WO2015123625A1

WO2015123625A1 - Durable thermoplastic pavement markings

Info

Publication number: WO2015123625A1
Application number: PCT/US2015/016016
Authority: WO
Inventors: Eugene H. Carlson; Matthew D. Wilding; Gregg A. Patnode; James P. Endle
Original assignee: 3M Innovative Properties Company
Priority date: 2014-02-17
Filing date: 2015-02-16
Publication date: 2015-08-20

Abstract

The present disclosure generally relates to thermoplastic pavement markings and to thermoplastic pavement marking compositions that include more than about 7 wt% EVA.

Description

DURABLE THERMOPLASTIC PAVEMENT MARKINGS

Technical Field

The present disclosure generally relates to thermoplastic pavement markings, to thermoplastic pavement marking compositions, and to methods of making and applying these pavement markings and compositions.

Background

Pavement or road markings (e.g. , paints, tapes, and individually mounted articles) guide and direct motorists and pedestrians traveling along roadways and paths. Pavement or road markings can be used on, for example, roads, highways, parking lots, and recreational trails, to form stripes, bars, and markings for the delineation of lanes, crosswalks, parking spaces, symbols, legends, and the like. Paint was a preferred pavement marking for many years. However, modern pavement marking materials offer significant advantages over paint, such as increased visibility, retroreflectance, improved durability, and temporary and/or removable marking options. Further, currently available road marking materials can be, for example, sheets, films, tapes, sprayable compositions, and raised pavement markers.

Pavement or road markings are subject to continuous wear and exposure to the elements as well as road chemicals. Consequently, there is a need for pavement or road marking compositions and materials that provide durability and retained reflectivity once applied to a surface and dried and/or hardened. Thermoplastic polymers are often included in road markings because they are highly durable. Additionally, the use of thermoplastic polymers in road markings results in shorter track- free time.

"Track- free time," as used herein, is the time between application and the point where material will no longer transfer to vehicle tires. Shorter track-free times increase marking efficiency by reducing or eliminating the need for traffic disruption through such measures as closing lanes or placing traffic control devices to protect such markings.

Examples of thermoplastic road marking materials include, for example, ethylene acrylic acid ("EAA") polymers (see, for example, U.S. Patent No. 6,217,252 (Tolliver)) or ethylene vinyl acetate ("EVA") polymers (see, for example, U.S. Patent No. 5,536,569 (Lasch et al.)).

Summary

Current pavement markings or pavement marking compositions include less than about 7 wt% EVA. The inventors of the present disclosure recognized that various benefits result from including more than 7 wt% EVA in thermoplastic pavement markings, especially in, for example, preformed

thermoplastic pavement markings or compositions.

The pavement marking compositions and pavement markings described herein have numerous advantages. One exemplary advantage of the pavement markings described herein is that they have increased flexibility compared to existing pavement markings. This flexibility reduces the incidence of preformed pavement marking break during rolling, shipment, and/or application. Additionally, the improved flexibility makes application of these pavement markings easier. Increased flexibility can also reduce stress induced cracking on the road after application, which results in a longer- lasting pavement marking.

Another exemplary advantage is that at least some of the pavement markings are equally or more durable than existing pavement markings. In embodiments where durability is improved, thinner pavement markings can be formed. Thinner pavement markers can cover the same area using less material, and are thus more cost-effective to manufacture and apply. Alternatively, preformed pavement markers of traditional thickness can be made and, due to the increased durability, these will last longer, resulting in fewer lane closures due to pavement marking application.

Another exemplary advantage of the pavement markings described herein is that at least some of the pavement markings exhibit equal or improved surface energy and toughness, which results in pavement markings that do not retain or adhere dirt. Consequently, the daytime and/or nighttime visibility of the pavement markings may be improved.

Some embodiments of the present disclosure relate to a thermoplastic pavement marking composition including greater than about 7 wt% ethylene vinyl acetate based on the total weight of the composition. In some embodiments, the thermoplastic pavement marking composition further includes less than about 80 wt% ethylene vinyl acetate based on the total weight of the composition. In some embodiments, the thermoplastic pavement marking composition includes ethylene vinyl acetate having a melt flow index of between about 10 g/ 10 min and about 800 g/ 10 min at 190°C. In some embodiments, the thermoplastic pavement marking composition includes ethylene vinyl acetate having a melt flow index of between about 150 g/ 10 min and about 800 g/ 10 min at 190°C.

In some embodiments, the thermoplastic pavement marking composition further includes a resin selected from a group consisting essentially of rosin esters, hydrogenated rosin resins, dimerized rosin resins, modified rosin resins, hydrocarbon resins, C5 aliphatic resins, hydrogenated C5 aliphatic resins, C5 aromatic resins, C9 aromatic resins, pure monomer C9 aromatic resins, hydrogenated C9 aromatic resins, C5/C9 aliphatic / aromatic hydrocarbon resin,C10 resins, modified CIO resins, pure monomer resins, hydrogenated pure monomer resins, pure aromatic monomer resins, low molecular weight fully hydrogenated inert thermoplastic resin derived from petrochemical feedstocks, and combinations thereof. In some embodiments, the thermoplastic pavement marking has a ratio of ethylene vinyl acetate to resin is between about 80:20 to about 40:60. In some embodiments, the thermoplastic pavement marking has a ratio of ethylene vinyl acetate to resin is between about 3 : 1 to about 1.5: 1.

In some embodiments, the thermoplastic pavement marking includes ethylene vinyl acetate has a vinyl acetate content of between about 18 wt% and about 28 wt%. In some embodiments, the thermoplastic pavement marking includes an adhesive adjacent to the thermoplastic pavement marking composition. In some embodiments, the adhesive is selected from a group consisting essentially of pressure sensitive adhesives, thermoplastic resin-containing compositions, hot melt adhesives, thermoset adhesives, contact adhesives, acrylic adhesives, epoxy adhesives, urethane adhesives, non-thermoplastic hydrocarbon elastomers, natural rubber, butyl rubber, synthetic

polyisoprene, ethylene-propylene rubber, ethylene -propylene-diene monomer rubber (EPDM), polybutadiene, polyisobutylene, poly(alpha-olefm), styrene -butadiene random copolymer rubber, acrylate based pressure sensitive adhesive compositions, and combinations thereof.

In some embodiments, the thermoplastic pavement marking composition includes greater than about 10 wt% ethylene vinyl acetate based on the total weight of the composition. In some embodiments, the thermoplastic pavement marking composition includes greater than about 15 wt% ethylene vinyl acetate based on the total weight of the composition. In some embodiments, the thermoplastic pavement marking composition includes greater than about 20 wt% ethylene vinyl acetate based on the total weight of the composition.

Some embodiments relate to a pavement marker including the pavement marking composition of the type described herein. In some embodiments, the pavement marker is preformed. In some embodiments, the pavement marker has a contact angle of at least 64°. In some embodiments, the pavement marker has an energy at break of at least 0.1 ft*lbf / in³. In some embodiments, the pavement marker has a mandrel bend flexibility of 6 inches of diameter or less. In some embodiments, the pavement marker has a CAP-Y of greater than 80.

Detailed Description

Exemplary thermoplastic pavement marking compositions and pavement markings of the present disclosure include more than about 7 wt% EVA. In some embodiments, the thermoplastic pavement marking compositions and pavement markings include more than about 10 wt% EVA. In some embodiments, the thermoplastic pavement marking compositions and pavement markings include more than about 12 wt% EVA. In some embodiments, the thermoplastic pavement marking compositions and pavement markings include more than about 15 wt% EVA. In some embodiments, the thermoplastic pavement marking compositions and pavement markings include more than about 17 wt% EVA. In some embodiments, the thermoplastic pavement marking compositions and pavement markings include more than about 20 wt% EVA. In some embodiments, the thermoplastic pavement marking compositions and pavement markings include more than about 22 wt% EVA. In some embodiments, the thermoplastic pavement marking compositions and pavement markings include more than about 25 wt% EVA.

Exemplary thermoplastic pavement marking compositions and pavement markings of the present disclosure also include less than about 80 wt% EVA. Exemplary thermoplastic pavement marking compositions and pavement markings of the present disclosure also include less than about 70 wt% EVA. Exemplary thermoplastic pavement marking compositions and pavement markings of the present disclosure also include less than about 60 wt% EVA. Exemplary thermoplastic pavement marking compositions and pavement markings of the present disclosure also include less than about 50 wt% EVA. Exemplary thermoplastic pavement marking compositions and pavement markings of the present disclosure also include less than about 40 wt% EVA.

In some embodiments, the EVA has a vinyl acetate content of between about 18 wt% and about 40 wt%. In some embodiments, the EVA has a vinyl acetate of between about 18 wt% and about 28 wt%. Some exemplary commercially available EVA copolymers for inclusion in the composition or pavement markings of the present disclosure include, for example, Elvax™ 150, Elvax 250, Elvax 260, Elvax 350, Elvax 410, Elvax 450, Elvax 550, Ateva™ 1241, Ateva 1615, Ateva 1641, Ateva 9020, Ateva 9030,

Evatane™ 20-20, Evatane 28-25, Evatane 28-40, Evatane 33-25, Evatane 33-45, Evatane 40-55, Escorene Ultra™ FL 01418, Escorene Ultra UL 02518CC, and Escorene Ultra UL 05540EH2.

Some EVA copolymers capable of use in the compositions and pavement markings described and claimed herein have a melt flow index of between about 10 g/ 10 min and about 800 g/ 10 min at 190°C. In some embodiments, the EVA copolymers have a melt flow index of between about 150 g/ 10 min and about 800 g/ 10 min at 190°C. In some embodiments, the EVA copolymers have a melt flow index of between about 300 g/ 10 min and about 500 g/ 10 min at 190°C.

The pavement marking composition of the present disclosure may also include thermoplastic reinforcing polymers, of the type generally described in, for example, U.S. Patent No. 4,490,432. In some embodiments, thermoplastic reinforcing polymers generally comprise from about 1 to about 25 wt% of the total composition. In some embodiments, the range is between about 1 wt% and about 5 wt%.

The pavement marking composition may optionally include up to about 75 wt% of other ingredients selected from reflective elements (e.g., glass beads), extender resins, fillers, and pigment. The proportions can be varied within the stated ranges depending upon the amount of other ingredients included in the composition, especially the amount and kind of optional fillers.

In addition to the EVA, the compositions and pavement markings of the present disclosure may also include, for example, one or more resins (i.e., low molecular weight amorphous polymers).

Exemplary resins include those selected from a group consisting essentially of rosin esters, hydrogenated rosin resins, dimerized rosin resins, modified rosin resins, hydrocarbon resins, C5 aliphatic resins, hydrogenated C5 aliphatic resins, C5 aromatic resins, C9 aromatic resins, pure monomer C9 aromatic resins, hydrogenated C9 aromatic resins, C5/C9 aliphatic / aromatic hydrocarbon resin, CIO resins, modified CIO resins, pure monomer resins, hydrogenated pure monomer resins, pure aromatic monomer resins, low molecular weight fully hydrogenated inert thermoplastic resin derived from petrochemical feedstocks, and combinations thereof. In some embodiments, the EVA to resin ratio is between about 80:20 and about 40:60. In some embodiments, the EVA to resin ratio is between about 3: 1 and about 1.5: 1. In some embodiments, at least some of the resins are tackifiers. In some embodiments, retroreflective or reflective articles, transparent microspheres, and/or skid- resisting particles are included in the composition or are placed on top of or adjacent to the composition. In some embodiments, these increase visibility or signaling performance of the road marker. Methods of applying the retroreflective or reflective articles, transparent microspheres, and/or skid-resisting particles are disclosed in, for example, U.S. Patent No. 3,451,537, incorporated in its entirety herein.

Some embodiments include a stabilizing agent that assists in providing UV or heat resistance. Exemplary stabilizing agents include, for example, hindered amine light stabilizers (HALS), phosphonate heat stabilizers, benzophenones, and zinc compounds. Stabilizing agents may be present at levels up to about 5 wt%. Some embodiments include a rheology control agent that assists in providing settling resistance. Exemplary rheology control agents include, for example, bentone and fumed silica. Some embodiments include one or more plasticizers. In some embodiments, extender resins, often halogenated polymers such as chlorinated paraffins, but also hydrocarbon resins or polystyrenes, are preferably included with the non-crosslinked elastomer precursor ingredients, and are miscible with, or form a single phase with, the elastomer precursor ingredients.

In some embodiments, the non-cross-linked thermoplastic materials are admixed with the additional materials forming a relatively homogeneous mixture, wherein the non-crosslinked

thermoplastic materials are dispersed randomly three- dimensionally throughout the polymeric material. A high shear mixer is suitable for this purpose. Alternatively, in forming a sheet the non-crosslinked thermoplastic materials may be deposited in a substantially planar orientation. After mixing, the composition is processed on calendering rolls where the composition forms a smooth band and is processed into sheets of the desired thickness. Exemplary sheeting thickness is between about 1/4 millimeter and about 5 millimeters. In some embodiments, the sheets are at least about 1 millimeter. In some embodiments, the sheets are less than 3 millimeters thick.

The pavement markers of the present disclosure can be any desired color, including, for example, white or yellow. The pavement markers can be colored in any way known in the art, including, for example, inclusion of one or more of T1O2, CaCC>3, crushed quartz, crushed glass, talc, iron oxide yellow, or yellow pigment 83. The pavement markers of the present application can also include an ultramarine blue pigment that increases whiteness.

Retroreflective elements (e.g., transparent microspheres, cube-corner particles derived from ground sheeting) and/or and skid-resisting particles (e.g., sand particles) may be included in the compositions or pavement markings described and claimed herein. In some embodiments, these are included at a concentration of up to about 60 wt%. In some embodiments, they are included in a concentration of about 35 wt% to about 50 wt%. Retroreflective elements assist in providing reflectivity at night. For example, reflective glass beads may be dispersed on or throughout the thickness of the pavement marking sheet or composition. Skid-resisting particles provide skid-resisting qualities. An exterior layer of such particles may be provided on the top of the sheet material, partially embedded in the sheet material and partially protruding from the sheet material, to provide immediate reflectivity and skid- resistance; and other particles may be embedded in the sheet material to become exposed as the sheet material is worn away. The particles may be held in the partially protruding position by use of a support film adhered to the sheet material of the invention, for example, as taught in column 4 of U.S. Patent No. 4,988,541.

In some embodiments, the pavement marking includes an adhesive composition or layer that is capable of bonding the sheet to a roadway surface. As used herein in this context, the term "adhesive" refers to a composition capable of bonding the pavement marking to the roadway. Some exemplary adhesive compositions include those selected from a group consisting essentially of pressure sensitive adhesives, thermoplastic resin-containing compositions, hot melt adhesives, thermoset adhesives, contact adhesives, acrylic adhesives, epoxy adhesives, urethane adhesives, and combinations thereof. Some implementations of these include a wide variety of non-thermoplastic hydrocarbon elastomers including, natural rubber, butyl rubber, synthetic polyisoprene, ethylene -propylene rubber, ethylene-propylene- diene monomer rubber (EPDM), polybutadiene, polyisobutylene, poly(alpha-olefm), styrene-butadiene random copolymer rubber, acrylate based pressure sensitive adhesive compositions.

As used herein, the term "preformed pavement marking" means a pavement marking that has been formed into the desired shape or configuration prior to installation. These can be applied directly to the pavement by heating or with an adhesive. One benefit of using a preformed marking is that it requires less equipment and less material for small-area applications. Another advantage is the ability to use smaller equipment which aids in the application of intersection markings and symbols where it is difficult to use hand-liners or truck applicators.

Desired surfaces for preformed pavement marking attachment include, for example, vehicle surfaces for driveways, parking lots, bicycle paths, golf course paths, decks, patios and generally any surface where there may be pedestrian, powered vehicle traffic or building structures. Other examples of potential uses include crosswalks, custom logos, entryways, driveways, parks and horizontal signage, etc. Because these pavement markers are produced in a factory, and not on site, the pavement markers may have higher quality and improved visual appearance. Examples describing preformed markings are in US 8,247,054 B2 and US 6,270,871.

Typical roadway surfaces are rough (rather than smooth). As such, good adhesion of the pavement marking to the roadway surface is preferred. The pavement markings of the present disclosure may adapt to and accommodate road surface irregularities.

The pavement markers and pavement marking composition of the present disclosure have various performance or physical attributes. For example, in some embodiments, the pavement marking composition and/or pavement markers described herein have a contact angle of 64°. In some

embodiments, the pavement markings of the present disclosure have a mandrel bend flexibility of 6 inches of diameter or less. In some embodiments, the pavement markings of the present disclosure have a CAP-Y of at least 80. In some embodiments, the pavement markings of the present disclosure have an energy at break of greater than 0.1 ft*lbf / in³. Each of these physical parameters are measured as described in the examples below.

Advantages and embodiments of this disclosure are further illustrated by the following examples, but the particular materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit this application. In these examples, all percentages, proportions and ratios are by weight unless otherwise indicated.

Examples

Test Methods

CAP-Y: Samples were cut from the extruded web and minimum of 2 inch by 2inch area and Cap Y was measured using a colorimeter (model COLORFLEX obtained from Hunter Associates Laboratory, Reston, VA) using a D65 illuminant and 10 degree observer, following the procedure outlined in ASTM E313-10, "Standard Practice for Calculating Yellowness and Whiteness Indices from Instrumentally Measured Color differences".

Energy at break: tensile elongation testing was performed on a tensile testing machine with MTS Renew upgrade package (model SINTECH 1). A 200 lb load cell (Eaton Model 3397-200), pneumatic grips, and MTS TESTWORKS 4 software were used. Testing was performed following the procedure outlined in ASTM D638-XX, "Standard Test Method for Tensile Properties of Plastics", using a 0.2 in/min crosshead rate at standard conditions (25.deg. C and 50% relative humidity), except specimens measured 0.5 inch wide (12.7 mm) by 4 inch long (101.6 mm), by 0.1 +/- 0.02 inch (2.54 +/- 0.5 mm) thick with 2 inch (50.8 mm) gage length. Energy at break was calculated using the TESTWORKS 4 software.

Contact Angle: static water contact angle was measured following the procedure outlined in

ASTM D7334-XX, "Standard Practice for Surface Wettability of Coatings, Substrates and Pigments by Advancing Contact Angle Measurement". A Brighton Surface Analyst Model No. SAIOOI obtained from Brighton Technologies Group, Cincinnati, OH, was used. Results are reported as the average of a minimum of three repeat measurements.

Flexibility: flexibility was tested according to the procedure outlined in ASTM D31 1 1 - 10, "Standard Test Method for Flexibility Determination of Hot-Melt Adhesives by Mandrel". Bend radius samples were tested on 6 in (15 cm), 2 in (5 cm), 1 in (2.5 cm), ¾ in (1.9 cm), ½ in (1.27 cm), and ¼ in (0.64 cm) in diameter mandrels. An asterisk (*) indicates that failure mode is break.

Melt Index: measured as described in ASTM D 1238. Materials

Material Description Supplier

UL 7510 Ethylene vinyl acetate copolymer resin, 18.7% vinyl Exxon Mobil Corp., acetate, and a melt flow index of 500 g/lOmin. Irving, TX

UL 8705 Ethylene vinyl acetate copolymer resin, 27.6% vinyl Exxon Mobil Corp.

acetate, and a melt flow index of 800 g/lOmin.

AD2528 Ethylene vinyl acetate copolymer resin, 27.6% vinyl Exxon Mobil Corp.

acetate, and a viscosity of 2800 mPa.s at 190oC.

NUCREL 3990 Ethylene acrylic acid copolymer resin, 9.5% acrylic DuPont, Wilmington acid. Delaware

EL VAX 210 W Ethylene vinyl acetate copolymer resin, 28% vinyl DuPont

acetate, and a melt flow index of 400 g/lOmin.

EL VAX 420 Ethylene vinyl acetate copolymer resin, 18% vinyl DuPont

acetate, and a melt flow index of 150 g/lOmin.

ESCOREZ 5400 Light color cycloaliphatic hydrocarbon resin Exxon Mobil Corp.

AC 5120 Resin, Ethylene acrylic acid copolymer (EAA) MN = Honeywell International,

1005g/mol, 15 weight% acrylic acid Inc., Morristown, NJ

AC 540 Resin, Ethylene acrylic acid copolymer (EAA) MN = Honeywell International,

1005g/mol, Acid number 40, acrylic acid content 5% Inc.

R-960 Titanium dioxide, 5 micron particle DuPont

OMYACARB 5 Calcium Carbonate Extender pigment, 6 micron Omya Inc., Proctor, VT particle

"MEGA-LUX Glass spheres with a refractive index (RI) of 1.5 and Swarco Industries, TYPE average diameter between 1.0 mm and 1.18 mm. Columbia, TN

3 GLASS

SPHERES"

"MEGA-LUX Glass spheres having a RI of 1.5 and average Swarco Industries TYPE diameter between 0.3 mm and 0.6 mm.

1 GLASS

SPHERES"

WEST REZ 5101P Resin acids and rosin acids, esters with Mead Westvaco, North pentaerythritol Charleston, SC

VECTOR 4411 A Styrene-Isoprene-Styrene (SIS) Block Copolymer Dexco Polymers,

Houston, TX

3M BONDING Light-colored thermoplastic adhesive bonding film 3M Company, St. Paul, FILM 615 MN Examples

Examples 1 and 2 are dual-layer thermoplastic pavement markings, and Examples A-H are single-layer pavement markings according to the present disclosure.

Example 1

A dual-layer thermoplastic pavement marking was prepared by simultaneously extruding a thermoplastic pavement marking composition and an adhesive layer through a die. The pavement marking composition was obtained by mixing the materials listed in Table 1, below in a 50mm twin screw extruder (model MPC/V - 50, obtained from Baker Perkins, from Saginaw, Michigan) set to a temperature of about 300-350°C, coupled to a 12-inch wide dual layer die. An adhesive layer was prepared by melting a thermoplastic adhesive bonding film as described below. The die had a 100 mil (2.54 mm) shim for the pavement marking composition and an 8 mil (0.2 mm) shim for the adhesive layer. The amount of materials listed in Table 1 is expressed as weight percent (wt%) based on the total weight of the composition.

Table 1. Example 1 Composition Information

The UL 7510 and ESCOREZ5400 were obtained in pellets and premixed, forming a polymer premix. The T1O2 and CaCCb were obtained in powder form and also separately premixed to form a powder premix. All materials were then fed with twin screw feeders, with the polymer and powder premixes being fed into the first port and mixed and the glass beads being fed into the second port (after which the material was conveyed without forced mixing) The feed rate for the polymer premix was 16.2 lb/hr, the feed rate for the powder premix was 19.81b/hr and the feed rate for the beads was 12 lb/hr each. The belt speed of the extruder was 1.5 fpm, and the screw speed was 200 rpm. The belt was covered with a 12 in wide 3 mil release coated paper liner and carried away the material at 1.5 fpm. The actual extrudate width was approximately 1 1.25 in.

3M Bonding Film 615 was delivered by a gridmelter targeted at 6 lb/hr. The resulting adhesive layer was approximately 8 mil thick in the center and about 10-14 mils thick toward the edges. The resulting dual-layer thermoplastic pavement marking was tested for: contact angle, flexibility, CAP Y and, using the procedures described above. Results are reported in Table 5, below.

Example 2

A dual-layer thermoplastic pavement marking composition was prepared as described in Example

1 , except that a different polymer composition and adhesive were used, and the maximum extruder temperature was 325°F. Materials for the thermoplastic pavement marking composition are shown in Table 2, below, expressed as weight percent (wt%) based on the total weight of the composition.

Table 2. Example 2 Composition Information

A hot-melt adhesive was prepared by extruding a mixture of 45 wt% of VECTOR 441 1 A (SIS block copolymer) and 55 wt% of WEST REZ 5101P (rosin ester tackifier), wherein the weight percentages are based on the total weight of the adhesive composition. The hot melt was extruded with a 30mm diameter MP 2030TC extruder (from APV, Saginaw, Michigan) at temperatures between 200- 325°F This mixture was fed into the die to form the co-extruded adhesive layer. The VECTOR 441 1 A was fed into the first port at 2.7 lb/hr using a twin screw feeder, while the hot melt was fed at 3.3 lb/hr into later ports using a gridmelter.

The resulting dual-layer thermoplastic pavement marking was subjected to the following test methods: surface contact angle, flexibility, CAP Y and flexibility, using the procedures described above. Results are reported in Table 5, below.

Examples A-H

Single layer thermoplastic pavement marking compositions were prepared as described in Example 1, above, except that (i) a 6 in (15.24 cm) single layer die was used (ULTRAFLEX R 75, from Extrusion Die Industries; Chippewa Falls, WI); and (ii) different materials and process conditions were used, as shown in Tables 3 and 4, below. Table 3. Examples A-H Composition Information

Table 4. Process Conditions for Examples A-H

Examples A - H were subjected to the following test methods: surface contact angle, flexibility, CAP Y and flexibility using the procedures described above. Results are reported in Table 5, below. Results

Thermoplastic pavement markings prepared as described in Examples A-H, and Examples 1 and 2 were tested for: contact angle, energy at break, flexibility and CAP Y, using the procedures described above. Results are reported in Table 5, below, wherein bend radius samples were tested on 6, 2, 1, 3/4, ½, and ¼ in diameter mandrels. An asterisk (*) indicates that failure mode is break.

Table 5. Performance Data for Examples 1-2 and A-H

The terms first, second, third and the like in the description and in the claims, are used for distinguishing between similar elements and not necessarily for describing a sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances and that the embodiments of the invention described herein are capable of operation in other sequences than described or illustrated herein.

Moreover, the terms top, bottom, over, under and the like in the description and the claims are used for descriptive purposes and not necessarily for describing relative positions. It is to be understood that the terms so used are interchangeable under appropriate circumstances and that the embodiments of the invention described herein are capable of operation in other orientations than described or illustrated herein.

The recitation of all numerical ranges by endpoint is meant to include all numbers subsumed within the range (i.e., the range 1 to 10 includes, for example, 1, 1.5, 3.33, and 10).

Those having skill in the art will appreciate that many changes may be made to the details of the above-described embodiments and implementations without departing from the underlying principles thereof. Further, various modifications and alterations of the present invention will become apparent to those skilled in the art without departing from the spirit and scope of the invention. The scope of the present application should, therefore, be determined only by the following claims.

Claims

What is claimed is:

1. A thermoplastic pavement marking composition, comprising:

greater than about 7 wt% ethylene vinyl acetate based on the total weight of the composition.

2. The thermoplastic pavement marking composition of claim 1, further comprising:

less than about 80 wt% ethylene vinyl acetate based on the total weight of the composition.

3. The thermoplastic pavement marking composition of any of the preceding claims, wherein the ethylene vinyl acetate has a melt flow index of between about 10 g/ 10 min and about 800 g/ lO min at 190°C.

4. The thermoplastic pavement marking composition of any of the preceding claims, wherein the ethylene vinyl acetate has a melt flow index of between about 150 g/ 10 min and about 800 g/ 10 min at 190°C.

5. The thermoplastic pavement marking composition of any of the preceding claims, further comprising:

a resin selected from a group consisting essentially of rosin esters, hydrogenated rosin resins, dimerized rosin resins, modified rosin resins, hydrocarbon resins, C5 aliphatic resins, hydrogenated C5 aliphatic resins, C5 aromatic resins, C9 aromatic resins, pure monomer C9 aromatic resins, hydrogenated C9 aromatic resins, C5/C9 aliphatic / aromatic hydrocarbon resin,C10 resins, modified CIO resins, pure monomer resins, hydrogenated pure monomer resins, pure aromatic monomer resins, low molecular weight fully hydrogenated inert thermoplastic resin derived from petrochemical feedstocks, and combinations thereof.

6. The thermoplastic pavement marking composition of claim 5, wherein the ratio of ethylene vinyl acetate to resin is between about 80:20 to about 40:60.

7. The thermoplastic pavement marking composition of either claim 5 or 6, wherein the ratio of ethylene vinyl acetate to resin is between about 3: 1 to about 1.5: 1.

8. The thermoplastic pavement marking composition of any of the preceding claims, wherein the ethylene vinyl acetate has a vinyl acetate content of between about 18 wt% and about 28 wt%.

9. The thermoplastic pavement marking composition of any of the preceding claims, further comprising:

an adhesive adjacent to the thermoplastic pavement marking composition.

10. The thermoplastic pavement marking composition of claim 9, wherein

the adhesive is selected from a group consisting essentially of pressure sensitive adhesives, thermoplastic resin-containing compositions, hot melt adhesives, thermoset adhesives, contact adhesives, acrylic adhesives, epoxy adhesives, urethane adhesives, non-thermoplastic hydrocarbon elastomers, natural rubber, butyl rubber, synthetic polyisoprene, ethylene -propylene rubber, ethylene-propylene- diene monomer rubber (EPDM), polybutadiene, polyisobutylene, poly(alpha-olefm), styrene-butadiene random copolymer rubber, acrylate based pressure sensitive adhesive compositions, and combinations thereof.

1 1. The pavement marking composition of any of the preceding claims, comprising:

greater than about 10 wt% ethylene vinyl acetate based on the total weight of the composition.

12. The pavement marking composition of any of the preceding claims, comprising:

greater than about 15 wt% ethylene vinyl acetate based on the total weight of the composition.

13. The pavement marking composition of any of the preceding claims, comprising:

greater than about 20 wt% ethylene vinyl acetate based on the total weight of the composition.

14. A pavement marker, comprising:

the pavement marking composition of any of the preceding claims.

15. The pavement marker of claim 14, wherein the pavement marker is a preformed pavement marker.

16. The pavement marker of claim 14 or claim 15, having a contact angle of at least 64°.

17. The pavement marker of any of claims 14-16, having an energy at break of at least 0.1 ft*M / in³.

18. The pavement marker of any of claims 14-17, having mandrel bend flexibility of 6 inches of diameter or less.

19. The pavement marker of any of claims 14- 18, wherein the pavement marker has a CAP of greater than 80.