Liquid pavement marking compositions

It is a significant need for a liquid pavement marking composition, the increased Durability and retained reflectivity provides, when heated to a surface is applied and dried or cured. compositions of this type are typically and on roads, highways, parking lots Leisure facilities used to strip bars and markers for Marking lanes, pedestrian crossings, Park spaces, Icons, labels, and the like to form. They are usually by spray coating (Ie painting) is applied to the road surface. There are also preformed pavement marking sheets or tapes have been used to road surfaces or Traffic bearing surfaces to mark.

Pavement marking tapes or road markings with other forms may reflective optical comprise elements that by using a binder on the road surface stick. Current traffic paint systems typically use conventional 1.5 n_D-Glasmikrokugeln For retroreflection. The microspheres are typically Aufschwimmbeschichtung applied immediately after coating onto the wet marking. This gives the color improved retroreflectivity and also covers the top surface of the uncured or undried Coating with a protective layer of microspheres. The protective layer allows that the labels earlier for the Traffic can be released, because the layer of microspheres on the surface of the transfer of the coating to the surface the vehicle tire prevented. This is important for the speed of the label application. The time between application and the point where material no longer transferred to vehicle tires is referred to herein as the "car-free" is defined time. Shorter increase traffic-free hours the labeling efficiency by eliminating the need of service disruption such measures such as closing roads or placing traffic control devices to Protection of such marks is reduced or eliminated.

EP-A-0 667 362 relates to a coating composition for producing a polyurea coating which comprises a) a polyisocyanate component, b) at least one compound of the formula <img img-content="cf" img-format="tif" he="33" wi="53" file="00020001.tif" />corresponds to, wherein X represents an organic Group which has a valency of n and isocyanate at a temperature of 100 ° C is or less inert, R₁ and R₂ may be the same or different and are for organic Groups are operating at a temperature of 100 ° C or lower isocyanate are inert, R₃ and R₄ equal may be or different and for Hydrogen or organic groups which at a temperature 100 ° C or less against Isocyanate groups are inert, and n is an integer having a Value of at least 2, and c) 0.1 to 15 wt .-%, based on the total weight of the coating compositions, of a water-absorbing zeolites contains.

JP-A-07 188 583 describes a resin composition for road marking, obtained by mixing (A) a blocked urethane prepolymer with (B) a polyamine compound is obtained, which one or more defined amino groups.

It would be beneficial Markings in a wider range apply to weather conditions, as with existing compositions possible is. There is also a need for marking compositions with improved cure profiles, to both the wetting of the substrate and short traffic-free Time to ensure. There are also improvements needed in order to obtain compositions that are substantially free of volatile organic components.

The present invention provides a pavement marking comprising a binder includes having polyurea. Conventional liquid Pavement marking compositions comprise binder compositions alkyd-based, as in US-A-2,897,732 (Shuger), US-A-2,897,733 (Shuger) and US-A-3,326,098 (Böttler) are described, and compositions epoxy, such as in US-A-4,088,633 (Gurney), US-A-4,185,132 (Gurney), and US-A-4,255,468 (Olson) are described. These&lt;?page 3?&gt;conventional Compositions are not at least one of the following reasons he wishes: they dry to generally slow; they require elevated temperatures for reasonable cure times; they may contain chemical linkages (eg. as ester linkages), the degradation subject (for example by hydrolysis), and / or require them the use of organic solvents, drying oils or drying accelerators, which can lead to discoloration.

It Numerous other conventional pavement marking compositions been developed to get faster drying times by used application of materials to road surfaces in the heated state has been. There are also water-borne coatings based on Acrylic latices, as disclosed in US-A-5,527,853 (Landy et al.) Discloses and epoxy resin, as in US Patent No. 4,906,716 (Cummings) is disclosed for use in road markings been proposed. Such labels have the advantage of a low content of volatile organic materials and one-component coating compositions, however, for Long-term presence in the street and retained reflectivity performance not sufficiently durable.

US-A-4,076,671 (Bright) discloses a resinous composition to be useful for marking marketable surfaces referred to as. The two-component coating compositions Acrylate are as a desirable Balance of stability and rapid curing referred delivering, but require the use of free monomers and ethylenically unsaturated Compounds of low molecular weight that have significant vapor pressures. They also require the use of peroxide catalysts. US-A-5,478,596 (Gurney) discloses liquid The pavement marking compositions consisting of a polyurethane forming two-component system of a first component with isocyanate Groups (a polyol) and a second component having isocyanate groups getting produced.

It A need exists for liquid The pavement marking compositions which contain one or more, and preferably can provide all of the following features: reduced exposure on the environment by formulations with a low content of volatile organic material; improved balance of coating rheology while the application and film formation to wetting of the substrate and rapid cure to promote non-marking films; widened the range of weather conditions for the application of the coating and / or improved marking performance through increased durability and retained reflectivity. By one or more, and preferably to achieve all of these characteristics, the present invention provides a pavement marking comprising a containing binder having polyurea.

Inventive road markings contain a binder having polyurea groups, wherein the binder is prepared from a coating composition comprising a or more aliphatic secondary Amines, one or more polyisocyanates, material selected from the group of fillers, Extenders, pigments, and combinations thereof, and reflective Elements (eg., Glass beads, etc.), wherein the pavement marking a retained reflectivity of at least about 100 mcd / m²/ Lux to at least about 2 years in use as longitudinal traffic markings as measured according to ASTM E 1710-95. The binder is preferably prepared from a two-component coating composition, have an amine component comprising one or more aspartic ester amines and optionally one or more amine-functional coreactants, and comprises an isocyanate component comprising one or more polyisocyanates includes. Also provided is a traffic bearing surface, takes one such pavement marking.

It Also provided is a pavement marking comprising a binder as defined above having polyurea, said. the binder from a sprayable Two-component coating composition is prepared which substantially free of volatile organic components and is an amine component or a more aspartic ester includes, and an isocyanate comprising comprising one or more polyisocyanates. At least comprises one of the amine component and / or the isocyanate component further selected material from the group of fillers, Extenders, pigments, and combinations thereof. The coating composition has a minimum application temperature of at least about 7 ° C and a track-free time of not more than about 5 minutes. Provided be a traffic tra ing surface such pavement marking comprising, and a pre-formed pavement marking wherein the pavement marking is applied as a coating to a substrate having on a Traffic bearing surface can be applied.

The This patent specification also describes coating compositions. The coating composition contains one or more aliphatic secondary Amines, one or more polyisocyanates and material selected from the group of fillers, Extenders, pigments, and &lt;?page 4?&gt;Combinations thereof. The coating composition has a minimum application temperature of at least about 7 ° C, a traffic-free Time of not more than about 5 minutes, and forms a pavement marking with reflective elements with a retained reflectivity at least about 100 mcd / m²/ Lux after at least about 2 years of use as a road marker measured in the longitudinal direction, according to ASTM E 1710-95.

It is also a sprayable liquid Two-component road marking composition described that an amine component comprising one or more aspartic ester and optionally one or more amine-functional coreactants includes, and comprises an isocyanate component, the one or more comprises polyisocyanates. The amine component, the isocyanate component or both further comprise material selected from the group of fillers, Extenders, pigments, and combinations thereof. The coating composition be sprayed and has a minimum application temperature of at least about 7 ° C and a track-free time of not more than about 5 minutes. The pavement marking composition preferably comprises an amine component comprising one or more aspartic ester and optionally one or more amine-functional coreactants includes, and an isocyanate component comprising one or more polyisocyanates includes.

It also methods for preparing the above pavement markings provided. There is for example a method for marking a traffic-bearing surface provided. This method includes providing an amine component, the one or more aspartic ester amines and optionally one or more amine-functional coreactants, providing an isocyanate component comprising one or more polyisocyanates, Providing material selected from the group of fillers, Extenders, pigments, and combinations thereof in either the amine component, the isocyanate component, or both, combining the amine component and the isocyanate component to form a Coating composition having a minimum application temperature of at least about 7 ° C and a traffic-free time of no more than about 5 minutes, spraying the Coating composition onto a traffic bearing surface, and Applying reflective elements to the composition, wherein the traffic-bearing surface is coated with the composition to form a pavement marking.

A another embodiment includes a method for preparing a pavement marking. This method includes providing an amine component, the one or more aliphatic secondary amines comprises providing an isocyanate component comprising one or more polyisocyanates, Providing material selected from the group of fillers, Extenders, pigments, and combinations thereof in either the amine component, the isocyanate component, or both, combining the amine component and the isocyanate component to form a Coating composition having a minimum application temperature of at least about 7 ° C and a traffic-free time of not more than about 5 minutes, Applying the coating composition to a surface, and Applying reflective elements to the composition, with the surface of the is coated to a pavement marking having reflective Elements with a retained reflectivity of at least about 100 mcd / m²/ Lux after at least about 2 years to make use of.

The Pavement marking compositions of the invention comprise a binder comprising urea groups (-NR-C (O) -NR-) comprises. This binder may be made of a two-component system be that includes an amine component and an isocyanate component. The containing amine component one or more secondary Amines, such as aspartic ester amine, which is an aliphatic secondary diamine. contains the amine component preferably primary or secondary Amines. The amine component contains at Most one or more aspartic ester preferably, optionally mixed with one or more amine-functional coreactants, which are different from an aspartic ester. The amine-functional Coreactants are polymeric polyamines, and particularly preferably essentially polymeric diamines. These amine-functional coreactants be selected the properties of the coating during the curing process and in its to keep the finished form balanced.

The Amine and isocyanate components are chosen such that the resulting Pavement marking generally resistant and durable to environmental and vehicle loads, and good visibility in daylight has. They also preferably has a good visibility at night. Durability, by good adhesion to many Substrate surfaces, including Concrete, asphalt and other markings, whether the markers are from the same or a different material can be detected.

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you can also be good adhesion (Often referred to as "anchoring") of Reflective elements are detected at the mark. The "durability" as used herein can be determined by the applied road marking on a road surface is exposed to the traffic conditions, and the power the mark is recorded over time. Reflectivity and Whiteness can instrumentally be measured in the field, and the durability of the marking to wear and erosion can be evaluated subjectively. Permanent markers have lasting adhesion to the substrate, good visibility and preferably good reflectance over a longer Period.

The from the composition according to the invention formed pavement markings are permanently have for (ie a period of use of) at least about 2 years (n), in particular at least about 3 years and most preferably at least about 4 years in use as Traffic markings in the longitudinal direction. The pavement markings have a retained reflectivity of at least about 100 mcd / m²/ Lux and in particular at least about 150 mcd / m²/ Lux during their Use time as traffic markings in the longitudinal direction. "Retained reflectivity" is used herein, to describe the effectiveness of maintained retroreflective performance a lane marking on their use time used. is retroreflectivity currently usually by a portable instrument in the field with specified Entrance and observation angles according to ASTM E 1710-95 measured. Past work (Transportation Research Record 1409 published 1994 by the Transportation Research Board) have shown that the entry angle is incident in the light, and the angle of observation, of which a driver actually sees a pavement marking, referred to herein as "approximate driver geometries", measured for retroreflective performance suitable road markings.

The Amine and isocyanate are preferably chosen so that the resultant pavement marking composition: (1) a liquid with a high solids content, which is essentially free of volatile organic components (preferably, less than about 5 wt .-% volatile organic components, typically solvents, based on the Total weight of the composition); (2) a generally rapid cure profile with a traffic-free time (ie, a drying time at ambient road conditions, if the coating is applied) of preferably not more than about 5 minutes, in particular not more than about 4 minutes, and most preferably not more than about 3 minutes, and a useful Open time (ie, the length of time that the composition after application on a surface in liquid State remains) has to adequately wet the substrate and particulates take or reflective element to anchor / (preferably a Open time of at least about 30 seconds, and particularly at least about 1 minute); (3) a wide application window (that can be a wide temperature range raise) with an emphasis on the use at lower temperatures (Preferably having a minimum application temperature of at least about 7 ° C, preferably at least about 4 ° C, more preferably at least about 2 ° C and most preferably at least about -4 ° C); (4) with static two-component mixing is or airless high pressure impingement mixing application equipment compatible; (5) commercially available, expensive containing raw materials and (6) generally shelf-stable (preferably a useful shelf life of at least 6 Months, in particular at least one year, and most preferably at least two years). is a volatile component (VOC) here is an organic compound having a vapor pressure of more than 0.01 mm Hg (13.33 Pascals) at 20 ° C. Such compounds usually have a boiling point higher than 250 ° C.

The Pavement marking compositions of the invention comprise a binder comprising urea groups (-NR-C (O) -NR-) comprises, although other groups may be present, such as biuret groups (-NR-C (O) -NR-C (O) -NR-), isocyanurate <img img-content="cf" img-format="tif" he="39" wi="30" file="00110001.tif" />as well as urethane groups (-NR-C (O) -O-) and the like, wherein R is a hydrogen or an organic group. Such polymers containing urea groups are here often referred to as polyureas. For road marking applications formulated polyureas should be resistant to abrasion and adhesion to &lt;?page 6?&gt;Road surfaces and reflective elements provide.

The Binder system is the reaction product of an amine with a Isocyanate to form a urea bond. The binder system is preferably the reaction product of a Polyasparaginesteramins, which is preferably difunctional, with a polyisocyanate, to form a polyurea.

Preferred Aspartic ester have the following formula: <img img-content="cf" img-format="tif" he="19" wi="67" file="00120001.tif" />where R¹ a divalent organic group (preferably having 1 to 40 carbon atoms) and each R² independently an organic group is that at temperatures of 100 ° C or less inert to Isocyanate is.

In the above formula, R¹ preferably a aliphatic group (preferably having 1 to 40 carbon atoms), which may be branched, unbranched or cyclic, and in particular is R¹ from the group of divalent hydrocarbon groups selected, obtained by removing the amino groups from 1,4-diaminobutane, 1,6-diaminohexane, 2,2,4- and 2,4,4-trimethyl-1,6-diaminohexane, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane, 4,4'-diaminodicyclohexylmethane or 3,3-dimethyl-4,4'-diaminodicyclohexylmethane are obtained. Also suitable are divalent hydrocarbon groups, with by the removal of amino groups from polyether amines relatively high molecular weight are obtained, the aliphatic bound amino groups, such as the products sold under the Tradenames "JEFFAMINE" by Texaco and Huntsman, and "HYCAR" by BF Goodrich be marketed. Other suitable polyamine precursors include ethylene diamine, 1,2-diaminopropane, 2,5-diamino-2,5-dimethylhexane, 1,11-diaminoundecane, 1,12-diaminododecane, 2,4- and / or 2,6-hexahydrotoluylene and 2,4'-diaminodicyclohexylmethane. Aromatic polyamines such as 2,4- and / or 2,6-diaminotoluene and 2,4'- and / or 4,4'-diaminodiphenylmethane are Also suitable but less preferred.

In the above formula, preferably, each R² independently a organic group having 1 to 40 carbon atoms, in particular each R² independently an alkyl group (preferably having 1 to 20 carbon atoms), branched or unbranched can be, and most preferably, each R² independently a lower alkyl group (having 1 to 4 carbon atoms).

Suitable Aspartic ester are commercially available from Bayer (Pittsburgh, PA, USA) For example, under the trade names "DESMOPHEN" XP 7053, XP 7059 and XP 7109 available.

"DESMOPHEN" XP-7053 is substantially from the following compound composed: <img img-content="cf" img-format="tif" he="20" wi="95" file="00130001.tif" />

"DESMOPHEN" XP-7059 is substantially from the following compound composed: <img img-content="cf" img-format="tif" he="18" wi="75" file="00130002.tif" />

"DESMOPHEN" XP-7109 is substantially from the following compound composed: <img img-content="cf" img-format="tif" he="22" wi="101" file="00130003.tif" />

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For more advantageous results can additionally a to Asparaginesteraminen or more amine-functional coreactants be used. These (different from the Asparaginesteraminen) amines generally act as a chain extender and / or impact modifier. The use of such amine-functional coreactants can contribute to the presence of soft segments in the polymer backbone, the toughness properties to improve. You can primary amines, secondary Amines or combinations thereof. Preferably, they are secondary amines, a mixture of secondary Amines or a mixture of secondary amines and primary amines. Some primary Amines tend to react so quickly that it only in small Amounts or in combination with a very slow isocyanate are useful, such as m-tetramethylxylene diisocyanate (TMXDI). In some make a significant amount of primary amines are used, and Gesamthärtungsgeschwindigkeit the coating can be obtained by using a slower Asparaginesteramins, such as "DESMOPHEN" XP-7053, moderate or decelerated. The amine-functional coreactant includes most preferably a secondary Amin.

Of the amine-functional coreactant is preferably a polymer with amine-terminated. Examples of Such polymers include those available from Huntsman Chemical under the trade designation "JEFFAMINE" Polypropylenglykoldiamine available are as "JEFFAMINE" D-2000, those who from BF Goodrich, Cleveland, Ohio, USA, under the trade designation "HYCAR" ATBN (Acylonitril-butadiene copolymers terminated Amine) available are, and those described in US-A-3,436,359 (Hubin et al.) and US-A-4,833,213 (Leir et al.) (Amine terminated polyethers, and especially Polytetrahydrofurandiamine) are disclosed, but not to this limited.

It can uses many different polyisocyanates in the preparation of the binders according to the invention will. "Polyisocyanate" means any organic Compound having in a single molecule two or more reactive isocyanate groups (NCO) has. Particularly useful polyisocyanates can be aliphatic, alicyclic or a combination thereof. This definition includes diisocyanates, Triisocyanates, tetraisocyanates, etc., and mixtures thereof. Most aliphatic isocyanates are preferred including cycloaliphatic Isocyanates used to improve the weatherability and the Yellowing decrease.

To Useful polyisocyanates include selected those from the group consisting of bis (4-isocyanatocyclohexyl) methane (H₁₂MDI, available from Bayer Corp., Pittsburgh, PA, USA), diphenylmethane diisocyanate (MDI available from Bayer Corp., Pittsburgh, PA, USA), isophorone diisocyanate (IPDI, available from Huls America, Piscataway, NJ, USA), toluene-2,4-diisocyanate (TDI, available from Aldrich Chemical Co., Milwaukee, WI, USA), hexamethylene diisocyanate (HDI, available from Aldrich Chemical Co., Milwaukee, WI, USA), m-tetramethylxylene diisocyanate (TMXDI, available from Aldrich Chemical Co., Milwaukee, WI, USA), and 1,3-phenylene diisocyanate, but not limited to. It can Mixtures of polyisocyanates can be used. Although monomeric Isocyanates may be useful, however, they are not preferred, but for the preparation of adducts and prepolymers be used, which would be preferred.

To Preferred polyisocyanates include Derivatives of the above monomeric polyisocyanates. These derivatives include polyisocyanates containing biuret groups, such as the Biuretaddukt of hexamethylene diisocyanate (HDI), available Bayer Corp., Pittsburgh, PA, USA, under the trade designations tion "DESMODUR" N-100, polyisocyanates, containing isocyanurate groups, such as those from Bayer Corp. Pittsburgh, PA, USA, under the trade designation "DESMODUR" N-3300 are available, and polyisocyanates containing urethane, uretdione, carbodiimide, contain, but are not allophanate groups and the like limited. These derivatives are preferred as they are polymeric and very low vapor pressures have and contain free isocyanate monomer in negligible quantities.

It are many useful commercially available adducts of the monomeric Isocyanates. There are also many useful adducts and prepolymers, currently not commercially available are, however, could be manufactured, such as the Reaction products of the above mentioned aspartic ester amines with diisocyanates, such as IPDI, TMXDI, and the like.

The stoichiometry the polyurea reaction is based on a ratio of isocyanate equivalents to equivalents to aspartic and optional Amincoreaktant. The isocyanate is preferably used in excess used. The isocyanate: amine ratio is preferably less than about 1.15:. 1 The isocyanate: amine ratio is more preferably less than about 1.1: 1st The isocyanate: amine ratio is most preferably less than about 1.05: 1st The lower ratios of isocyanate to amine can potentially the formation of a looser polymer network and increased viscoelastic damping in the cured Coating lead.

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Around the desired stoichiometries to obtain the amine and isocyanate are in a volume ratio of preferably about 1: 1 to about 5: 1 amine to isocyanate components combined. The relationship is, in particular in a range from about 1: 1 amine: 1 to 3 Isocyanate. Particularly preferred ratios are 2: 1 and 3: 1 amine to isocyanate.

The Pavement marking compositions of the invention are referred to as two-component systems, one or more Aspartic ester amines, optionally blended with one or more amine-functional coreactants (of an aspartic ester are different), and one or more polyisocyanates as the reactive Two-component system containing. It can further components, various additives are used to achieve desired results. Bewitterungsadditive, such as UV absorbers, hindered amine light stabilizers, Antioxidants, dispersants, Grinding aids, wetting agents, impact modifiers (Z. B. rubber toughening agents, such as those under the trade names "Paraloid" EXL 2691 and-2330 from Rohm and Haas available are), antifoams, Suspension stabilizers, biocides, for example, to the are given binder to the processability and the total permanence the markings of the invention to improve. There are what is important, however, no catalysts required to the desirable to achieve traffic-free hours.

pigments (Z. B. TiO₂), Fillers (eg. For example, talc, CaCO₃, Clay, ceramic microspheres, hollow polymeric microspheres and hollow glass microspheres), extenders, diluents, Plasticizers, leveling agents and surfactants agent can also be used. Pigments impart desirable properties of the visual appearance during the day and contribute to the reflection power of the marking at night at. fillers and extenders can be used to control the flow properties of the liquid coating modifying and using materials with a more favorable cost-to-volume ratio to contribute the bulk volume of the finished coating. fillers, as Kera mikmikrokugeln, hollow polymer microspheres (such as those under the trade name Expancel 551 DE from Akzo Nobel, Duluth, GA, U.S.A. are), and hollow glass microspheres (such as those under the trade designation K37 from Minnesota Mining and Manufacturing Co., St. Paul, MN, USA) available are, are especially useful and can also be added, to a specific volume ratio for the To achieve the two components of this two-component coating, without the reactive chemistry of the coating mixture to significantly influence. The pigments, fillers and extenders can a significant impact on the uncured formulation and density the cured Films that Filmhärtungsprofil and the track-free time, the modulus of the cured film coating adhesion to a substrate, the response to temperature changes, the possible shrinkage of the polymer components, the abrasion and the durability of the coating have. Typically, at least about 15 wt .-% of the final dried coating from such insoluble material, in particular at least about 20 wt .-%, and most preferably at least about 25 wt .-%. In some cases can about 30 wt .-% to about 42 wt .-% pigments, fillers and extenders be used.

On particularly preferred type of filler is hollow glass microspheres. Hollow glass microspheres are particularly advantageous because they have excellent heat resistance and a minimal Influence on the viscosity have and density of the dispersion. You will also quickly and easily dispersed by low shear mixing and demonstrate relatively little abrasion in the machine. The microspheres are elevated for Shelf Life preferably introduced in the amine component. have field trials shown that incorporation of at least about 30 vol.%, and preferably about 30 vol.% to about 40 vol.% of hollow glass microspheres into pavement marking compositions of the invention lead to improved durability of the pavement marking.

The Pavement marking compositions of the invention are usually directly with or without a primer layer on a traffic-bearing surface or applied to a substrate which is applied to the surface is. This can be done using spray coating techniques. The amine component and the isocyanate component are typically applied with a spray device, the combining of the components immediately before exiting the device allows. It can For example, air-free high-pressure two-component impingement mixing systems be used. It can multicomponent jetters be used with a static mixer.

On example for an air-free impact-mixing spray system is Gusmer (1 Gusmer Drive, Lakewood, NJ, USA, 08701-0110 produced). The system includes the following components: a Proportionierabschnitt, the meters the two components and the pressure to more than about 1500 psi (10.34 MPa) increases; a heating section to the temperatures of the two components (Preferably independently) to &lt;?page 9?&gt;increase, to adjust the viscosity to control, and an impingement spray gun which both the Components combined and mixing allowed immediately before atomization. Other producers for Impact systems are Binks Manufacturing (Chicago, Illinois, USA) and glass-Craft (Indianapolis, IN, USA).

On Another system for applying polyurea coatings is useful is a system that a static mixing tube used to achieve mixing of the two components. The system is that of the impingement unit similar in that the components metered, pressure builds up and heats it. At the spray gun the components are combined, and yet each by a length of tubing pumped containing elements, which are provided for mixing the components prior to atomizing. This System requires periodic flushing the static mixing tube, to prevent accumulation of cured polyurea, Spray guns could clog. An example for such a spray gun is a Binks Model 43P.

The viscosity behavior of each of the two components for two-component spray coating important. Upon impact, mixing the viscosities should both Components at high shear rates as close as possible to each other lie to adequate Mixing and uniform curing to enable. The static multicomponent mixing / spray system appears in viscosity differences to be good-natured between the two components. characterization the viscosities as functions of shear rate and temperature can Decision as the starting point of temperatures and Push facilitate the coatings in the two-component Sprühgerätestraßen.

The inventive liquid pavement marking compositions provide polyurea coatings with conventional visibility by daylight. You can also act as a binder to reflective optical elements to anchor. The reflective elements have generally not more than about a few millimeters in diameter. If the reflective Elements of glass or ceramic microspheres, they are typically in the range of about 200 microns to about 600 microns.

The reflective elements be in the form of glass beads (also as microspheres or microsphere lenses hereinafter), which are preferably transparent. The chemical treatment the bead surfaces, such as with an organochromium compound, may, as is known in the art is to increase adhesion use of resin to glass. Other chemical coupling agent such as silanes, titanates, and zirconates are also known. Fluorocarbon treatment the beads can also contribute a substantially uniform hemispherical sinking to reach the pearl.

After spraying applied elements in the form of glass or ceramic beads or Microspheres may additionally for their provision of reflectivity at night as Bindefüllstoff be used. You can like Mineral particulate materials on the wear surface of a coated abrasive (Sandpaper) act to the polymer binder before acting to protect loads. Of the average diameter of the microspheres of boarding or coverage rate (Weight per unit area) and surface chemistry (Z. B. Treatment with coupling agent) affect the durability of the road markings. Typical coverage rates preferably correspond more than about 4 lb of glass beads per gallon (479 g / L) binder, in particular more than about 10 lb per gallon (1200 g / L). This matches with preferably more than about 6 grams glass beads to 300 cm² Area for a 15 mil (0.4 mm) thick cured Film, in particular more than about 15 g of glass beads to 300 cm² area for one 0.4 mm thick cured Movie.

The reflective elements also be in the form of ceramic microspheres (ie, beads). "Ceramic" is used herein to refer inorganic materials are used which either crystalline (a Material with a patterned atomic structure sufficient to a characteristic X-ray diffraction spectrum to produce) or amorphous (a material with no long range order in its atomic structure, as indicated by the lack of a characteristic X-ray diffraction spectrum show) can be. Amorphous ceramics are more common as glasses. Ceramic beads are preferred because they are more durable and wear-resistant than glass microspheres are. Prior to the present invention, ceramic beads were in grinded Pavement markings are not used in practice, because the Binder not adhered sufficiently durable and roads was.

The Ceramic beads or other reflective microspheres can directly be applied to the binder as a coating on the road surface present. You can alternatively in the form of retroreflective optical elements with vertical surfaces be applied. Vertical Oberflä&lt;?page 10?&gt;chen provide better orientation for the Retroreflectivity. You can also the construction of a water layer over the retroreflective surface while prevent rain, otherwise the retroreflective mechanism to disturb could.

On Type of such retroreflective optical elements with vertical surfaces is composed of pellets having a thermoplastic core include having a coating of ceramic beads. Such reflective Elements and methods for their preparation are published in the International Patent Specification Nos. WO-A-97/03814 (Bescup et al.) disclosed. There are film elements using polymers been used with varying melting behavior. To the retroreflective elements include a plurality of optical elements, such as glass or ceramic microspheres partially in the vertical surfaces embedded central layer of the core of the reflective element are. Such reflective elements and methods for their preparation are described in International Patent Publication Nos. WO-A-97/28471 discloses.

It can pure ceramic retroreflective elements with significantly improved resistance to wear and Effects of weathering be prepared in pavement markings can be used. These retroreflective elements are preferably free of metals and polymeric materials. These retroreflective elements are of an opacified ceramic core and optical ceramic elements composed, which are partially embedded in the core. The opacified ceramic cores of these reflective optical composite elements often contain a mixture of amorphous (glass) and crystalline Phases. The retroreflective element may be irregular in shape have or be in the form of a sphere, disc, tile, etc. The diffuse reflecting ceramic core, in combination with to the surface embedded transparent optical elements, a surprisingly bright retroreflective element without the gray coloration and corrodibility, which are connected to metal reflectors. Such reflective Elements and methods for their preparation are described in US Patent Application Serial No.. 08 / 591.570 disclose.

It are many other variants of retroreflective Kompositelementen or from known aggregates, a polymer core with embedded in the core surface comprise optical elements. See, eg, US Patent 3,252,376; US-A-3,254,563; US-A-4,983,458; US-A-4,072,403; U5-A-4,652,172 and US-A-5,268,789. Other retroreflective elements with a ceramic core and glass optical elements with a metallic mirror coating being constructed. See, eg, US Patent 3,043,196; US-A-3,175,935; US-A-3,556,637; US-A-3,274,888 and US-A-3,486,952 and EP Publication No. 0 322 671. Retroreflective ceramic elements in the show Usually greater resistance opposite to Weathering and wear. Some known embodiments also contain optical elements dispersed throughout the core. The core may be irregular in shape or may be formed regularly be z. B. spheres, tetrahedrons, discs, square tiles, etc.

Retroreflective Elements are advantageous because they are inexpensive painted markings can be embedded.

Irrespective of the type of reflective element can on by Aufschwimmbeschichten the entire surface of the road surface painted binder are applied, this can in ceramic microspheres However, be quite expensive. Alternatively, the reflective elements are arranged only in the effective optical portion of the surface. The Controlling the position of the element on liquid markings is important to obtain lasting high retroreflectivity. You can also one of the components may be added prior to mixing and for example while spray coating the two-component liquid be applied.

It is also important to the mechanism of embedding elements, whether in the form of coated pellets or microspheres to understand. surface treatments can are used to appropriate sinking, not too deep and not too shallow to obtain, and the wetting and capillary action of the to control coating on the sides of the element upward. The cure rheology the two-component binder system, the ability of to sinking of elements also influence.

Some embodiments and Preferred Embodiments of the present invention are summarized in the following points:

<ul><li>1. pavement marking comprising: binder with polyurea groups, wherein the binder of a coating composition &lt;?page 11?&gt;produced is comprising: one or more aliphatic secondary amines; on or more polyisocyanates; and Material selected from the group consisting of fillers, Extenders, pigments, and combinations thereof; and reflective Elements, wherein the pavement marking a retained reflectivity of at least about 100 mcd / m²/ Lux after at least about 2 years of use as a road marker has longitudinally, measured according to ASTM E 1710-95.</li><li>2. The pavement marking of item 1 wherein the one or more aliphatic secondary Amines include an aspartic ester.</li><li>3. The pavement marking of item 1 wherein the coating composition a minimum application temperature of at least about 7 ° C and a free time of no more than about 5 minutes has.</li><li>4. The pavement marking of item 1 wherein the reflective Elements include ceramic microspheres.</li><li>5. The pavement marking of item 1 wherein the coating composition substantially free of volatile organic components.</li><li>6. The pavement marking of item 1 wherein the coating composition an open time of at least about 30 seconds has.</li><li>7. The pavement marking of item 1 wherein the filler comprises hollow glass microspheres.</li><li>8. pavement marking of item 1, the material selected from the group of fillers, Extenders, pigments, and combinations thereof in an amount of at least about 15 wt .-% to summarizes, based on the weight of the final dried coating.</li><li>9. pavement marking of item 8, the material selected from the group of fillers, Extenders, pigments, and combinations thereof in an amount from about 30 wt .-% to about 42 wt .-% comprising, based on the weight the final dried coating.</li><li>10. The pavement marking of item 1 wherein the binder consists of a sprayable Two-component coating composition is prepared which substantially free of volatile organic components and is an amine component or a more aspartic ester includes, and an isocyanate comprising comprising one or more polyisocyanates, wherein at least one of the amine component and the isocyanate component further material selected from the group of fillers, Extenders, pigments, and combinations thereof, and the Coating composition a minimum application temperature of at least about 7 ° C and a free time of no more than about 5 minutes has.</li><li>11 traffic-bearing surface, having thereon a pavement marking of item first</li><li>12 traffic-bearing surface, the on a road marking has to point 10th</li><li>13. Preformed pavement marking a pavement marking with a comprises according to item 10 coated substrate.</li><li>14. A method of manufacturing a pavement marking comprising: Provide an amine component comprising one or more aliphatic secondary amines includes; Providing an isocyanate component or an more polyisocyanates comprising; Providing Material selected from the group of fillers, Extenders, pigments, and combinations thereof in either the amine component, the isocyanate component, or both; Combine the amine component and the isocyanate component to form a Coating composition having a minimum application temperature of at least about 7 ° C and a traffic-free time of not more than about 5 minutes; apply the coating composition to a surface; and Applying reflective Elements to the composition, wherein said surface with is coated the composition to form a pavement marking with reflective elements with a retained reflectivity at least about 100 mcd / m²/ Lux after at least about 2 years of use as a road marker longitudinal, measured according to ASTM E 1710-95.</li><li>15. The method of item 14, wherein the surface of a Traffic bearing surface is.</li><li>16. The method of item 14, wherein the step of applying the coating composition comprises spraying the coating composition includes.</li><li>17. The method of item 14 wherein the amine and isocyanate in a volume ratio combine 1 amine to isocyanate: about. 2</li><li>18. The method of item 14 wherein the amine and isocyanate in a volume ratio combine 1 amine to isocyanate: from about. 3</li><li>19. The method of item 14, comprising: providing a Amine component comprising one or more aspartic ester amines and optionally a &lt;?page 12?&gt;or more amine-functional coreactants comprising; Provide an isocyanate component comprising one or more polyisocyanates; Provide selected by Material from the group of fillers, Extenders, pigments, and combinations thereof in either the amine component, the isocyanate component, or both; Combine the amine component and the isocyanate component to form a Coating composition having a minimum application temperature of at least about 7 ° C and a traffic-free time of not more than about 5 minutes; spraying the Coating composition to a traffic bearing surface; and apply reflective elements to the composition, wherein the traffic bearing surface with is coated the composition, to form a pavement marking.</li></ul>

The following examples are presented to the different special and preferred embodiments, and techniques to further illustrate. It should be noted, however, that many variations and modifications may be made while remaining within the scope of the present invention. Referred to in these examples, specific materials and their Amounts and other conditions and details are for example to be interpreted such that it generally used in the art be, and should not be considered unduly limiting the invention.

Examples

The following method is typically useful in making the amine component of two-component compositions of the invention

Pigment dispersion method

<ul><li>Stage 1: was in the suitably sized mixing vessel a half or less, based on the weight of the amine component (preferably the viskoseste) and the dispersant, if used, is introduced. It was mixed for one minute with a low shear (500 to 1000 rpm) to mix. It was TiO₂-Pigment, if used, is added in two portions. It was several minutes long with a blade Cowles low shear (500 to 1000 rpm) to uniform Consistency mixed.</li><li>Stage 2: other extenders were (those are not shear sensitive) added in several portions to the mixing vessel and then mixed to avoid clumping.</li><li>Step 3: After all not shear sensitive extenders had been added, was mixed with high shear to agglomerated to disperse pigment and extender. For this had usually the appropriately sized Cowles blade type (eg. B. 4 inches (10.2 cm) diameter for use in 5 gallon (19 L) tubs) with 2000 to 3000 revolutions per minute (rpm) over the course of 20 to 60 minutes or longer be used. The optimum rpm depends on the batch size, the viscosity and the component types. additional Amine / liquid component can be added as required to maintain a viscosity, which is suitable for grinding.</li><li>The batch temperature rose to 120 ° F to 140 ° F (49 ° C to 60 ° C). In order to monitor the progression of the dispersion was a Mahlmaß from Hegman type used. It was generally milling to a particle size of less achieved as a mil, which corresponds to the PC Mahlskala a 7.0.</li><li>Stage 4: At this point, residual amine and others were liquids with mixing added with low shear.</li><li>Step 5: Shear sensitive extenders, such as the hollow Glass or polymeric microspheres, were added in portions as needed added To avoid clumping, and with a shovel low Shear, such as a propeller or mixer from Jiffy-type, and rpm values of 500 or less for dispersed for 10 to 15 minutes.</li></ul>

to Preparation of the inventive examples were used the following materials.

&lt;?page 13?&gt;

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&lt;?page 14?&gt;

<img img-content="tb" img-format="tif" he="149" wi="150" file="00310001.tif" />

The following examples were prepared.

<img img-content="tb" img-format="tif" he="79" wi="147" file="00310002.tif" />

&lt;?page 15?&gt;

<img img-content="tb" img-format="tif" he="248" wi="152" file="00320001.tif" />

&lt;?page 16?&gt;

<img img-content="tb" img-format="tif" he="242" wi="152" file="00330001.tif" />

The Coatings were prepared from Example 1 by the pigmented Amine component in one chamber and the isocyanate component in the another chamber of a two-chamber syringe WUR introduced&lt;?page 17?&gt;the, the two Components injected simultaneously through a static mixing tube were to mix the amine and isocyanate components, and Doctor blade was used to the reactive mixture as a coating applied to metal and glass test plates. coatings were also applied to paper release liner and allowed to harden. The target thickness was 0.38 mm.

The Coatings were from large Batches (ie, 20 liters) of Examples 2 to 10 prepared by filled Amine and isocyanate in the separate reservoir chambers a Airtech Zweikomponentensprühsystems were charged, and the coating with a static Mischsprühpistole Binks 43P on a road surface sprayed has been. The coatings were also applied by spraying on metal test panels and Paper release liner applied and allowed to harden. The target thickness was 0.38 mm.

Out Examples 11 and 12 Coatings were prepared by indicated the amine component as in the pigment dispersion method were mixed. The indicated amount of amine and isocyanate was placed in a mixing vessel and mixed by low shear mixing. reactive Mixture with a knife as a coating on paper release liner, Metal or glass test plates applied. The target thickness was 0.38 mm.

at all samples was the cure profile recorded at intervals of 30 seconds by a tongue depressor across the drawn sample and finger tack was evaluated. The traffic-free Time was defined as the time at which the cure to the point expired was, on which the material flowed no longer and a coherent had formed film.

Test

The the following data are used to characterize the performance, cure profiles of and the durability of coatings of the invention useful: Drying time or track-free time (minutes), abrasion loss (grams) and retroreflective performance (mcd / m²/ Lx) marks with the retroreflective optical elements.

The abrasion resistance the coatings can be measured with a Taber Abraser. Samples of Example 7, the coating on the aluminum test plates had been applied, were weighed and after 2000 cycles with 500 g load with a CS-17 Abraderkörper at ambient laboratory conditions abraded. After abrasion, the wear debris material was wiped from the sample and the sample re-weighed. The average Weight loss in grams was 0.0472, compared with a loss of 0.112 grams for commercial Transport water-based paint.

road markings the method disclosed in this invention are used to define the type Lanes used and therefore as continuous lines on the edge a track or in dashed lines separating lanes applied, which is referred to as broken lines. These Markers are referred to as labels in the longitudinal direction, as they are parallel to the direction of traffic. In real use is a relatively small percentage of the road-use Vehicles these marks really cross.

It is to study the wear properties of a traffic marking practice that Material applied in a transverse pattern on a road surface, this means, it is across the lanes and applied perpendicular to the direction of traffic. In this way, each vehicle meets a portion of the test line. The wear pattern, generated, may also directly as "tire track", or that portion of the line in the path of a vehicle tire, the exposed to the highest wear is, or will be described as "borderline" the areas closer called on the border of the lane, which hit less frequently will. It is by analyzing the performance of an in this way applied test mark possible the wear properties a marking in an accelerated time frame to investigate an estimate the actual to provide durability.

It A test of this type constructed to evaluate the performance of the present Marking with two road marking products commercially available to compare. These were as controls or reference materials selected since they are known excellent durability and more than 2 years use time as markers in longitudinal directions delivered. The data below are reflectivity, measured according to ASTM E 1710-95a and taken in the wheel tracks or the region of the highest wear. As from the table can be seen intersecting the present material compared with the commercial Products despite the lower coating thickness quite advantageous from. &lt;?page 18?&gt;<img img-content="tb" img-format="tif" he="45" wi="144" file="00360001.tif" /><img img-content="tb" img-format="tif" he="59" wi="144" file="00370001.tif" /><ul><li>* Measurement was taken after 3 months.</li></ul>

The Samples 1 to 10 were applied as described above and evaluated. The highest Durability (defined as retained anchorage to substrates) was obtained using those formulations containing a high Loading of hollow glass bubbles / microspheres contained. Example 6, which contained 37 vol.% Glass bubbles behaved for example, better than Example 5, to the same co-reactants based, but only 10 vol.% of glass bubbles contained. Example 10 the 24 vol.% glass bubbles contained, showed better durability compared to Example 9, were installed in the identical coreactants, but not the glass bubbles contained. The "JEFFAMINE" co-reactant in the Examples 9 and 10 and the "HYCAR" amine terminated copolymer having increased both flexibility and tenacity the coatings produced. The selection of the amine, the durability also affect the coating. Example 8 was compared with Example 2 better durability. In this case, it has been found that in Example 8, using the stiffer XP-7053 and XP-7059 Asparaginesteraminkomponenten film formed higher modulus improved durability performance conferred compared to Example 2, on the flexible XP-7109 Amine based. reduced The addition of the dispersant in Example 8 the viscosity and improved the shelf life of the filled amine component.

at actual Use were applied markings based on Examples 2 and 8 at -8 ° C, and it was found that the coating with the traffic-free Times of less than 5 minutes hardened.