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WO2019016274A1 - Substance luminescente à surface fonctionnalisée, composition et composition durcie la contenant et utilisation correspondante ainsi que procédé pour la fabrication d'un article marqué par luminescence - Google Patents

Substance luminescente à surface fonctionnalisée, composition et composition durcie la contenant et utilisation correspondante ainsi que procédé pour la fabrication d'un article marqué par luminescence Download PDF

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Publication number
WO2019016274A1
WO2019016274A1 PCT/EP2018/069526 EP2018069526W WO2019016274A1 WO 2019016274 A1 WO2019016274 A1 WO 2019016274A1 EP 2018069526 W EP2018069526 W EP 2018069526W WO 2019016274 A1 WO2019016274 A1 WO 2019016274A1
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WIPO (PCT)
Prior art keywords
luminophore
functionalized
composition
radical
particle
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PCT/EP2018/069526
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German (de)
English (en)
Inventor
Janet ARRAS
Stefan BRÄSE
Rainer Reimert
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Individual
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Individual
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Priority claimed from DE102017006841.0A external-priority patent/DE102017006841A1/de
Priority claimed from DE102017006843.7A external-priority patent/DE102017006843A1/de
Priority claimed from DE102017006842.9A external-priority patent/DE102017006842A1/de
Application filed by Individual filed Critical Individual
Publication of WO2019016274A1 publication Critical patent/WO2019016274A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/7774—Aluminates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/22—Luminous paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/62—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing gallium, indium or thallium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7707—Germanates
    • E—FIXED CONSTRUCTIONS
    • E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
    • E01F—ADDITIONAL WORK, SUCH AS EQUIPPING ROADS OR THE CONSTRUCTION OF PLATFORMS, HELICOPTER LANDING STAGES, SIGNS, SNOW FENCES, OR THE LIKE
    • E01F9/00—Arrangement of road signs or traffic signals; Arrangements for enforcing caution
    • E01F9/50—Road surface markings; Kerbs or road edgings, specially adapted for alerting road users
    • E01F9/506—Road surface markings; Kerbs or road edgings, specially adapted for alerting road users characterised by the road surface marking material, e.g. comprising additives for improving friction or reflectivity; Methods of forming, installing or applying markings in, on or to road surfaces

Definitions

  • 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.
  • 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).
  • 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.
  • 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 Rad michs entrysmark isten 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).
  • 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.
  • 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.
  • 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.
  • 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.
  • Photoluminescent materials that emit in the NIR or SWIR range are, for example:
  • SWIR short-wave infrared light
  • NIR near infrared light
  • 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.
  • a specific composition of the paint its macroscopic properties can be influenced.
  • the chosen binder is of crucial importance.
  • 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).
  • Hybrid polymers are enjoying increasing popularity due to their compelling properties.
  • 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).
  • 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.
  • 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.
  • the invention thus likewise provides luminescence coding from photoluminescent luminophores for road traffic and the method according to the invention for application.
  • 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.
  • the control of the vehicle can emit warning signals for the driver's knowledge and, if appropriate, also initiate correction controls of the vehicle.
  • 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.
  • 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.
  • a luminophore particle (1) 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),
  • 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 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.
  • 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,
  • the luminophore particle (1) emits UV, VIS and / or IR light, preferably NIR and / or SWIR light.
  • a sol-gel process precursor preferably Si (OEt) 4
  • 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,
  • Y is an alkylidene or heteroalkylidene group
  • n 1, 2 or 3
  • (1) represents the luminophore particle with silicate layer (2).
  • composition wherein the composition
  • 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
  • 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,
  • Aralkyl or heteroaralkyl radicals are,
  • R 14 to R 17 are each a hydrogen atom or alkyl radical
  • p 1, 2 or 3.
  • 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.
  • 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.
  • composition of claim 12 wherein the composition contains photoinitiators.
  • 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.
  • hardeners preferably dibenzoyl peroxide, accelerators, stabilizers, inhibitors, plasticizers, solvents, waxes, wax-water emulsions and paraffins.
  • 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.
  • 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.
  • composition of claim 12 wherein the composition contains a reactive plasticizer and no solvent.
  • composition according to claim 12 wherein the composition contains no more than a single additive, preferably contains no additive.
  • 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.
  • 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.
  • composition of claim 12 wherein the composition further comprises polymer fibers.
  • composition of claim 12 wherein the composition further comprises paints, high solids dispersions or road marking thermoplastics. 34.
  • the composition co-initiators preferably UV absorbers and radical scavengers and / or photoinitiators, such as.
  • UV absorbers and radical scavengers and / or photoinitiators such as.
  • photoinitiators such as.
  • hydroxyalkyl ketones benzophenones and Acylphosphanoxide contains.
  • composition of claim 12 wherein the composition emits white light.
  • 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
  • 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))
  • 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
  • n 0 or an integer.
  • 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.
  • 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.
  • composition serves as a signal generator for a driver assistance system.
  • 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 ,
  • 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.
  • radical R 2 is hydrogen or an alkyl or heteroalkyl radical
  • 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
  • radicals R 14 -R 17 are hydrogens or alkyl radicals
  • 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
  • n 1, 2 or 3
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • pigments 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,
  • 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 Reaktiwer oiler.
  • 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), Leitleaneden 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.
  • 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.
  • radical R 2 is hydrogen or an alkyl or heteroalkyl radical
  • 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
  • radicals R 14 -R 17 are hydrogens or alkyl radicals
  • 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
  • n 1, 2 or 3
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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,
  • heteroarylheterocycloalkyl heteroarylheterocycloalkenyl, arylcycloalkyl, heteroarylcycloalkyl, arylheterocycloalkyl, heteroarylheterocycloalkyl, heteroarylcycloalkenyl, arylcycloalkenyl, arylcycloalkynyl, heteroarylcycloalkynyl, arylheteroalkenyl, heteroarylheteroalkenyl, arylheteroalkynyl,
  • Heteroaryl heteroalkynyl, heteroarylalkyl, heteroalkenyl and heteroarylalkynyl groups are heteroaryl heteroalkynyl, heteroarylalkyl, heteroalkenyl and heteroarylalkynyl groups.
  • 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.
  • 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.
  • 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 ⁇ i ⁇ 2 . Fillers are used for reasons of cost reduction and viscosity reasons in particular embodiments.
  • 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 ,
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the coating or marking of articles and products for road traffic 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.
  • 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 element
  • 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.
  • 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.
  • 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
  • FIG. 1 show schematic representations of a grain (or particle (1) with silicate layer (2)) of the monomers of the formulas VII-X functionalized (R) luminophore.
  • 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.
  • the chemical incorporation of the individual grains into the resin is generally represented by the radical R '.
  • 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.
  • 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.
  • 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 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.
  • 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.
  • 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.
  • 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.
  • UVKL 4 U For UV curing, a UV lamp designated UVKL 4 U was used by Aug. Hedinger GmbH & Co. KG.
  • Nd 3+, Ce 3+, Cr 3+ is an emitting yellowish and an NIR light photoluminescent compound. was functionalized as follows:
  • composition was shown as follows:
  • composition was applied to asphalt using a hand-held paint roller.
  • composition using a hand-held paint roller was also applied to an article on road safety equipment, e.g. on a guardrail, applied.
  • 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.
  • a UV lamp designated UVKL 4 U was used by Aug. Hedinger GmbH & Co. KG.
  • Light-emitting photoluminescent compound was functionalized as follows:
  • composition was shown as follows:
  • composition was applied to asphalt using a hand-held paint roller.
  • composition using a hand-held paint roller was also applied to an article on road safety equipment, e.g. on a guardrail, applied.
  • 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 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
  • connection group i.e., chemical description of the connection between

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Architecture (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne un agent pour le revêtement d'articles et de produits pour la sécurité dans la circulation routière, un procédé pour la fabrication et des utilisations de celui-ci et sa composition spécifique correspondante ainsi qu'un procédé pour le codage d'équipements routiers, de panneaux signalétiques et d'autres équipements de la circulation routière par un matériau luminescent et pour le marquage multifonctionnel de surfaces de la circulation routière, par exemple d'une bande d'une voie de circulation par un matériau synthétique. La présente invention permet ainsi d'obtenir des performances élevées et une visibilité optique augmentée, en particulier la visibilité nocturne. À cette fin, l'invention concerne une substance luminescente à surface fonctionnalisée présentant une meilleure aptitude à la dispersion.
PCT/EP2018/069526 2017-07-19 2018-07-18 Substance luminescente à surface fonctionnalisée, composition et composition durcie la contenant et utilisation correspondante ainsi que procédé pour la fabrication d'un article marqué par luminescence Ceased WO2019016274A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
DE102017006841.0 2017-07-19
DE102017006841.0A DE102017006841A1 (de) 2017-07-19 2017-07-19 Kodes aus lumineszierenden Materialien für den Straßenverkehr und Verfahren zur Anwendung
DE102017006843.7A DE102017006843A1 (de) 2017-07-19 2017-07-19 Multifunktionale Straßenfahrbahnmarkierung mit großer Performanz und Verfahren zur Anwendung
DE102017006843.7 2017-07-19
DE102017006842.9 2017-07-19
DE102017006842.9A DE102017006842A1 (de) 2017-07-19 2017-07-19 Ausstattungen zur Sicherheit im Straßenverkehr mit großer Performanz und Verfahren zur Anwendung

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