EP4098801A1 - Method of producing multilayer marking elements for marking horizontal and vertical surfaces - Google Patents

Abstract

The present patent application relates to a method for producing a multi-layer floor marking comprising the steps: a. applying at least a first polymer blend to a surface of a solid support to form a base layer,b. applying at least one second polymer mixture to the at least one base layer to produce at least one intermediate layer, andc. Applying at least one third polymer mixture to the at least one intermediate layer to produce a top layer, wherein the at least one first polymer mixture, the at least one second polymer mixture and the at least one third polymer mixture comprise at least one uncured duromer mixture or elastomer mixture and steps a. to c. done by screen printing.

Description

TECHNICAL AREA

The present invention relates to the field of marking vertical, horizontal and inclined surfaces, in particular floor and wall marking.

BACKGROUND OF THE INVENTION

Markings fulfill a number of tasks as colored markings on surfaces. Road or lane markings, for example, are used on the one hand to mark traffic routing and to identify different traffic areas and on the other hand as traffic signs.

According to ÖNORM EN 1436, road markings together with road marking buttons form the horizontal signaling devices on roads. Road markings include longitudinal markings, arrows, transverse markings, text and symbols on the road surface, etc.

Line-like markings can be used to divide up traffic areas and allocate different traffic flows or driving directions. Road markings are an economical and effective method of directing and influencing traffic and fulfill their tasks together with the other traffic control devices on the road. They also contribute to the safety of road users (pedestrians, cyclists, rail traffic). Stationary traffic facilities (e.g. parking areas) are also clearly separated from moving traffic with lane markings. Road traffic structures (e.g. traffic islands) can also be marked accordingly.

Road markings play an important role in warning road users of possible dangers. In addition, lane markings can be an orientation aid for road users.

The coloring of the marking contrasts with the color of the road, which means that the information to be conveyed is sufficiently visible to road users during the day and at night night is guaranteed. Special compositions of the marking materials and the use of special glass beads as drop-on materials in the form of agglomerate markings enable sufficient visibility even in poor visibility (e.g. on wet roads, in tunnels, at dusk and in the dark).

The application of temporary marking elements, in particular road markings, in the construction site area is of great importance in order to ensure safe traffic flow in cramped conditions.

For safety reasons, road markings are subject to a number of international and national STANDARDS in order to guarantee compliance with the requirements. Examples include EN 1790, BS-EN 1871, ASTM-E 1710, BS 3262, DIN EN 1436, ENV 13459, 1-3 and DIN EN 1423/24.

In addition to these primary traffic line markings, the urban environment and also the increasing number of different participants and traffic areas in traffic events increasingly require further markings that are intended to serve as information and orientation aids. For example, traffic areas such as exits, detours, bike paths, sidewalks, meeting zones, quiet zones, playgrounds, bus and taxi lanes, areas for emergency vehicles and restricted zones are marked with marking elements. Chilling zones, blooming streets, flower streets, cooling zones (water mist), schools, kindergartens, hospitals, old people's homes, bus stops, swimming pools, parks, but also storage and production halls, workshops and garages can be marked with marking elements.

In addition to marking a wide variety of traffic areas, the identification of groups of people who use certain traffic areas or are reserved for traffic areas is of great importance in order to ensure their safety. Therefore, traffic areas used or reserved for elderly people, children, the visually impaired (elevated structures), wheelchair users, hikers, visitors, customers or other users are provided with appropriate road markings.

In addition to all these aspects, roads can also be marked with pictograms, trademarks, signposts, lettering, short descriptions, locators, decorations and advertisements.

Such marking elements are also increasingly applied to suitable vertical surfaces such as walls, boundary surfaces and barriers.

Due to the diverse applications and fields of application of floor markings, e.g. road markings, additional requirements such as variety of colors, irregular shapes, small quantities, attention to detail, special resistance to oils (e.g. motor oil), fuels, solvents, hydraulic fluids and ecological aspects must be taken into account in the manufacture and use of road markings .

In addition, road markings should be advantageous in terms of layer thickness (min/max), durability in use (4-6 years), abrasion, reflection, visibility (day/night), UV resistance, water resistance (snow, rain, fog, dew), de-icing agents, Spreading agent, homogeneity (avoid open joints, gaps, cracks), temperature resistance (frost, heat), grip (dry/wet), rollover ability, adhesion to the substrate (paving, concrete, asphalt), ease of application, price, mechanical strength and strength after aging be. Since road markings are sometimes also intended to have a warning effect, they must also be able to be produced with special colors.

The oldest and at the same time cheapest way to apply markings on roads is based on a simple application of paint. Typical applications are: lane separations, road boundaries, strip markings in continuous application using special vehicles. Such markings are usually based on water or solvent-based synthetic resin preparations mixed with pigments, dyes and functional additives (UV protection, reflectors...). Here, acrylates, methacrylates, polyvinyl acetate, alkyd resins, etc. have proven themselves.

In addition to the application of paints such as emulsion paints as road markings, there are other materials that are widespread are used and which include hot spray plastic, hot plastic, cold plastic (including preformed; so-called "Preformed-Cold-Plastic", PCP), preformed thermoplastics, foils and marking buttons.

In the case of road markings with hot spray plastic or hot plastic, thermoplastic resins based on hydrocarbon resins and/or colophony esters, which are provided with pigments, dyes and other additives and are melted at approx. 200°C, are applied to a dry surface. In order to impart reflective properties to the marking, glass beads and the like are usually applied immediately after application. In addition, hot plastic can be introduced into pre-milled depressions on the surface of roads, which can increase the layer thickness and thus the durability. In addition, it is also possible to create an even surface, although the high values for night visibility, especially when wet, cannot be achieved here due to the reduced drainage ability.

Cold plastic is also used for road markings. Preparations made from polymers, dissolved in polymerizable solvents, mixed with suitable fillers, pigments, dyes and additives, are homogeneously mixed with a suitable curing system immediately before application and applied to the prepared surface. The polymer then cures at ambient temperatures (i.e. "in the cold"). During curing, the surface can be sprinkled with reflectors, etc.

Typical polymers that can be used for cold plastic applications include poly-methacrylates, two-part epoxy resin formulations and polyurethanes. Poly-methacrylates, dissolved in mono/or polyfunctional methacrylate monomers with a peroxide amine hardener system, are characterized by high lightfastness, resistance to yellowing and rapid curing (a few minutes). In addition, both thin-layer applications (cold spray plastic) and thick-layer applications (cold plastic) are possible with poly-methacrylates (see e.g DE 199 28 436 ).

Two-component epoxy resin formulations (liquid epoxy resins cured in the presence of polyamines/polyamides at ambient temperature) have the advantage of very good adhesion, adjustable elasticity, high mechanical strength and rapid to medium curing speed.

Polyurethane systems based on oligomers containing hydroxyl and/or amine groups, optionally in liquid, solvent-free form, crosslinked with suitable isocyanates, are characterized by very good adhesion to dry surfaces and are also elastic and abrasion-resistant. Rapid curing occurs during application, whereby the yellowing tendency/resistance depends on the isocyanate used.

Starting with prefabricated thermoplastic marking tapes (typical applications in construction site areas), which are usually self-adhesive, there are also preformed thermoplastic markings such as zebra crossings, mandatory signs, turning arrows, etc. (see U.S. 6,116,814 ). These are usually flamed onto the dried road sections using gas burners. This leads to a temporary softening/liquefaction and, as a result, binding to the soil surface. Multicolored symbols can also be applied in this way by assembling different stamped parts on site and fusing them together by flame treatment and fastening them at the same time. The disadvantage lies in the high processing temperature, the relatively uncontrolled introduction of heat and the associated stress on matrix polymers (embrittlement) and color pigments, the selection of which is made more difficult and limited. The suitable (and usual) hydrocarbon resins are sometimes very brittle (prone to fracture) at ambient temperatures of 0°C to 30°C, so that larger areas of application are only possible with the utmost care, even during transport, but especially under construction site conditions.

However, it has been shown that preformed cold thermoset plastic (PCP) has disadvantages in its manufacture, in contrast to prefabricated thermoplastic pavement markings. The pronounced adhesive properties of such Systems require complex molds, usually based on elastic silicones, with a short service life, which is known to those skilled in the art. 2-component systems, such as in the EP 0 493 733 described, place high demands on the mixing systems due to their generally short pot lives: either continuous discharge or recurring cleaning costs. In addition, multicolored applications are only possible to a limited extent.

It is therefore an object of the present invention to provide a method for the production of multi-layer marking elements, in particular road markings, which allows production independent of shape, a layer thickness of 100 to 3000 μm, no limitation in terms of coloring/color combination, possibility of combination in the functional layer structure, freedom from raw materials and possible combinations of different raw materials in road markings, for example.

SUMMARY OF THE INVENTION

1. a. Auftragen mindestens einer ersten Polymermischung auf eine Oberfläche eines festen Trägers zur Herstellung einer Grundschicht,
2. b. Auftragen mindestens einer zweiten Polymermischung auf die mindestens eine Grundschicht zur Herstellung mindestens einer Zwischenschicht, und
3. c. Auftragen mindestens einer dritten Polymermischung auf die mindestens eine Zwischenschicht zur Herstellung einer Deckschicht, wobei
   die mindestens eine erste Polymermischung, die mindestens eine zweite Polymermischung und die mindestens eine dritte Polymermischung mindestens ein ungehärtetes Duromergemisch oder Elastomergemisch umfasst und die Schritte a. bis c. mittels Siebdruck erfolgen.

The present invention relates to a method for producing a multilayer marking element, comprising the steps:

1. a. applying at least a first polymer blend to a surface of a solid support to form a base layer,
2. b. applying at least one second polymer mixture to the at least one base layer to produce at least one intermediate layer, and
3. c. Applying at least one third polymer mixture to the at least one intermediate layer to produce a top layer, wherein
   the at least one first polymer mixture, the at least one second polymer mixture and the at least one third polymer mixture comprises at least one uncured duromer mixture or elastomer mixture and steps a. to c. done by screen printing.

Surprisingly, it has been shown that multi-layer marking elements can be produced by using screen printing can be produced, which have the advantages mentioned above. In addition, it was shown that screen printing processes can also be carried out with curable polymers.

The use of screen printing methods for the production of marking elements also has the advantage that this method can enormously expand the design freedom for marking elements such as road markings. As a result, it is now possible to produce marking elements which can be graphically designed freely and which can have different material properties.

In addition, by using the screen printing process and the associated layered production of the marking elements according to the invention, defined functions (e.g. increased retroreflective properties, abrasion resistance) can be assigned to individual layers, which result in an otherwise unattainable overall structure.

Accordingly, a further aspect of the present invention relates to a multi-layer marking element, in particular a multi-layer road marking, which can be produced using a method according to the invention.

The marking element produced using the method according to the invention can be attached to a surface in different ways. Accordingly, a still further aspect of the present invention relates to a method for applying a marking element according to the invention to a surface, preferably to a substantially horizontal or substantially vertical surface, comprising the step of mechanically attaching or chemically adhering the marking element to the surface, wherein the mechanical fastening is effected by at least one nail, at least one rivet and/or at least one screw and the chemical attachment is effected by at least one adhesive adhesive, at least one hot-melt adhesive and/or at least one pressure-sensitive adhesive.

DESCRIPTION OF THE EMBODIMENTS

A marking element within the meaning of the present invention includes any type of marking that is suitable on a to be mounted on a horizontal, vertical or inclined surface. The marking element according to the invention can be designed as a reference, information or guide element. The marking element is particularly preferably designed as a floor marking or as a floor marking element that is attached to traffic areas, in particular for restricted areas, parking areas, disabled parking areas, bus stops, cycle paths, directional arrows and traffic signs (e.g. speed limits, marking of level crossings). In addition, marking elements can also include pictograms, trademarks, signposts, labels, short descriptions, search instructions, decorations and advertising.

Screen printing is a printing process in which inks can be printed through a fine-meshed fabric onto the material to be printed using a rubber squeegee. In those areas of the fabric where no color is to be printed in accordance with the printed image, the mesh openings of the fabric are made color-impermeable using a stencil.

Surprisingly, it has been shown that screen printing processes can also be carried out with curable polymers. For this purpose, instead of the printing ink usually used in screen printing, at least one polymer mixture based on duromer or elastomer, preferably on a duromer basis, is applied (stacked) to a surface in relatively thick layers before it is cured/crosslinked. This makes it possible to produce multi-layer marking elements, the layers preferably being applied to a non-adhesive release liner for isolating the "print layers per se" after they have cured.

With the method according to the invention it is possible to produce multi-layer marking elements. In this case, at least one first polymer mixture is first applied as a base layer to the surface of a solid carrier with the aid of the screen printing process. The base layer is that part of the marking element according to the invention which is in direct or indirect contact via an adhesive layer with the surface to which the element is applied (eg road or traffic surface in the case of road markings). On the base layer at least one intermediate layer is applied using the screen printing process. The intermediate layer comprises at least one second polymer blend. Finally, a top layer is applied to the intermediate layer applied last, which is also done using the screen printing process. Thus, the multilayer marking element produced using the method according to the invention has a base layer, at least one intermediate layer and a top layer.

As mentioned above, the marking elements that can be produced using the method according to the invention can include different colors, patterns or other characters. These are produced in that the individual polymer mixtures of the base, intermediate and/or top layer are colored/pigmented differently and appropriate templates are optionally used in the course of the screen printing. Stencils prevent a polymer mixture from being applied to hidden areas during the screen printing process.

In order to avoid intermediate cleaning of the screens or to keep the corresponding cleaning effort low, it is advantageous to use polymer mixtures that have the longest possible pot lives (e.g. 15 minutes to 2 hours, 30 minutes to 1.5 hours or 45 to 60 minutes).

The layers are preferably cured at least partially, preferably completely, after they have been applied to the solid support or the previous layer. Depending on the composition of the polymer mixture applied, curing takes place chemically (by adding compounds that lead to crosslinking of the polymer) and/or physically (e.g. UV and/or IR radiation). The intermediate curing of the individual layers should take place as quickly as possible (e.g. 1 to 30 minutes, 1 to 20 minutes or 2 to 15 minutes) in order to increase productivity to an economical level.

Depending on the polymer mixture used, the individual layers can be cured using two different curing mechanisms. This makes it possible for individual layers, for example in the course of an intermediate curing, ie curing after the application of a layer, more quickly and die Final curing of the entire multi-layer marking element can take place later in the production. In such a case, the intermediate curing is reduced to the minimum level that allows another print job, but the final curing is reserved for the entire composite. Suitable curing mechanisms include thermally sensitive (IR-affine) and radiation-sensitive systems (eg UV radiation) for rapid intermediate curing. For example, it is possible to carry out intermediate UV curing of thin, in particular transparent layers, and then to subject the overall composite, ie the multilayer marking element, to thermal final curing.

Partial cross-linking of the layers can be sufficient to enable short-term and rapid "stacking" of further layers. Secondary crosslinkers that can be initiated thermally (e.g. peroxides) have proven their worth in particular, in order to ultimately subsequently harden the entire stack.

Surprisingly, it was found that crosslinking of the polymer layers, which is insufficient per se during the process according to the invention, leads to an excellent end product due to end crosslinking in the overall stack.

The marking elements produced using the method according to the invention can be applied to surfaces (vertical or horizontal) or fastened to them using different means and methods. The simplest way of attaching the marking elements according to the invention to a surface is by mechanical methods such as hanging them up using nails, rivets or screws, for example. Alternatively, adhesives such as dispersions, hot-melt adhesives (hot bitumen or synthetic polymers such as polyamides, ethylene-vinyl acetate copolymers, polyvinyl acetate or butadiene polymers) and/or pressure-sensitive adhesives can be used.

A polymer which is essentially identical to that of the base layer can preferably also be used to attach the marking elements, with epoxy resins, polymethyl methacrylates and polyurethanes (preferably as a rapidly curing 2-component material) being particularly preferably used. The polymers to attach can with functional silanes, for covalent binding to siliceous materials (such as paving, concrete surfaces, but also siliceous fillers in asphalt pavements, especially on aged asphalt surfaces).

Accordingly, a further aspect of the present invention relates to a method for applying a marking element according to the invention to a surface, preferably to a substantially horizontal or substantially vertical surface, comprising the step of mechanically attaching or chemically adhering the marking element to the surface, the mechanical Fastening by means of at least one nail, at least one rivet and/or at least one screw and chemical adhesion by means of at least one adhesion adhesive, at least one hot-melt adhesive and/or at least one pressure-sensitive adhesive. One advantage of screen printing is that the different fabric finenesses (thread count: threads/cm), the application quantity of the polymer mixture (determined as Vth cm ³ /m ² = theoretical paint volume) can be varied. The lower the number of threads n (n/cm), the greater the free passage (degree of openness DC) and thus the theoretical application volume.

According to a preferred embodiment of the present invention, the screen printing is carried out with a screen which has a thread count between 5 and 50, preferably between 8 and 40, even more preferably between 8 and 24, even more preferably between 12 and 24, even more preferably between 18 and 21.0 per centimeter with a preferred yarn diameter of 50 to 300 µm, preferably 90 to 200 µm.

According to a further preferred embodiment of the present invention, the screen printing is carried out with a screen which has an ink volume of 10 to 1000 cm ³ /m ² , preferably 50 to 170 cm ³ /m ² .

With the method according to the invention it is possible to produce layers based on uncured duromer mixtures or elastomer mixtures. According to a particularly preferred embodiment of the present invention, the base layer, the at least one intermediate layer and the top layer are each coated with a layer thickness of 10 to 1000 μm, preferably from 15 to 500 µm, more preferably from 20 to 250 µm.

The thickness of the layers preferably refers to the dry layer thickness, i.e. the thickness after curing of the respective polymer.

According to a preferred embodiment of the present invention, the top layer, i.e. the finally applied polymer layer, has a layer thickness of 50 to 300 μm, preferably 80 to 150 μm, more preferably 100 to 120 μm, or a layer thickness of 10 to 50 microns, preferably from 10 to 20 microns applied.

According to a further preferred embodiment of the present invention, the multilayer marking element has a total layer thickness of 100 to 3000 μm, preferably 200 to 3000 μm, even more preferably 500 to 3000 μm.

In order to produce the marking element according to the invention, at least three layers (a base layer, an intermediate layer and a top layer) are required in order to achieve a specific total layer thickness on the one hand and to obtain marking elements with preferably different functional properties on the other. The polymer mixtures for producing the individual layers or the uncured duromer or elastomer mixture contained therein can have an identical or different composition. This allows layers to be produced that either consist of an identical material or comprise different materials.

The method according to the invention for producing multi-layer marking elements is preferably not carried out directly on a surface, such as a street or traffic area, but ideally at a location which allows continuous production of marking elements. This makes it possible to provide a transportable and storable end product after the curing/crosslinking of the polymer mixtures applied in layers. The base layer of the marking element according to the invention is applied to a solid support.

According to a particularly preferred embodiment of the present invention, the solid support is a planar support comprising a film, preferably a plastic film, paper, metal, ceramic or glass, with metal, ceramic and glass plates being particularly preferred.

In order to detach the end product from the surface of the solid support, the at least one first polymer mixture for producing the base layer is applied to a separating layer or separating film, or the surface of the solid support is provided with a separating agent. Thus, according to a preferred embodiment of the present invention, prior to step a. a release agent, a release layer or a release film is applied.

A release film can be siliconized paper, for example, as is also used in the baked goods industry. But also release films with integrated release properties, as is the case with polytetrafluoroethylene (PTFE), for example.

The separating layer itself can become an integral part of the multilayer marking according to the invention. For example, a polymer-based fleece could be used as the separating layer, which can contribute to improved adhesion or mechanical stabilization of the marking element.

Alternatively, if metal, ceramic and glass plates are used as solid carriers, they can be designed to be heatable. This can be of advantage on the one hand when curing the polymer mixtures and when detaching the marking element produced from the solid support. If appropriate, the surface of the solid support can additionally be provided with a suitable release agent.

The polymer mixtures used according to the invention should have a specific viscosity in order to have sufficient stability when applied with a specific amount. Without this stability, the polymer mixtures would run out on the surface of a carrier. Therefore, the at least one first polymer mixture, the at least one second polymer mixture and the at least one third polymer mixture preferably have a viscosity of 1000 to 10000 mPa.s, preferably 3000 to 8000 mPa.s, at 25°C. Such viscosities in Combination with sufficient thixotropy and high-solids materials (ideally 100% solvent-free) allows a corresponding ink volume application of 100 - 250 µm dry film thickness per print pass, for example.

In order to adjust the viscosity, rheological additives can be added to the polymer mixtures. These are preferably selected from the group consisting of bentonites, amorphous silicic acids, polymeric thickeners and soya lecithins.

According to a particularly preferred embodiment of the present invention, the at least one uncured thermoset mixture or elastomer mixture comprises at least one reactive resin, at least one hardener and at least one filler.

According to a further preferred embodiment of the present invention, the at least one reactive resin is selected from the group consisting of acrylic resins, epoxy resins, polyol resins, polyurea resins, polysiloxane resins and combinations thereof.

The acrylic resin preferably includes (meth)acrylates such as methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, hydroxyethyl (meth)acrylate, stearyl (meth)acrylate, benzyl (meth)acrylate or lauryl (meth)acrylate and as a crosslinking agent Ally(meth)acrylates, di- or tri(meth)acrylates such as 1,4-butanediol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate or trimethylolpropane tri(meth)acrylate.

According to yet another preferred embodiment of the present invention, the uncured polymer mixture comprising the acrylic resin comprises a curing agent selected from the group consisting of peroxides, azo compounds, preferably azobisisobuthydronitrile (AIBN), persulfates, preferably potassium persulfate, curing catalysts and photoinitiators.

Preferably, the curing agent is a peroxide selected from the group consisting of dibenzoyl peroxide, lauroyl peroxide, methyl isobutyl ketone peroxide, di(4-tert-butylcyclohexyl) peroxydicarbonate), tert-butyl peroctoate, di(tert-)amyl peroxide and butyl peroxybenzoate.

Preferably the curing catalyst is an amine selected from the group consisting of N,N-dimethyl-p-toluidine, N,N-bis-2-(hydroxyethyl)-p-toluidine and N,N-bis-(2-hydroxypropyl)- p-toluidine.

The epoxy resin is preferably selected from the group of liquid glycidyl ethers of bisphenols or phenol/formaldehyde condensates, optionally in a mixture with low-molecular solid epoxy resins of comparable bases, consisting in particular of bisphenol A glycidyl ethers.

According to a preferred embodiment of the present invention, the uncured polymer mixture comprising the epoxy resin comprises a curing agent selected from the group consisting of aliphatic amines, tertiary amines, amidoamines, imidazoles, dicyandiamide, guanidines and photoinitiators.

According to a further preferred embodiment of the present invention, the uncured polymer mixture comprising the polyol resin and/or the polyurea resin comprises a curing agent selected from the group consisting of di- or polyisocyanates, optionally adducts thereof with oximes, dialkyl malonic esters or pyrazoles, trimeric isocyanates, tertiary amines, tin alkyls , aliphatic secondary diamines and polyamines.

According to yet another preferred embodiment of the present invention, the uncured polymer mixture comprising the polysiloxane resin comprises a curing agent selected from the group consisting of dialkyl peroxides, alkylaryl peroxides and aromatic diacyl peroxides.

According to a preferred embodiment of the present invention, the at least one filler is selected from the group consisting of calcium carbonate, barium sulfate, quartz, precipitated or pyrogenic silica, cristobalite, corundum and aluminum silicate.

The polymer mixtures used according to the invention can comprise solvents, in which case, in particular, polymer mixtures with epoxy resins, polyol resins and polyureas can additionally comprise solvents. Preferred solvents are C ₁ -C ₄ alkyl acetates and alkyl glycol acetates.

According to a particularly preferred embodiment of the present invention, the at least one first polymer mixture, the at least one second polymer mixture and/or the at least one third polymer mixture comprises at least one color pigment, metal particles, glass beads and/or at least one sensor for detecting and/or transmitting data.

The individual layers of the multilayer marking element can fulfill different functions. Depending on the function, the polymer mixtures can include different components. For informational, warning and visibility purposes, the polymer blends may include colored pigments. In order to improve the reflection properties of marking elements, the polymer mixtures can include metal particles and/or glass beads. If the marking element is used to interact with electronic devices such as measuring instruments or navigation systems, the polymer mixtures can include metal particles and sensors.

Polymer mixtures comprising color pigments and/or metal particles, which can be used to produce the base, intermediate and top layers and are UV-curing, preferably have a layer thickness of less than 100 μm, preferably less than 50 μm. Pigments or particles contained in the polymer mixture can absorb some of the UV rays that are necessary for curing. The reactive radiation penetrates more easily and deeply into non-pigmented layers, so that these can be crosslinked without any problems. The pigments in a paint layer, for example, scatter and/or absorb a significant part of the UV radiation, so that the thicker the layer, the less radiation can penetrate to the bottom. In extreme cases, the radiation and thus its effect does not reach the critical interface of the matrix. An uncured layer in this sensitive area may result in insufficient adhesion. In order to be able to cure paints with a high pigment concentration, a critical layer thickness should not be exceeded.

The color pigments used in the polymer mixtures according to the invention are preferably selected from the group consisting of TiO ₂ , FeO(OH), Fe ₂ O ₃ , Cu phthalocyanine, preferably halogenated Cu phthalocyanine, carbon black, diketopyrrolopyrrole (DPP), quinophthalone yellow, bismuth vanadate (BiVO ₄ ), isoindoline, benzimidazolone, (Ti,Cr, Sb)O ₂ , quinacridone and dioxazines .

Metal particles that can be used in the polymer mixtures according to the invention serve to reflect light in the marking element and preferably include aluminum, copper or brass. The particles can have a wide variety of shapes, such as the shape of metal flakes. The size of the metal particles or metal flakes is preferably 5 to 50 μm.

Glass beads can be added to the polymer mixture as preferred reflection agents. The glass beads used are preferably introduced into the polymer mixture before screen printing (premix beads) and have a diameter of 50 to 1000 μm, more preferably 100 to 850 μm. As an alternative to this, the glass beads can be scattered (drop-on glass beads) after application by screen printing onto the applied layer which has not yet hardened, preferably the top layer. Such glass beads preferably have a diameter of 50 to 1700 μm, preferably 100 to 1400 μm.

According to a further preferred embodiment of the present invention, the at least one third polymer mixture comprises fluoropolymers, preferably polytetrafluoroethylene, functional pigments such as thermochromic pigments, hydrochromic pigments, fluorescent pigments, luminescent pigments and/or ferromagnetic pigments.

According to a preferred embodiment of the present invention, after the top layer has been applied, its surface is structured.

The top layer of the marking element according to the invention can be structured on the surface. The surface structures can, for example, be produced mechanically or using templates. The surface structuring can contribute to better orientation for the visually impaired or improve the optical impression of the marking.

According to a particularly preferred embodiment of the present invention, the base layer, the at least one Intermediate layer and the top layer, preferably independently of one another, cured by supplying heat and/or by UV radiation.

A further aspect of the present invention relates to a multilayer marking element that can be produced using a method according to the invention.

EXAMPLES Example 1: Formulation of a methacrylate-based printing ink

Component A PMMA binder 20-35 parts by weight MMA crosslinker 0.5-2 parts by weight acrylate monomers 5-15 parts by weight color pigment 1-7 parts by weight filler 25-60 parts by weight Reflex/glass beads 0-15 parts by weight Additives (rheology) 1-3 parts by weight curing catalyst (amine) 0.2-0.5 parts by weight

Component A was mixed with a peroxide hardener (component B) in the ratio A:B 99.5:0.5 to 98:2. The viscosity of the mixture was 5800-6800 mPa.s. The pot life was 15-45 min.

PMMA binders used were Degaroute 465, Degaroute 650, Degaroute 622, Domacryl 935, Domacryl 992 and Degaroute 941.

MMA crosslinkers used were polyfunctional (meth)acrylates such as ally(meth)acrylates, di- or tri(meth)acrylates such as 1,4-butanediol di(meth)acrylates, tetraethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylates, trimethylolpropane tri(meth )acrylates.

As acrylate monomers, (meth)acrylates such as methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, hydroxyethyl (meth)acrylate, stearyl (meth)acrylate, benzyl (meth)acrylate and lauryl (meth)acrylate were used.

Calcium carbonate (Calplex 5, Omyacarb 5, Omyacarb 40), barium sulphate, quartz, ground quartz, precipitated and pyrogenic silica and cristobalite (Sibelite M06, Sibelite M72) were used as fillers. Quartz, cristobalite corundum and aluminum silicate were used as coarse fillers.

Swarco reflex beads of different grain sizes, e.g. Swarcoflex or Solidplus beads, white core beads were used as reflex/glass beads.

Bentone SD1, Bentone SD2, Antiterra 204, soya lecithin, Disperbyk 164 and Aerosil were used as rheological additives.

Amine catalysts were substituted amines such as in particular N,N-dimethyl-p-toluidine, N,N-bis-2-(hydroxyethyl)-p-toluidine or N,N-bis-(2-hydroxypropyl)-p-toluidine, Perkaquick A 150 or PTE.

Kronos 2310 (TiO ₂ ), Bayferrox 3910 LV (FeO(OH)), Bayferrox 132M (Fe ₂ O ₃ ), Heliogen Green L8730 (Cu phthalocyanine, halogenated), Special Black 100 (soot), Heliogen Blue L7101F (Cu Phtalocyanine), Irgazin Red 2030 (DPP), Irgacolor Yellow 3GLM (Chinophthalone Yellow), Paliotol Yellow L 0968 HD (BiVO ₄ ), Paliotol Yellow 2140-HD (Isoindoline), Novoperm Orange HL 70-NF (Benzimidazolone), Irgacolor Yellow 10406 ((Ti, Cr, Sb)O ₂ ), Hostaperm Red Violet ER02 (quinacridone), Hostaperm Violet RL Special TS (dioxazine) and Hostaperm Rosa E-TS (quinacridone) are added to the polymer mixture.

Dibenzoyl peroxide, lauroyl peroxide, methyl isobutyl ketone peroxide, di(4-tert.butylcyclohexyl peroxydicarbonate), tert.butyl peroctoate, di(tert.)amyl peroxide and butyl peroxybenzoate were used as peroxides with different pot lives or thermal activation.

Example 2: Formulation of a printing ink with epoxy resin

Component A Liquid epoxy resin 5-10 parts by weight Solid epoxy resin 5-10 parts by weight solvent 15-25 parts by weight color pigments 1-7 parts by weight filler 30-60 parts by weight Reflex/glass beads 0-10 parts by weight Additives (rheology) 1-3 parts by weight

Component A was mixed with a polyamine as hardener (component B) in the ratio A:B 10:0.7 to 10:1.5. The viscosity of the mixture was 5600-7200 mPa.s. The pot life was 30-120 min.

Bisphenol A glycidyl ether, such as Rütapox, Araldit GY250, Epidon, Kalopox, Epikote 828 or 1001 or Olin DER 916, was used as the epoxy resin.

Solvents used were C ₁ -C ₄ alkyl acetates and alkyl glycol acetates.

It was found that suitable amine hardeners are Beckopox VEH 2133, VEH 2177, Araldit HY 516, Epidiant and Epilox.

The other substances listed in Example 2 can be found in Example 1.

Example 3: Formulation of a printing ink with polyurethane

Component A polyol resin 15-35 parts by weight solvent 10-25 parts by weight color pigments 1-7 parts by weight filler 25-35 parts by weight Reflex/glass beads 0-10 parts by weight Additives (rheology) 1-3 parts by weight

Component A was mixed with an isocyanate hardener (component B) in a ratio of A:B from 4:1 to 10:1. The viscosity of the mixture was 6500-7500 mPa.s. The pot life was 240-360 min.

Domacryl 545 50 BAc and polyester resin type 670/80 were used as the polyol resin.

Isocyanate Desmodur Ultra N 3600 proved to be particularly suitable in this formulation.

Example 4: Formulation of a printing ink with polyurea

Component A aspartic acid ester 20-30 parts by weight solvent 10-20 parts by weight color pigments 1-7 parts by weight filler 25-35 parts by weight Reflex/glass beads 0-10 parts by weight Additives (rheology) 1-3 parts by weight light stabilizers 1-3 parts by weight

Component A was mixed with an isocyanate hardener (component B) in a ratio of A:B 3:1 to 2:1. The viscosity of the mixture was 3800-5200 mPa.s. The pot life was 20-60 min.

Desmophen NH 1423 was used as the aspartic acid ester.

Light stabilizers were trialkyl phosphites, HALS, benzotriazoles, hindered amines, Tinuvin 1130 and Tinuvin 292.

Example 5: Production of a multi-layer floor marking

The polymer mixtures mentioned in Examples 1 to 4 can be used to produce a wide variety of multilayer floor markings.

For example production of a mandatory sign for "cycle path" first a 150 μm thick base layer with the formulation from Example 1 (blue color pigment, no reflective beads) was applied to a solid support using a sieve (21 thread count). After applying this base layer, the polymer was (intermediate) cured thermally at 80°C for 60-90 seconds. After the base coat had cured, the same composition was applied a second time as an intermediate coat to the base coat in the same manner. After a further thermal intermediate curing, a second intermediate layer with the formulation according to Example 1 comprising reflective beads was applied and thermally cured. The third intermediate layer (formulation according to Example 1, white) was in the form of a Bicycle applied to the second intermediate layer and again thermally hardened. The final top layer comprising the formulation according to Example 1 (without pigments and without filler) was applied to the third intermediate layer in a layer thickness of 100 μm using a screen (21 thread count). Before the final thermal curing, the uncured top layer was sprinkled evenly with reflective beads.

In addition to the color pigments and/or glass or reflective beads, sensors such as RFID sensors or luminescent pigments were also incorporated into the individual layers, with sensors preferably being incorporated into an intermediate layer.

In the surface layers (e.g. intermediate layer or top layer), reactive pigments such as luminescent pigments can be introduced instead of and/or in addition to the color pigments.

After the marking element had hardened, it was embedded on the surface of the cycle path in a reactive, still liquid adhesive layer 1-2 mm thick, based on methacrylate, based on the printing ink according to Example 1 (which is identical to the base layer of the marking element described). Immediately after curing within a few minutes, the floor marking could already be walked on or driven on at the destination.

Depending on the substrate (e.g. fresh asphalt), the use of a primer, preferably based on a PUR formulation, can further improve adhesion.

Claims (16)

Method for producing a multilayer marking element, comprising the steps: a. applying at least a first polymer blend to a surface of a solid support to form a base layer, b. applying at least one second polymer mixture to the at least one base layer to produce at least one intermediate layer, and c. Applying at least one third polymer mixture to the at least one intermediate layer to produce a top layer, wherein
the at least one first polymer mixture, the at least one second polymer mixture and the at least one third polymer mixture comprises at least one uncured duromer mixture or elastomer mixture and steps a. to c. done by screen printing. Method according to Claim 1, characterized in that the screen printing is carried out with a screen which has a thread count of between 5 and 50, preferably between 8 and 40 per centimeter with a preferred yarn diameter of 50 to 300 µm, preferably 90 to 200 µm. Method according to Claim 1 or 2, characterized in that the screen printing is carried out with a screen which has an ink volume of 10 to 1000 cm ³ /m ² , preferably 50 to 170 cm ³ /m ² . Method according to one of Claims 1 to 3, characterized in that the base layer, the at least one intermediate layer and the top layer are each applied with a layer thickness of 10 to 1000 µm, preferably 15 to 500 µm, even more preferably 20 to 250 µm . Method according to one of Claims 1 to 4, characterized in that the multilayer floor marking has a total layer thickness of 100 to 3000 µm, preferably 200 to 3000 µm, even more preferably 500 to 3000 µm. Method according to one of Claims 1 to 5, characterized in that the solid support is a planar support comprising a film, preferably a plastic film, paper, metal, ceramic or glass. The method according to any one of claims 1 to 6, characterized in that on the surface of the solid support before step a. a release agent, a release layer or a release film is applied. Process according to one of Claims 1 to 7, characterized in that the at least one first polymer mixture, the at least one second polymer mixture and the at least one third polymer mixture have a viscosity of 1000 to 10000 mPa.s, preferably 3000 to 8000 mPa.s 25°C. Method according to one of Claims 1 to 8, characterized in that the at least one uncured duromer mixture or elastomer mixture comprises at least one reactive resin, at least one hardener and at least one filler. The method of claim 9, characterized in that the at least one reactive resin is selected from the group consisting of a methacrylic resin, an epoxy resin, a polyol resin, a polyurea resin, a polysiloxane resin, and combinations thereof. The method according to any one of claims 1 to 10, characterized in that the at least one first polymer mixture, the at least one second polymer mixture and / or the at least a third polymer mixture comprise at least one colored pigment, metal particles, glass beads and/or at least one sensor. Method according to one of Claims 1 to 11, characterized in that the at least one third polymer mixture comprises fluoropolymers, preferably polytetrafluoroethylene, thermochromic pigments, hydrochromic pigments, fluorescent pigments, luminescent pigments and/or ferromagnetic pigments. Method according to one of Claims 1 to 12, characterized in that after the covering layer has been applied, its surface is structured. Method according to one of Claims 1 to 13, characterized in that the at least one base layer, the at least one intermediate layer and the at least one top layer are cured, preferably independently of one another, by supplying heat and/or by UV radiation. Multilayer marking element producible with a method according to one of Claims 1 to 14. A method of applying a marking element according to claim 15 to a surface, preferably a substantially horizontal or substantially vertical surface, comprising the step of mechanically attaching or chemically adhering the marking element to the surface, the mechanical attachment being by at least one nail, at least one Rivets and/or at least one screw and the chemical adhesion is effected by at least one adhesion adhesive, at least one hot-melt adhesive and/or at least one pressure-sensitive adhesive.