

[41] The coating or marking of articles and products for road traffic according to the invention is characterized by the areas of application mentioned below: Shut-off devices for work, damage, accident and other places (beacons, traffic cones, mobile barrier panels, mobile barrier panels with flashing arrows ), Guiding systems on roads (delineators, directional signs in curves), Guards on roads (crash barriers / crash barriers)

The road marking according to the invention or the luminescent coding according to the invention or the coating and / or marking of articles and products according to the invention for road traffic is characterized in Characterized in that they contain photoluminescent luminophores (1) of rare earth metal and / or of elements of the main groups and / or subgroups of doped, mixed and pure metal and / or elemental oxides, silicates, aluminates, gallates, phosphates, -germanate, -stannates, -nitrides, -sulfides, -fluorides, -chlorides, - niobdate, -titanates, -zirconates, -wolframates, -borates as flour, powder or (nano) particles may contain the UV, VIS and / or emit NIR light.

The road marking according to the invention is also characterized by the fact that it mixtures of luminescent luminophores (1) of rare earth metal and / or elements of the main and / or sub-groups doped, mixed and pure metal and / or elemental oxides, silicates , aluminates, gallates, phosphates - germanates, stannates, nitrides, sulfides, fluorides, chlorides, niobates, titanates, zirconates, tungstates, borates of various composition as flour, powder or -) may have particles which can emit white light according to the composition of the mixture in the sum.

[44] In addition, the luminophores (1) according to the invention are characterized in that they are functionalized on the surface of their grains by the formulas VII-X, whereby they themselves become a constituent of the binder and are therefore u.a. an excellent distribution of the luminescent pigments in the paint and / or the paint during curing is possible.

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

[46] A schematic representation of a grain (or particle (1)) of the functionalized luminophore,

2 is a schematic representation of several chemically linked (Z) and chemically bound in the surrounding resin (R ') grains of the functionalized luminophore, 3 a) -d a chemical representation (structural formula) of the manner of

Linkage (Z) of two grains of the functionalized luminophore.

In the drawings, only the elements essential for the immediate understanding of the invention are shown. show schematic representations of a grain (or particle (1) with silicate layer (2)) of the monomers of the formulas VII-X functionalized (R) luminophore. In this exemplary embodiment, the grain of the luminophore (1) is first coated with a layer of SiO ₂ (2) and functionalized by the monomer by means of chemical bonding to Si-OH groups present at least partially on the surface of the SiO ₂ layer (2) Service.

Fig. 2 shows a schematic representation of several chemically linked and chemically bound in the surrounding resin grains (or particles (1)) of the functionalized luminophore, which are each constructed before the linkage as shown schematically in Fig. 1. The chemical linkage of the grains (Z) is particularly illustrated in FIG. 3. Schematically, the chemical incorporation of the individual grains into the resin is generally represented by the radical R '.

In FIG. 3a) -d structural formulas of the chemical linkage (Z) of two grains are obtained

(or the particle (1) of the functionalized luminophore, which are each constructed before the linkage as shown schematically in Fig. 1, and the connection in the resin shown.

The road marking according to the invention or the coating and / or marking of articles and products according to the invention for road traffic 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 formula I-VI), 5-100% by weight of functionalized luminophores (of formulas VII-X), 0-10% by weight of photoinitiators and 0-50% by weight of further additives and pigments / Filler is. [48] Depending on the latitude or climatic zone of the location of application of the composition, the composition of the mixture of the road marking of the invention or the inventive coating and / or marking of articles and products for road traffic may vary, so that in particular embodiments, depending on the relative saturation stimulation Marker may have more or less addition of the luminescent pigment.

The road marking according to the invention or the coating and / or marking of articles and products according to the invention for road traffic can in a particular embodiment be cured by UV light, in which case it must contain photoinitiators.

[50] The road marking and / or marking and / or marking of road traffic products and products presented herein can be used to ensure and significantly improve the guidance of road users during the day and at night, and in poor lighting conditions. The composition of the road marking according to the invention, coding or the coating and / or marking of articles and products according to the invention for road traffic ensures application at low temperatures, rapid drying, few formation fractures and detachments, good color fastness, high resistance to stresses such as impact forces, high scratch and abrasion resistance and thus a long service life. The photoluminescent pigment can increase night-time visibility. Long-luminescent pigments that emit special wavelengths (UV, VIS, IR) can 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 functionalization of the luminophore ensures an excellent distribution of the pigment in the paint and / or the paint.

[51] The luminescent coding of traffic facilities, traffic signs and other features of road traffic with a luminescent material presented herein may guide the operator Road users during the day and / or at night, and in poor lighting, guaranteed and significantly improved. In particular, hazardous situations and hazardous situations such as construction sites can be clearly recognizable for special driver assistance systems and in special execution systems for the human eye, so that appropriate responses to circumvent the hazard and hazard situation can be initiated.

[52] 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.

[53] Embodiment I

Y3Al2Ga30i2: Nd ^3+, Ce ^3+, Cr ³⁺ was (by literature cf. J. Xu, S. Tanabe, AD Sontakke, J. Ueda, Appl Phys Lett 2015, 107, 081903-1-081903-.... 4). 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.

In Y3Al2Ga30i2: Nd ^3+, Ce ^3+, Cr ³⁺ is an emitting yellowish and an NIR light photoluminescent compound. was functionalized as follows:

wurde mit Na-Wasserglas behandelt und dadurch die Körner des Pigments von einer Silikat-Schicht umzogen/überzogen bzw. mit SiO₂ oberflächenbehandelt (abgewandelte Oberflächenbehandlung nach US 3,591 ,398). Anschließend wurde das oberflächenbehandelte Pigment durch Reaktion mit 3- (Trimethoxysilyl)propylmethacrylat funktionalisiert (vgl. Van Der Voort, P., Vansant, E. F. J. Liq. Chromatogr. Related Technol. 1996, 79(17&18), 2723-2752).

was treated with Na water glass and thereby the grains of the pigment of a silicate layer coated / coated or surface-treated with SiO ₂ (modified surface treatment according to US 3,591, 398). Subsequently, the surface-treated pigment was functionalized by reaction with 3- (trimethoxysilyl) propyl methacrylate (see Van Der Voort, P., Vansant, EFJ Liq. Chromatogr. Related Technol., 1996, 79 (17 & 18), 2723-2752).

A composition was shown as follows:

A homogeneous mixture of the following composition was produced:

2-ethylhexyl acrylate (M = 184.28 g / mol, p =

 0.885 g / mL (25 ° C); Tsiede (bp) = 215-219 ° C)

• 49 g functionalized

1 g 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.

In addition, composition using a hand-held paint roller was also applied to an article on road safety equipment, e.g. on a guardrail, applied.

wurde nach Literaturvorschriften (vgl. J. Xu, D. Murata, J. Ueda, S. Tanabe, J. Mater. Chem. C 2016, 4, 1 1096-1 1 103) hergestellt. 2- Ethylhexylacrylat, Phenyl-bis(2,4,6-trimethylbenzoyl)phosphanoxid und 3- (Trimethoxysilyl)propylmethacrylat wurde von Sigma-Aldrich Chemie GmbH bezogen. Zur UV-Härtung wurde eine UV-Lampe mit der Bezeichnung UVKL 4 U von Aug. Hedinger GmbH & Co. KG verwendet. Subsequently, the mixture was cured by UV light. Exemplary embodiment II

was prepared according to literature procedures (see J. Xu, D. Murata, J. Ueda, S. Tanabe, J. Mater Chem C 2016, 4, 1096-1 1 103). 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 it is a yellowish and a SWIR

 Light-emitting photoluminescent compound. was functionalized as follows:

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 funktionalisiert (vgl. Van Der Voort, P., Vansant, E. F. J. Liq. Chromatogr. Related Technol. 1996, 79(17&18), 2723-2752).

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 according to US 3,591, 398). Subsequently, the surface-treated pigment was functionalized by reaction with 3- (trimethoxysilyl) propyl methacrylate (see Van Der Voort, P., Vansant, EFJ Liq. Chromatogr. Related Technol., 1996, 79 (17 & 18), 2723-2752).

A composition was shown as follows:

A homogeneous mixture of the following composition was produced:

^• 50 g (0.27 mol = 5 = 56.50 mL) of 2-ethylhexyl acrylate (M = 184.28 g / mol, p = 0.885 g / mL (25 ° C); Tsiede (bp) = 215-219 ° C)

^• 49g functionalizer

^• 1 g of (± 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.

In addition, the composition using a hand-held paint roller was also applied to an article on road safety equipment, e.g. on a guardrail, applied.

Subsequently, the mixture was cured by UV light. [0001] This application claims priority to the patent applications DE 10 2017 006 843.7, DE 10 2017 006 841.0 and DE 10 2017 006 842.9, which are hereby incorporated by reference in their entirety into a part of the documents of this application.

[55] list of reference numerals

1: photoluminescent luminophore

2: silicate layer

 R: Polymerizable organic radical such as chemically bound monomer represented by the formulas VII-X to the silicate layer (1) silicate layer (2)

 R ': linking group between the silicate layer (2) of a luminophore particle (1) and the resin, such as polymerized monomers of the 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 the formula II

R ⁶ -R ⁸ : variables of the monomer of formulas II and VIII

R ¹¹ -R ¹³ : variables of the monomer of formulas V and X

R ¹⁴ -R ¹⁷ : Variables of the monomer of the formulas VI

 Y: variable of the monomer of formulas IV and VII-X

 X: variable of the monomer of formulas III and IV

x: variable

m: variable of Fig. 3; m = 0, 1, 2, ...

 Z: connection group (i.e., chemical description of the connection between

 2 grains of the luminophore)

Claims

claims 1. Surface-functionalized luminophore wherein the surface-functionalized luminophore  a luminophore particle (1),  a silicate layer (2) on the surface of the luminophore particle (1), and a polymerizable organic radical (R) bonded to the silicate layer (2),  includes. The surface-functionalized luminophore of claim 1, wherein the luminophore particle (1) is a particle having one of the following molecular formulas:

3. The surface-functionalized luminophore according to claim 1 or 2, wherein the silicate layer (2) is prepared by treating the luminophore particle (1) with Na water glass or a sol-gel process precursor, preferably Si (OEt) ₄ the luminophore particle is coated / coated with the silicate layer (2). 4. Surface-functionalized luminophore according to one of claims 1 to 3, wherein the polymerisable organic radical (R) is bonded to the Si-OH groups present on the surface of the silicate layer (2). 5. Surface-functionalized luminophore according to one of claims 1 to 4, wherein the surface functionalization of the luminophore has a structure selected from the following formulas VII to X, preferably from formulas VIII to X.

 wherein in the formulas VII to X R ² to R ⁴ , R ⁶ to R ⁸ and R ¹¹ to R ¹³ are independent of one another, R ^{2 is} a hydrogen atom or an alkyl or heteroalkyl radical, R ³ , R ⁴ , R ⁶ to R ⁸ and R ¹¹ to R ^{13 represent} a hydrogen atom or an alkyl, Cycloalkyl, alkylcycloalkyl, heteroalkyl, heterocycloalkyl, Heteroalkylcycloalkyl, aryl, heteroaryl, aralkyl, or heteroaralkyl radical are, Y is an alkylidene or heteroalkylidene group, n is 1, 2 or 3, and (1) represents the luminophore particle with silicate layer (2). The surface-functionalized luminophore of claim 5, wherein the surface functionalization of the luminophore has more of the structures shown in formulas VII-X. 7. Composition, wherein the composition  0-95% by weight of oligomeric binder resin (s),  20-60% by weight of monomer (s), in particular represented by one or more of the formulas I to VI,  5-100 wt .-% surface-functionalized luminophore after one of Claims 1 to 6,  0-10 wt .-% of photoinitiators, and  0-50% by weight of further additives and pigments / fillers;

V

 where in the formulas I to VI the radicals R ¹ to R ⁸ and R ¹¹ to R ^{17 are} independent of one another, R ^{1 represents} a hydrogen atom, an alkyl, cycloalkyl, alkylcycloalkyl, heteroalkyl, Heterocycloalkyl, heteroalkylcycloalkyl, aryl, heteroaryl, aralkyl or heteroaralkyl Radical, or a Si (R) _x (OR) 3 _-x radical with R = one  Alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl,  Alkylcycloalkyl, heteroalkyl, heterocycloalkyl, heteroalkylcycloalkyl, aryl, Heteroaryl, aralkyl, heteroaralkyl radical, where x = 0, 1, 2 or 3, R ^{2 is} a hydrogen atom or an alkyl or heteroalkyl radical, R ³ to R ⁸ and R ¹¹ to R ^{13 are} each a hydrogen atom or alkyl, cycloalkyl, Alkylcycloalkyl, heteroalkyl, heterocycloalkyl, heteroalkylcycloalkyl, aryl, heteroaryl Are aralkyl, or heteroaralkyl radicals, R ¹⁴ to R ^{17 are} each a hydrogen atom or alkyl radical,  Y is an alkylidene or heteroalkylidene group if p = 3,  Y is a group derived from an alkylidene or heteroalkylidene group by removal of the corresponding number of hydrogen atoms if p = 1 or 2, X is an alkylidene, cycloalkylidene, alkylcycloalkylidene, heteroalkylidene, heterocycloalkylidene, heteroalkylcycloalkylidene, arylidene, heteroarylidene, aralkylidene or heteroaralkylidene group, an Si (R) _x (OR) 2 _-x radical where R = a Alkyl, cycloalky, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, alkylcycloalkyl, heteroalkyl, heterocycloalkyl, heteroalkylcycloalkyl, aryl, heteroaryl, aralkyl, or heteroaralkyl radical and x = 0, 1 or 2 is, and p is 1, 2 or 3. The composition of claim 7, wherein the composition emits white light. A cured composition wherein the cured composition is a resin and  a surface-functionalized luminophore comprising  a luminophore particle (1), a silicate layer (2) on the surface of the luminophore particle (1); a group (R ^' ) which is a linking group between the silicate layer (2) and the resin, and  a group (Z) which represents a link between the silicate layer (2) of a luminophore particle (1) and a further silicate layer (2) of a further luminophore particle (1),  contains. A cured composition according to claim 9, wherein the linking group (Z) is represented by one of the following formulas

wherein in the above formulas R ¹ to R ⁴ , R ⁵ to R ⁸ and R ¹¹ to R ¹³ are independent of one another,  Y as defined in claim 5 R ¹ to R ⁴ , R ⁵ to R ⁸ and R ¹¹ to R ¹³ are defined according to claim 7,  X as defined in claim 7, and  m is 0 or an integer. Road marking containing the cured composition according to one of claims 9 or 10. 12. Use of the surface-functionalized luminophore as defined above for crosslinking with other polymerizable substances. 13. Use of the surface-functionalized luminophore, as defined above, according to claim 12 for marking, in particular for coating, or for luminescence coding of articles for road traffic, in particular a roadway. 14. Use according to claim 12 or 13, wherein the surface-functionalized luminophore serves as a signal generator for a driver assistance system. 15. A method of producing a luminescent-labeled article or a pavement marking, comprising applying the composition as defined above by means of a spraying device, by dipping, gluing or rolling onto an article on road safety equipment, in particular on a guardrail or on a roadway ,