High content polyamide hot-applied thermoplastic composition

Abstract

A hot applied thermoplastic pavement composition and method of using a hot applied thermoplastic pavement composition includes a modified polyamide resin in the range of between 3 and 10 percent by weight, wherein the composition contains rosin-modified esters, a copolymer, 30-70 percent by weight of a glass bead intermix, a range of between 1 and 15 percent by weight of either white or yellow pigment, the balance of the composition being selected from the group consisting of one or more plasticizers, inorganic fillers, waxes, antioxidants and light stabilizers.

Claims

1. A hot applied thermoplastic pavement marking composition comprising: 3 to 10 weight percent of a modified polyamide resin comprising a di-functional amine; a rosin-modified ester; a copolymer; 30 to 70 weight percent of a glass bead intermix; 1 to 15 weight percent of a white or yellow pigment; and one or more of a plasticizer, an inorganic filler, a wax, an antioxidant or a light stabilizer, wherein the ester comprises one or more of a pentaerythritol modified ester, a maleic modified glycerol rosin ester or ethylene maleic anhydride.

2. The composition of claim 1, wherein the glass bead intermix comprises AASHTO Type 1 glass beads and one of AASHTO Type 3 glass beads or AASHTO Type 4 glass beads.

3. A thermoplastic marking for a substrate comprising the composition of claim 1.

4. A thermoplastic marking for a substrate, the marking comprising: a polyamide resin comprising a di-functional amine; a rosin-modified ester; a copolymer; and up to 50 weight percent of a glass bead intermix comprising AASHTO Type 1 glass beads and one of AASHTO Type 3 glass beads or AASHTO Type 4 glass beads, wherein the marking has a softening point from 115° C. to 140° C.

5. The marking of claim 4, wherein the marking is a profiled marker that forms textures, bumps, profiles, or combinations thereof, wherein the profiled marker extends above a top surface of the substrate.

6. The marking of claim 5, wherein the profiled markers are configured to be located at varying intervals along a length of the substrate.

7. The marking of claim 4, wherein the marking is an inlaid marker, applied to grooves in a substrate, wherein the inlaid marker is substantially even with a top surface of the substrate.

8. The marking of claim 4, further comprising a plasticizer, an inorganic filler, a wax, a pigment, an antioxidant or a light stabilizer, or combinations thereof.

9. The marking of claim 4, wherein the marking comprises 3 to 10 weight percent of the polyamide resin.

10. The marking of claim 4, wherein the glass beads have a retro-reflectivity value that ranges from 200 to 2000 mcd/m.sup.2/1x.

11. The marking of claim 4, wherein the marking has an Gardner Impact resistance value of greater than 15 inch-pounds at 0° C.

12. The marking of claim 4, wherein the marking has an Gardner Impact resistance value of 15 to 40 inch-pounds at 0° C.

13. The marking of claim 4, further comprising a top dressing of at least one of AASHTO Type 1 glass beads or AASHTO Type 4 glass beads.

14. The marking of claim 4, wherein the marking has abrasion loss in weight of less than 0.5 mg according to test California Test 423 (CTM 423).

15. A method for applying a thermoplastic marking to a substrate, comprising: heating the composition of claim 1; and applying a portion of the heated composition onto a substrate to form a thermoplastic marking.

16. The method of claim 15, further comprising applying a primer to the substrate prior to applying the composition.

17. The method of claim 16, wherein a bond strength between the thermoplastic marking and the primed substrate is greater than 250 psi at 90% failure according to ASTM D 4796.

18. The method of claim 16, wherein a bond strength between the thermoplastic marking and the substrate is greater than 400 psi at 50% failure according to ASTM D 4796.

19. The method of claim 15, further comprising applying a top dressing of glass beads to the thermoplastic marking on the substrate.

20. The method of claim 15, wherein the substrate comprises asphalt or concrete.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a schematic diagram of the AASHTO NTPEP Test Deck Configuration.

(2) FIGS. 2a-2c provide photographic comparisons of the bond strength of white increased polyamide hot-applied thermoplastic pavement markers and the conventional white AASHTO hot-applied thermoplastic pavement marker.

(3) FIGS. 3a-3c are photographic comparisons of the bond strength of yellow hot-applied thermoplastic pavement marker with increased polyamide content and a conventional yellow AASHTO hot-applied thermoplastic pavement marker.

(4) FIGS. 4a-4d provide photographic records of the Abrasion test results for white and yellow conventional AASHTO and increased polyamide content hot-applied thermoplastic pavement markers.

(5) FIGS. 5a-5d are photographic records of the Gardner Impact test results, at 0° C., for white and yellow conventional AASHTO and increased polyamide content hot-applied thermoplastic pavement markers.

DETAILED DESCRIPTION

(6) The schematic diagram provided in FIG. 1 is an AASHTO NTPEP conventional test deck configuration [100] used for testing of pavement marking materials by the NTPEP Pavement Marking Materials (PMM) Technical Committee (TC). Application of permanent products and non-removable tapes [120] are provided as four (4) lines per manufacturing run of pavement with two (2) lines of either marked at two different locations within the AASHTO NTPEP conventional test deck configuration [100]. Multiple products by different manufacturing runs are denoted as product A [122], B [124], C [126] etc. Temporary Removable Tapes [130] are directed to a test deck application of six (6) transverse lines [132] and 6 longitudinal lines [134].

(7) Readings are taken from the test deck at specified areas of the applied marking and are termed the “skip” reading and the “wheel” reading. The “skip” reading is taken from the marking closest to the skip line [140] of the road, termed the skip reading location [142]. Readings taken in the wheel path closest to the skip line [140] of the road, labeled as the upper wheel path [144], are provided as “wheel” readings and are taken from the wheel reading location [146].

(8) In accordance with the ASTM 2177 wet recovery test, wet retroreflectivity readings are taken within nine (9) inches of the line closest to the road edge line [148], known as the wet reading location [150].

(9) FIG. 2a is a photographic comparison of the bond strength test results [200] for the white increased polyamide content hot-applied thermoplastic [202] and the conventional AASHTO white hot-applied thermoplastic pavement marker [210] (marked “Control”), as applied to a concrete substrate [212]. The conventional AASHTO white hot-applied thermoplastic pavement marker [210] exhibited significant failure of the marking [214] while the white marker having significantly increased polyamide content hot-applied thermoplastic [202] exhibited significant substrate failure [216].

(10) FIG. 2b provides a more detailed photographic depiction of the bond strength of a conventional AASHTO white hot-applied thermoplastic pavement marker [210], as applied to a concrete substrate [212] also exhibiting significant failure of the marking [214].

(11) FIG. 2c is a more detailed photograph depicting the bond strength of the white increased polyamide hot-applied thermoplastic pavement marker [202], as applied to a concrete substrate [212], where significant failure of the substrate [216] is again shown.

(12) FIG. 3a is a photographic comparison of the bond strength test results [200] illustrating the differences between the yellow markers with increased polyamide content hot-applied thermoplastic [302] and the conventional AASHTO yellow hot-applied thermoplastic pavement marker [304], as applied to a concrete substrate [212]. The conventional AASHTO yellow hot-applied thermoplastic pavement marker [304] exhibited significant failure of the marking [214] while the yellow marker with increased polyamide content hot-applied thermoplastic [302] exhibited significant substrate failure [216].

(13) FIG. 3b provides a closer view of the bond strength difference with a conventional AASHTO yellow hot-applied thermoplastic pavement marker [304], as applied to a concrete substrate [212], where significant failure of the marking [214] is exhibited

(14) FIG. 3c is a photograph of the bond strength of the yellow increased polyamide hot-applied thermoplastic pavement marker [302], as applied to a concrete substrate [212], illustrating significant failure of the substrate [216].

(15) FIGS. 4a through 4d yield photographic records of the Abrasion test results [400] for a conventional and improved hot-applied thermoplastic marking. The conventional AASHTO white hot-applied thermoplastic pavement marker [210], serving as a control, was prepared as a hot-application mold to a base plate (not shown). FIG. 4a provides an abrasive blasting of the hot-application mold to a base plate showing significant wear of the conventional AASHTO white hot-applied thermoplastic marker [210] as evidenced by heavily abraded regions [410]. FIG. 4b provides the Abrasion test results [400] for a white increased polyamide hot-applied thermoplastic pavement marker [202]. The abrasive blasting of the increased polyamide content marker shows minimal wear, as evidenced by the scantily abraded regions [410] of the hot-application mold to a base plate. FIGS. 4c and 4d offer photographic records of the Abrasion test results [400] for a conventional AASHTO yellow hot-applied thermoplastic pavement marker [304], serving as a control, and a yellow increased polyamide hot-applied thermoplastic pavement marker [302].

(16) FIGS. 5a through 5d provide the Gardner impact test results, at 0° C., for the conventional and increased polyamide content hot-applied thermoplastic pavement markers. FIG. 5a shows the Gardner Impact test results at 0° C. [500] for a conventional AASHTO white hot-applied thermoplastic pavement marker [210], while FIG. 5b is a photographic record of the Gardner Impact test results [500] for a white pavement marker with increased polyamide hot-applied thermoplastic [202]. FIG. 5c shows the Gardner Impact test results [500] for a conventional AASHTO yellow hot-applied thermoplastic pavement marker [210], while FIG. 5d yields a photographic record of the Gardner Impact test results [500] for a yellow increased polyamide hot-applied thermoplastic pavement marker [202]. Each sample provides a point of impact [510]; however, the conventional white [210] and conventional yellow AASHTO yellow hot-applied thermoplastic markers display in impact failure [512] that is not evidenced with the white [202] and yellow [302] increased polyamide content hot-applied thermoplastic markers.

WORKING AND COMPARATIVE EXAMPLES

(17) In order to more precisely describe representative compositions of the present disclosure, example formulations of the hot-applied thermoplastic are provided, in total weight percent, in the following working examples:

Working Example 1

(18) Material Composition—White Extrude (W.sub.Ex)

(19) TABLE-US-00003 Polyamide (2526c-01) 7.0% Maleic modified rosin (Arizona 7021) 10.0% EVA Copolymer (Exxon UL7510) 1.0% Polyethylene Wax (Coschem CS-42F) 2.0% Plasticizer (Castor Oil #1 Raw) 2.0% HALS (Unitechem 622) 0.2% Antioxidant (BASF Iraganox 1010) 0.2% TiO2, Rutile Type II (Tronox CR-828) 12.0% Blue Pigment 29 (Nubiola CP-84) 0.025% Fumed Silica (Evonik Aerosil R208) 0.5% Calcium Carbonate (Huber G260A) 15.075% Beads Type 3 (Weissker AASHTO M 247-11, 25.0% 80% rounds, dual coated) Beads Type 1 (Weissker AASHTO M 247-11, 25.0% 80% rounds, dual coated) Total % 100.00% Total % Binder 22.0% Total % Beads 50.0%

(20) The material can be applied, as an extrudate, at a thickness of 60-150 mil and an application temperature of 400-440° F., as is the general requirement for a hot-applied thermoplastic composition for pavement marking.

(21) White extrudate of the composition provided above was applied on a pavement marking industry test site (AASHTO NTPEP Test Deck, Asphalt and Concrete, Minnesota, Jul. 31, 2013) at a thickness of 90-120 mil at a temperature of 400-440° F. A top dressing of drop-on beads was applied as follows: 8-12 lbs./100 ft.sup.2 Type 4 beads, 4-8 lbs./100 ft.sup.2 Type 1 beads. Application of the marking material was performed by the use of a hand liner extrusion.

Working Example 2

(22) Material Composition—Yellow Extrude (Y.sub.Ex)

(23) TABLE-US-00004 Polyamide (2526c-01) 7.0% Maleic modified rosin (Arizona 7021) 9.75% EVA Copolymer (Exxon UL7511) 1.2% Polyethylene Wax (Coschem CS-42F) 2.25% Plasticizer (Castor Oil #1 Raw) 1.8% HALS (Unitechem 622) 0.4% Antioxidant (BASF Iraganox 1010) 0.2% TiO2, Rutile Type II (Tronox CR-828) 1.4% Yellow 83 Pigment (Clariant HRT) 1.1% Calcium Carbonate (Huber G260A) 24.9% Beads Type 3 (Weissker AASHTO M 247-11, 25.0% 80% rounds, dual coated) Beads Type 1 (Weissker AASHTO M 247-11, 25.0% 80% rounds, dual coated) Total % 100.00% Total % Binder 22.0% Total % Beads 50.0%

(24) Yellow extrudate of the composition provided above was applied on a pavement marking industry test site (AASHTO NTPEP Test Deck, Asphalt and Concrete, Minnesota, Jul. 31, 2013) at a thickness of 90-120 mil at a temperature of 400-440° F. A top dressing of drop-on beads was applied as follows: 8-12 lbs./100 ft.sup.2 Type 4 beads, 4-8 lbs./100 ft.sup.2 Type 1 beads. Application of the marking material was performed by hand liner extrusion.

Working Example 3

(25) White High Performance Pavement Marker (See Table 4a)

(26) TABLE-US-00005 Polyamide (2526c-01) 7.0% Maleic modified rosin Ester (highly 10.3% maleated) EVA Copolymer 0.5% Polyethylene Wax (Coschem CS-14N) 2.0% Ethylene Maelic Anhydride 0.5% HALS (Unitechem 622) 0.2% Antioxidant (BASF Iraganox 1010) 0.2% DINP 1.7% TiO2, Rutile Type II (Tronox CR-828) 12.0% Blue Pigment 29 (Nubiola CP-84) 0.0125% Calcium Carbonate (Huber G260A) 15.5875% Beads Type 3 (Weissker AASHTO M 247-11, 25.0% 80% rounds, dual coated) Beads Type 1 (Weissker AASHTO M 247-11, 25.0% 80% rounds, dual coated) Total % 100.00% Total % Binder 22.0% Total % Beads 50.0%

(27) For working Example 3, a full set of testing was performed by Future Labs of Madison, Miss., regarding a white thermoplastic W5E-5X-AA Sample A provided by Ennis-Flint. The results are shown in Table 3 below. These test results confirm the use of greater than 50% glass content with a complete binder content of 22.31 wt. %, for which 7 wt. % polyamide content was used in the overall final composition. Reflectance was reported per ASTM D 4960 as 83.12% using a Type 3 and Type 1 50% bead content (25% each). Impact resistance at ambient and cool-weather conditions (32° F. and 75° F.) was reported as 10.10 in. lbs. and 12.000 in. lbs., respectively, and low temperature resistance, tested per AASHTO T 250, exhibited no cracks. The sand blast abrasion test, also referred to as the box abrasion test, provided a 0.1 g loss, while the taber abrasion test provided a 118 mg loss. The bond strength of the white improved thermoplastic was tested with primer, with no primer and with primer and extended cure. The bond strength results were obtained per ASTM D 4796 and showed 50% failure of the concrete substrate at 443 psi with the use of no primer. Using a primer, the bond strength was determined to provide 90% failure of the primer-thermoplastic joining at 255 psi. The combined use of a primer and allowance for extended curing also provided a 90% failure of the primer-thermoplastic joining at 335 psi.

(28) TABLE-US-00006 TABLE 3 Test Methods Specification Results Binder Content ASTM D 4797 22.31% Glass Bead Content ASTM D 4797 50.94% TiO2 Pigment Content (assuming >92% TiO2 Purity) ASTM D 4764 21.63% Color after 4 hrs (@ 425° F.) AASHTO T 250 Matches Fed. Std. 17886 Reflectance ASTM D 4960 83.12% Yellowness Index ASTM E 313 0.05 Softening Point ASTM D 36 204° F. Impact Resistance (@ 32° F.) ASTM D 4812 10.10 in. lbs. Impact Resistance (@ 75° F.) ASTM D 4812 12.00 in. lbs. Low Temp Resistance AASHTO T 250 no cracks Specific Gravity ASTM D 792 1.98 Inert Filler 5.12% Flowability (4 hrs) AASHTO T 250 10.62% Extended Flowability (8 hrs) AASHTO T 250 8.72% Drying Time (@ 50° F.) ASTM D 711 <2 minutes Drying Time (@ 90° F.) ASTM D 711 <10 minutes Drop Impact (@ 32° F.) ASTM D 5420 PASS Drop Impact (@ 75° F.) ASTM D 5420 PASS Sand Blast Abrasion CTM 423 0.1 g loss Taber Abrasion ASTM D 4060 118 mg loss Tensile Strength (avg of 3) ASTM D 638 233 psi Tensile Elongation (avg of 3) ASTM D 638 43.70% Compressive Strength (avg ASTM D 695 961 psi of 3) Bond Strength (no Primer) ASTM D 4796 443 psi/50% Concrete Failure Bond Strength (with Primer) ASTM D 4796 255 psi/90% Primer- Thermo Failure Bond Strength (Primer & ASTM D 4796 335 psi/90% Primer- Extended Cure) Thermo Failure Pull Test FL DOT 971-7.9 PASS Flexibility ASTM D 3111 PASS Product: Working Example #5 (Future Labs, LLC, Madison, MS; Results dated Jan. 24, 2014)

Working Example 4

(29) See Table 4—referred to as “Yellow High Performance”

(30) TABLE-US-00007 Polyamide (2526c-01) 7.0% Maleic modified rosin ester (highly maleated) 9.7% EVA Copolymer (Exxon UL7510) 1.25% Polyethylene Wax (Coschem CS-42F) 2.25% Plasticizer (Castor Oil #1 Raw) 1.8% HALS (Unitechem 622) 0.4% Antioxidant (BASF Iraganox 1010) 0.2% TiO2, Rutile Type II (Tronox CR-828) 1.35% Yellow 83 Pigment (Clariant HRT) 1.25% Calcium Carbonate (Huber G260A) 24.8% Beads Type 3 (Weissker AASHTO M 247-11, 25.0% 80% rounds, dual coated) Beads Type 1 (Weissker AASHTO M 247-11, 25.0% 80% rounds, dual coated) Total % 100.00% Total % Binder 23.425% Total % Beads 50.0%

Working Example 5

(31) Referred to in Table 4 as “Yellow High Performance”

(32) TABLE-US-00008 Polyamide (2526c-01) 7.0% Maleic modified rosin ester (highly maleated) 10.5% EVA Copolymer (Exxon UL7510) 0.25% Polyethylene Wax (Coschem CS-14N) 2.2% Ethylene Maleic Anhydride 0.25% Plasticizer (Castor Oil #1 Raw) 1.8% HALS (Unitechem 622) 0.4% Antioxidant (BASF Iraganox 1010) 0.2% TiO2, Rutile Type II (Tronox CR-828) 1.35% Yellow 83 Pigment (Clariant HRT) 1.25% Calcium Carbonate (Huber G260A) 24.8% Beads Type 3 (Weissker AASHTO M 247-11, 25.0% 80% rounds, adhesion coated) Beads Type 1 (Weissker AASHTO M 247-11, 25.0% 80% rounds, dual coated) Total % 100.00% Total % Binder 22.0% Total % Beads 50.0%

Comparative Example 1

(33) As an illustration, Comparative Example 1 uses a lower percentage by weight of polyamide Permaline is a proprietary formulation manufactured by Ennis-Flint, using a polyamide content of less than 3% and rosin ester combinations, filler and additional additives including, polymer(s), wax(s) and vegetable oil(s) and demonstrating a 30% Type 1 glass bead content by weight.

Comparative Example 2

(34) As a further illustration, Comparative Example 2 is an AASHTO conventional yellow formulation that uses no polyamide, and is referred to in Table 4 as “Yellow AASHTO M 249”

(35) TABLE-US-00009 Binder 18.0% min. Glass Bead 30-40% Calcium Carbonate and inert fillers ** Yellow Pigments ** **Per AASHTO Designation M 249-09, the amount of yellow pigment, calcium carbonate, and inert fillers shall be at the option of the manufacturer, providing all other requirements of the specification are met.

Comparative Example 3

(36) In yet another comparative illustration, Comparative Example 3 is an AASHTO conventional white formulation that uses no polyamide, and is referred to in Table 4 as “White AASHTO M 249”

(37) TABLE-US-00010 Binder 18.0% min. Glass Bead 30-40% TiO2 10.0% min. Calcium Carbonate and inert fillers 42.0% max.

(38) Formulation differences in the AASHTO conventional compositions and the improved polyamide containing hot-applied thermoplastic marking material, as detailed in the working examples are provided in Table 4.

(39) All of the newly disclosed compositions completely replace the use of a maleic modified rosin ester and rosin ester with the use of a highly maleated maleic modified rosin ester and ethylene maleic anhydride. The new compositions also show the inclusion of a hindered amine light stabilizer (HALS) and an antioxidant. The amount of calcium carbonate required for the new formulations is at least half or more of the amount provided in the conventional AASHTO formulations.

(40) TABLE-US-00011 TABLE 4 Yellow White Yellow High White High Yellow High Perfor- AASHTO Perfor- AASHTO Perfor- mance % Wt. M 249 mance M 249 mance (Alternate) TiO2 10 12 1.5 1.35 1.35 (Rutile) Blue 0.005 0.0125 0 0 0 Pigment Yellow 83 0 0 0.75 1.25 1.25 Pigment Maleic 8.55 0 8.55 0 0 Modified Rosin Ester Maleic 0 10 0 9.7 10.25 Modified Rosin Ester (highly maleated) Rosin Ester 7.5 0 8.25 0 0 Polyamide 0 7 0 7 7 PE Wax 0.5 2 0.25 2.25 2.35 Ethylene 0 0.5 0 0 0.25 Maleic Anhydride EVA 0.25 0.5 0.25 1.25 0.25 HALS 0 0.2 0 0.4 0.4 Antioxidant 0 0.2 0 0.2 0.2 Type 3 Glass 0 25 0 25 25 Beads Type 1 Glass 30 25 30 25 25 Beads Castor Oil 2.2 0 2.2 1.8 1.8 DINP 0 2 0 0 Calcium 41.595 15.5875 48.25 24.8 24.4 Carbonate Total 100 100 100 100 100 % Binder 19 22.00 19.5 23.425 22.00

(41) Test Methodology

(42) Testing methods used to determine the improved characteristics of the disclosed polyamide composition in comparison with current thermoplastics include Abrasion testing, Gardner Impact testing and NTPEP desk deck application NTPEP evaluations conducted in the field include retro-reflectivity, durability, daytime color, nighttime color (for yellow materials) and wet night retro-reflectivity for products that are permanent or temporarily applied.

(43) Gardner Impact, also known as Falling Dart Impact, is a traditional method for the evaluation of impact strength or toughness of a plastic material. The test is often used to specify appropriate materials for applications involving impact or to evaluate the effect of secondary finishing operations or other environmental factors on plastic impact properties.

(44) The test sample is placed on a base plate over an opening of specified diameter. An “impactor” sits on top of the test sample with a nose of specified radius in contact with the center of the test sample. A weight is raised inside a guide tube to a predetermined height, and then released to drop onto the top of the impactor, forcing the nose through the test sample. The drop height, drop weight, and the test result (pass/fail) are recorded. For this disclosure, ASTM Standard D4812-11, entitled “Standard Test Method for Unnotched Cantilever Beam Impact Resistance of Plastics”, was followed using a two (2) pound drop weight from a height of 5.05 in per pound.

(45) The Box Abrasion test was employed as described in California Test 423 (CTM 423 or CALTRANS Method) entitled “Method for Testing Thermoplastic Traffic Line Material”, Part 14, Abrasion Test (Dec. 1, 2006). As described in the standard, CTM 423 14.A.2, the abrasive media used were glass beads having a gradation size of 100% pass-through of a #25 sieve (710 micron) and 100% retention on a #30 sieve (590 micron). Glass beads (400 g.) were directed at the hot-applied thermoplastic at a pressure of 40 psi and a specimen distance of 4⅞″ from the spray nozzle per CTM 423 14.B.5 and CTM 423 14.B.7. The specimen is then rotated approximately 90 degrees from the original position and a new corner of the sample is subjected to abrasive blasting with the specified glass beads. The loss of each corner is measured for each of the four corners of the sample. Conventionally, a loss of 7-8 grams is considered normal wear resistance and optimal for applications provided herein, and a maximum deviation of 0.5 g is tolerated among the corners. A determined loss of 10 g is considered by the CALTRANS Method to be a failure.

(46) Improvements in durability and significantly increased wear resistance versus that of conventional and available AASHTO hot-applied thermoplastics and Permaline® are provided in Table 5.

(47) TABLE-US-00012 TABLE 5 Conventional Improved Hot Test Method Thermoplastic Permaline ® Applied Abrasion (g.) 4-10 2.5-4.0  0-0.5 Gardner Impact, 0-15 15-30 40-100 RT (in-lb.) Gardner Impact, 0-10 10-20 15-40  0° C. (in-lb.)

(48) As seen in Table 5, the high impact resistance advantage is apparent for the polyamide-based road marking product over the currently available hot-applied thermoplastic markings as seen by the vast improvement in the low-temperature and ambient temperature measurements of the Gardner Impact test. In addition, the increase in wear resistance (i.e. highly resistant to road traffic tire wear) is evidenced by the results of the Abrasion test, where significant reduction in gram loss is shown.

(49) The National Transportation Product Evaluation Program (NTPEP) tests and reports the results of pavement marking material performance to AASHTO member states. According to the NTPEP Pavement Marking Materials (PMM) and Data Usage Guide, all performance testing is performed on an asphalt concrete roadway and a Portland cement concrete roadway, known as “test decks”. These “test decks” are located at snowplow (northern state) and non-snowplow (southern state) test sites where field evaluations of the applied product are recorded. Evaluations on temporary products are conducted for a period of six (6) months, while permanent markings are evaluated for three (3) years. Application specifications of the markings, for example bead type, application rate, and application thickness, are recorded, as are conditions during application such as air/surface temperatures and humidity. Test Deck product comparisons are undertaken in compliance with ASTM Standard D713-12.

(50) Readings taken from the test deck at specified areas of the applied marking are termed either the “skip” reading or the “wheel” reading. The “skip” reading is taken from the marking closest to the skip line of the road. Readings taken in the wheel path closest to the skip line of the road are provided as “wheel” readings. A visual representation of a conventional test deck configuration is as provided and described by FIG. 1.

(51) Retroreflectivity

(52) Retroreflectivity is the ability of a retroreflector (e.g. glass bead or reflective prism) to reflect light back to its source with minimal scattering. Dry and wet retroreflectivity readings are taken from the test deck. Dry retroreflectivity readings are taken from the first nine (9) inches of the skip line and in the wheel path closest to the skip line. Wet retroreflectivity is a measure of a marking's ability to ‘recover’ following a rain event, and is measured after a timed interval following a period of ‘wetting down’ by a portable garden hose. “Wet” readings are taken in the first nine (9) inches of the line closest to the road edge line and are taken in accordance with ASTM Standard E2177-11, entitled “Standard Test Method for Measuring the Coefficient of Retro-reflected Luminance (R.sub.L) of Pavement Markings in a Standard Condition of Wetness”. Retro-reflectivity readings taken from the ‘skip area’ should be considered as a representation of long line retro-reflectivity performance, while ‘wheel track’ data can be considered for lines used in a longitudinal fashion (e.g. stop bars, cross walks, legends, signage, and areas of excessive wear due to braking, stopping and turning movements. ‘Wheel track’ measurements can also be used to determine the future wear reflectivity under accelerated wear conditions.

(53) Day and Nighttime Color

(54) Transverse and longitudinal markings can be evaluated for color compliance, color fastness related to weathering and fading in accordance with ASTM Standard D6628. Daytime and nighttime color readings are recorded as chromaticity values of x and y coordinates. Luminance factors, the measure of the lightness of a marking, are also recorded.

(55) Durability

(56) Durability is rated on a scale of one (1) to ten (10), with ten (10) being the best rating to be obtained by a road marking. A durability rating is obtained through examination of an eighteen (18) inch length of line centered on the wheel track area (the “wheel” reading) and the nine (9) inches of the skip line area (the “skip” reading). A percentage of the marking material remaining in this area is translated to a rating scale of one (1) to ten (10). Durability ratings are obtained in accordance with ASTM D913. Data obtained by this method can be used to determine the ‘toughness’ of a pavement marking binder under long-term field conditions and weathering. Bead retention is not implied by this measurement.

(57) Application of the provided Working Examples 1-5 on a pavement marking industry test site (AASHTO NTPEP Test Deck, Asphalt and Concrete, Minnesota, Jul. 31, 2013) exhibited excellent durability and retro-reflectiveness after three (3) months, the results of which are as summarized in in Table 6. These initial values will be exceeded for both the initial and retained retroreflective properties of the higher content (up to 9%) polyamide hot-applied thermoplastic marker as these formulations have a higher bead content. The initial values from the 2013 Minnesota NTPEP Test Deck exceeded the minimums shown in Table 7 as well. Minimum requirements, by individual states, of retroreflective performance specifications require the use of Type 3 and Type 1 glass beads be incorporated into the thermoplastic marking material. The formulations of the working examples described herewithin include these in the compositions provided.

(58) TABLE-US-00013 TABLE 6 Results of Testing for High Durable Formulations of Working Examples 1-4 - Initial and 3 Months after Application White HD White HD Yellow HD Yellow HD Asphalt Concrete Asphalt Concrete Skip Wheel Skip Wheel Skip Wheel Skip Wheel Retroreflectivity (mcd) Initial 649 718 695 777 332 385 341 373 3 months 564 521 691 557 306 254 345 305 Wet Retro (mcd) Initial 118 169 25 50 3 months 104  54 28 53 Durability (1-10) Initial 10 10 10 10 10 10 10 10 3 months 10 10 10 10 10 10 10 10 Nighttime Color (x, y) Initial .4936 .4406 .4925 .4458 3 months .4960 .4442 .4956 .4457

(59) TABLE-US-00014 TABLE 7 Initial and 3 Year Retain Retro-reflectivity Requirements for HD (High Durability) Formulations Florida Alabama White Yellow White Yellow Initial Retroreflectivity 450 min. 350 min. 450 min. 300 min. (mcd) 3 Year Retained 150 min. 150 min. n/a n/a Retroreflectivity (mcd)

(60) The preceding description of specific embodiments of the present invention is not intended to be a complete list of every possible embodiment of the invention. Persons skilled in this field will recognize that modifications can be made to the specific embodiments described here that would be within the scope of the present invention.