DESC:FIELD OF INVENTION
The present invention relates to the development of thermoplastic marking coating formulation/composition preferably for marking roads based on involving synergistic combination of cycloaliphatic hydrocarbon resin with flexibiliser, polyamide and polyethylene homopolymer wax additive, silicon coated glass beads, and aggregates taken at select levels which is applicable at lower temperature on surfaces for marking the surfaces as compared to conventional thermoplastic road marking. Modified hydrocarbon resin suitable for application on surfaces by consumption of less energy required for melting of such marking paints.

BACKGROUND ART
Hot melt thermoplastic road marking paint used on the bitumen/asphalt and RCC/Concrete Roads, in Parking Markings etc. Thermoplastic paint has significant characteristics of fast drying, thick coating, good wear-resistant, long service life, and outstanding reflection property. Thermoplastic road marking, also known as hot melt road marking paint, which is in powder form. When applied at road surface; hot melt kettle is used to heat it up to 180 – 200 ? after which it is applied by screed methods on the road surface.
The heating temperature must be controlled between 180 – 200 ? to achieve required flow of material. The melting of paint is responsible directly to the quality of adhesion and performance of marking, so as to provide enough energy to achieve required temperature & flow is a key part during thermoplastic paint application on road, which needs to be reduced due to energy efficiency.
On this reference is invited to US7825186B2 teaching the use of polyolefin waxes in hot melt road marking compositions relating to hot melt compositions comprising polyolefin waxes prepared using metallocene catalysts, have a dropping point or ring & ball softening point of between 80 and 165° C., have a melt viscosity, measured at a temperature of 170° C. of between 20 and 40 000 mPa·s, and have a glass transition temperature of not more than -10° C. and also to their use as hot melt adhesives and as binders for producing road markings.
US3619224A on hot melt road-marking compositions having 30 to 75 weight percent of filler and pigment; said phthalimide derivative having a melting point of 90 °C to 120 °C and capable of dissolving said thermoplastic resin binder therein when fused but having substantially no compatibility with the resin binder at a room temperature. A hot melt road-marking composition is thus taught which comprises 15 to 40 weight percent of a thermoplastic binder resin having a softening point of 50 to 160 ° C 10 to 30 weight percent of at least one species of phthalimide derivatives having the structural formula.
US3523029A discloses about hot melt highway marking composition based on thermoplastic resin mixtures which are especially adapted for hot melt application as highway marking stripes. In particular, the thermoplastic resin mixtures of this prior art are suitable for production of thick stripes containing glass beads for reflex reflectance effect. Generally speaking, the advancement is concerned with thermoplastic resins which are an unreacted combination of high molecular weight alcohols with rosin or acidic rosin derivatives.
US3935158A directed to road marking paint compositions relates to a novel hot-melt road marking paint composition and more particularly to a hot-melt road marking paint composition comprising as thermoplastic resin components both at least one aliphatic hydrocarbon resin and at least one ethylene-vinyl ester copolymer. There has heretofore been known spontaneously drying type, hot-spray type, melt bonding type and other type paint compositions as road marking paint compositions for painting roads to form thereon road marking or signs for lanes, pedestrians' crossings, and the like. Among these conventional paint compositions, the so-called melt bonding paint composition is a normally solid and solvent-free type, one which contains as essential components a thermoplastic resin and a pigment and contains, for example, a plasticizer, stabilizer, antioxidant, and filler as well as glass beads as required. When the paint composition of this conventional type is used in the formation of, for example, thick film-type road marking such as indicating lines, is accomplished by melting the paint composition at temperatures of as high as 150°-250°C, applying the molten composition to a road surface so that it forms the desired shape and then allowing the applied composition to cool. When the melt bonding type paint composition is used in the formation of road marking or signs in such a manner as mentioned above, the composition coated on a road will be cooled spontaneously and solidified in only several minutes.
EP0192439B1 relates to road marking compositions, in particular hot melt road marking blends of improved color and viscosity consist of aggregate including pigment and a binder resin and it is desirable that the aggregate and the resin have good compatibility both in application and use and that the composition is stable particularly to withstand the high temperatures used in application over an extended period.
Reference is also invited to WO2015020020 A1 that discloses compositions for moldings, fibers heat-resistant adhesives, color filters, etc., contain (A) polyimides having repeating units I and II (R1 = C6-22 divalent group containing =1 alicyclic hydrocarbon structure; R2 = C5-20 divalent linear aliphatic group; X1, X2 = C6-22 tetravalent group containing =1 aromatic ring) and (B) additives. Thus, a blend composed of 4000 g 1,3-Bis(aminomethyl)cyclohexane-4,4’-diaminodiphenyl ether-1,6-hexamethylenediamine-pyromellitic dianhydride copolymer and 10.8 g Micron White 5000S (talc) was extruded with 25% T 275H (glass fiber), pelletized, and injection-molded to give test pieces having high mech. properties. Thus discloses compositions for moldings
KR740296B1 discloses a thermoplastic hot-melt tape for road signs, which enables a driver to easily discern road signs even at night or in a rainy day and reduces a construction period, and a construction method using the same. The thermoplastic hot-melt tape for road signs comprises: an adhesive layer which adheres to a road in predetermined thickness; a thermoplastic hot-melt tape which is provided beneath the adhesive layer and consists of a main material obtained by mixing a petroleum-based cycloaliphatic hydrocarbon and an ethylene-vinyl acetate copolymer, a calcium carbonate as a filler, a titanium dioxide as a pigment for discerning a hot-melt tape for road signs, a polyethylene wax as a surface leveling agent, a dioctyl phthalate as a plasticizer for preventing cracks of the hot-melt tape, a calcium stearate as a heat stabilizer, and ceramic glass beads as a discernible reflector; and an anti-slippery part which is applied to the underside of the thermoplastic hot-melt tape, consists of a mixture of an epoxy adhesive and a steel making slag, and forms a surface layer. This prior art involves epoxy adhesive part.
JP62011704A teaches resins, useful in paints, prepared by polymerizing 20-98 (mol)% unsaturated chain hydrocarbons and/or vinylidene group-containing cyclic hydrocarbons with 2-80% 9,10-dihydrodicylopentadiene (I) and further reacting with a, ß-unsaturated carboxylic acids (derivatives). Thus, 96 g 71.2% I and 9 g 1.3-pentadiene were polymerized by 1.1 g AlCl3 in 62 g xylene and 16 g hexane to give a product containing 48% I, which (100 parts) was treated with 0.5 part maleic anhydride at 200° for 2 h, giving a maleinated resin (II). A traffic paint containing II 100, Tokushinol TS-110 12, powder CaCO3 4.00, TiO2 668, and glass beads 100 parts exhibited melt viscosity 2350 cP at 200° and compression strength 552 kg/cm, vs. 3600 and 285, respectively, when a compositional resin was used to replace II. The compositional and viscosity data is valid for 200 °C melting temperature.
In spite of the above known conventional knowledge flowing from the state of the art as above, it is a long felt need in the art to explore for alternate hot melt thermoplastic marking paint formulation/ composition preferably for marking roads which would be applicable onto surfaces/roads at reduced melting temperature of thermoplastic paints so as to be energy efficient.
While generally, hot melt thermoplastic road marking paint is heated up to 200 °C to achieve flow for application on surfaces/roads, it is the requirement of the day to provide for a thermoplastic marking formulation/ composition that would achieve excellent flow at 140 °C ~ 160 °C, to be thus applicable at lower temperature to show excellent whiteness and less yellowness effect, excellent adhesion on bituminous and concrete surface with primer, that would pass cold crack cycles, and would also show good dirt pick up resistance.
OBJECTS OF THE INVENTION
The basic object of the present invention is to provide for thermoplastic marking formulation/composition preferably a hot melt thermoplastic formulation which can be applied on surfaces at lower temperature at 140- 160 ?, to save fuel energy and heating time and to ultimately improve productivity.

It is yet another object of the present invention to provide for said thermoplastic hot melt marking formulation/composition preferably for marking road which can be applied at 140-160 deg C. by means of this energy is saved during application.

It is another object of the present invention to provide for said formulation/ composition for surface marking that would enable reduction in application fuel cost leading to save energy.

It is still another object of the present invention to provide for said hot melt marking formulation/ composition which would require lower application temperature (<200 deg C), to enable coatings with excellent adhesion over surfaces including bituminous and primed concrete surface.

It is another object of the present invention to provide for said hot melt marking formulation/ composition that would cause relief to customer for not requiring high melting time to be melted in approx. 50 % lower time against regular conventional thermoplastic hot melt road marking that would enable increase pf speed and productivity.

It is further an object of the present invention to provide for said thermoplastic hot melt marking formulation/ composition that would be not only applicable at lower temperature to show excellent whiteness and less yellowness effect, but would also show excellent adhesion on bituminous and concrete surface with primer, that would pass cold crack cycles as well as would also show good dirt pick up resistance.
SUMMARY OF THE INVENTION

In the primary embodiment of the present invention is directed to provide a hot melt thermoplastic paint marking formulation comprising synergistic combination of ingredients at select levels of cycloaliphatic hydrocarbon resin and derivatives thereof, together with copolymers of ethylene and vinyl acetate, polyamide and polyethylene homopolymer wax, silicon coated glass beads, and aggregates.

Another embodiment of the present invention is directed to provide said hot melt thermoplastic paint marking formulation wherein said ingredients incorporated in wt.% levels includes 10 to 30 weight % of said cycloaliphatic hydrocarbon resin, from 1 to 5 weight % of said ethylene and vinyl acetate as flexibiliser, from 0.8 to 8 weight % of said polyamide and polyethylene homopolymer wax as leveling and softening additive, from 18 to 50 weight % of an aggregate, and from 25 to 45 weight % of said silicon coated glass bead, and,
also includes, pigments 5 to 15 weight % of white pigments including titanium di-oxide, and, hydro treated heavy paraffinic oil in levels of 0.5 to 1 by weight % as flow additive.

Further embodiment of the present invention is directed to provide said hot melt thermoplastic paint marking formulation which when heated to upto only 140 °C ~ 160 °C much lower than 200 ?C achieves flow for application on surfaces/roads and is thus applicable at lower temperature saving fuel energy and low heating time also imparting improved whiteness and less yellowness effect, improved adhesion on bituminous and concrete surface coated with primer even when free of epoxy adhesive, and also passes cold crack cycles, and shows good dirt pick up resistance.

Still further embodiment of the present invention is directed to provide said hot melt thermoplastic paint marking formulation wherein said cycloaliphatic hydrocarbon resin and derivatives thereof have molecular wt. in the range of 500 to 2500, softening point in the range of 90–110 deg C, glass transition temperature in the range of 40–60 deg C and includes unsaturated aliphatic olefins and diolefins derived of naphtha and on aliphatic hydrogenated resin and tricyclic monocarboxylic acids esterified with Pentaerythritol or derivatives thereof, with flexibiliser including copolymers of ethylene and vinyl acetate, leveling and softening additive including combination of Ethylene Bis Stearamide and linear low density polyethylene wax oil, silicon coated glass beads which is solid spherical glass beads have sphericity more than 70 %, and combination of aggregates including calcium magnesium carbonate or silicates and/ or combination with sand.
Another preferred embodiment of the present invention is directed to provide a process for manufacturing the hot melt thermoplastic paint marking formulation comprising the steps of providing a synergistic combination of ingredients at select levels of cycloaliphatic hydrocarbon resin and derivatives thereof, together with copolymers of ethylene and vinyl acetate, polyamide and polyethylene homopolymer wax, silicon coated glass beads, and aggregates, and processing by blending the same to obtain therefrom said hot melt thermoplastic paint marking formulation.
Yet another embodiment of the present invention is directed to provide said process for manufacturing the hot melt thermoplastic paint marking formulation including the sub-steps of
i. Filling required quantity of hydro treated heavy paraffinic oil into liquid feed tank as per batch size;
ii. Charging ~50% of powder material extenders including calcium magnesium carbonate and mixing started for 10-15 sec;
iii. Charging the remaining quantity of powder material aggregates including silica, marble sand, optionally magnesium silicate based extender and copolymers of ethylene and vinyl acetate and continuing mixing for 180 sec;
iv. Starting the Tulip Mill 1,2,3,4 and spray system for liquid heavy paraffinic oil;
v. Automatically stopping the mixer after 180 sec;
vi. Switching off the Tulip Mill 1,2,3,4;
vii. Charging the remaining raw materials as per formulation including TiO2, ultramarine violet cycloaliphatic hydrocarbon resin, copolymers of ethylene and vinyl acetate and silicon coated glass beads towards total batch size of 1200 Kg;
viii. Mixing again for 120 seconds and completing the batch;
ix. Opening bottom door of mixer and starting the rotor for 10-15 sec. to transfer all processed material into hopper and obtaining hot melt thermoplastic paint marking formulation.

DETAILED DESCRIPTION OF THE INVENTION
As discussed hereinbefore, the present invention relates to hot melt thermoplastic paint formulation/ composition preferably for marking roads comprising synergistic combination of cycloaliphatic hydrocarbon resin with flexibiliser, polyamide and polyethylene homopolymer wax additive, silicon coated glass beads, and aggregates taken at select levels which is applicable at lower temperature on surfaces for marking the surfaces as compared to conventional thermoplastic road marking.
According to an aspect of the present invention thus there is provided a hot melt thermoplastic paint formulation/ composition comprising,
10 to 30 weight % of hydrocarbon resin, 1 to 5 weight % of flexibiliser, 5 to 15 weight % of white pigments, 0.8 to 8 weight % of flow and levelling additive, 18 to 50 weight % of an aggregate, and 25 to 45 weight % of a glass bead wherein all the weight % are based on the formulation.
Preferably said formulation/ composition is provided wherein said hydrocarbon resin or derivatives thereof, includes unsaturated aliphatic olefins and diolefins derived of naphtha, esterified aliphatic hydrogenated resin or tricyclic monocarboxylic acids with Pentaerythritol or derivatives thereof, at 10 to 30% by weight % of the resin in said composition.
Thus the hot melt thermoplastic paint formulation/ composition of the present invention is workable at reduced temperature based on select synergistic combination of ingredients including: Cycloaliphatic hydrocarbon resin (derivatives thereof and on unsaturated aliphatic olefins and diolefins derived of naphtha and on aliphatic hydrogenated resin and on tricyclic monocarboxylic acids esterified with Pentaerythritol or derivatives thereof), with flexibiliser (copolymers of ethylene and vinyl acetate), white pigments, flow leveling additive (combination of Ethylene Bis Stearamide and linear low density polyethylene wax oil), silicon coated glass beads and combination of aggregates (Calcium magnesium carbonate or silicates and or combination of sands) which is applicable at lower temperature as compared to conventional thermoplastic road marking compositions.
The above formulation/composition of the present invention in being based on a heterogeneous combination of ingredients and in being free of any epoxy adhesive could yet provide for good adhesion attributes of the hot melt material melting at lower temperatures of melting at 140–160 °C which when applied on roads by screed method post melting at 140–160 °C enables film formation on the roads achieved by hot melt flow. Adhesion on bituminous road is achieved by thermal bonding of said hot melt material with bitumen of concrete road, with the adhesion further strengthened by application of primer coat even when such primer coats are free of epoxy based primers.
More preferably said formulation/ composition is provided wherein molecular weight of hydrocarbon resin is in the range of 500 to 2500 gm/mol as determined according to Gel permeation chromatography
According to another preferred aspect of the present invention there is provided said formulation/ composition wherein glass transition temperature of hydrocarbon resin is in the range of 40 – 60 deg C as determined according to Differential scanning calorimetry.
Preferably in said formulation/ composition the softening point of hydrocarbon resin is in the range of 90–110 deg C as determined according to ring and ball method.
According to yet another preferred aspect of the present invention there is provided said formulation/ composition wherein said white pigment is titanium di oxide whiting at 5 to 15 by weight % of white pigment in said composition.
According to another preferred aspect of the present invention there is provided said formulation/ composition, wherein said flexibiliser, which are copolymers of ethylene and vinyl acetate at 1 to 5 by weight % of flexibiliser in said composition.
Preferably in said formulation/composition said flow additive, which is hydro treated heavy paraffinic oil is present at the levels of 0.5 to 1 by weight % of flow additive in said composition.
More preferably said formulation/ composition is provided wherein said leveling and softening additive, is present as a select combination of Ethylene Bis Stearamide and linear low density polyethylene wax oil at 0.8 to 8 by weight % of levelling additive in said composition.
According to another preferred aspect of the present invention there is provided said formulation/ composition wherein said aggregates are Calcium magnesium carbonate or silicates and or combination of sands at 18 to 50 by weight % of aggregates in said composition.
Preferably said formulation/ composition is provided wherein said glass beads, which is solid spherical glass beads have sphericity more than 70 % at 25 to 45 by weight % of glass beads in said composition.
According to another preferred aspect of the present invention there is provided said formulation/ composition wherein the said coating can be applied at 140 -160 deg C using conventional techniques of thermoplastic hot melt road marking at 2500 – 3000 µm thickness of dry film thickness.
One of the requirement for thermoplastic road marking materials as specified by The Ministry of Road Transport & Highways (MORT&H) to conform to Clause 803.4 of the "Specification for Road & Bridge Works" that the material must have excellent wear resistance and adhesion on asphalt roads.
Said formulation/composition comprising, Binder (Resin and Oil)-18 % Min., Solid glass beads 30-40 %, Titanium Dioxide 10 % Min. and aggregate together with pigments, extender, and solid glass beads 42 % Max when applied on surfaces including bituminous or concrete surface with primer shows excellent adhesion.
Said formulation/composition is provided wherein said coating when applied on bituminous or concrete surface at 140-160 deg C shows energy saving.
Examples
The process to reach the formulation

During the processing of formulation the Tulip Mill is not started while mixing of Cycloaliphatic hydrocarbon resin, copolymers of ethylene and vinyl acetate and Silicon coated glass beads which would be otherwise broken because of high shear (1400 -1500 rpm) of Tulip Mill.

PROCESS

i. Fill the required quantity of hydro treated heavy paraffinic oil into liquid feed tank as per batch size;
ii. Charge ~ 50% of powder material (viz. Calcium magnesium carbonate-based Extender) and start the mixer for 10-15 sec;
iii. Charge the remaining quantity of powder material (Silica & Marble Sand, Magnesium silicate-based Extender (If any) and copolymers of ethylene and vinyl acetate) and mix for 180 sec;
iv. Start the Tulip Mill 1,2,3,4 and spray system for liquid;
v. Mixer automatically stops after 180 sec;
vi. switching off the Tulip Mill 1,2,3,4;
vii. Charge the remaining raw materials as per formulation (Viz. TiO2, Ultramarine Violet Cycloaliphatic hydrocarbon resin, copolymers of ethylene and vinyl acetate and Silicon coated glass beads) making the total batch size of 1200 Kg;
viii. Mixing for 120 sec. completes the batch;
ix. Open the bottom door of mixer and start the rotor for 10-15 sec. to transfer all processed material into the Hopper.

After QA approval sieving the material through 4-5 mesh renders the formulation ready for packing.

Selection of formulation

As stated hereinbefore to provide a thermoplastic marking formulation/ composition having excellent flow at 140°C~160°C, show excellent whiteness and less yellowness effect, excellent adhesion on bituminous and concrete surface with primer, passes cold crack cycles, and show good dirt pick up resistance, different formulations with variation of the components with varying wt.% were designed and prepared as disclosed in Table 1 below.
Table-1
Example No. 1 2 3 4 5 6
Raw Materials Wt. %
Calcium magnesium carbonate based Extender 22.00 22.00 22.00 22 22 22
Magnesium silicate based Extender 2.00 2.00 - - - -
Aggregates (Silica & Marble Sand) 19.57 19.57 21.57 20.37 18.82 18.17
Polyamide and polyethylene homopolymer wax additive 0.90 0.90 0.90 2 1.5 1.80
Hydro treated heavy paraffinic oil 0.50 0.50 0.50 0.6 0.65 1.00
White pigment 10.00 10.00 10.00 10.00 10.00 10.00
Ultraviolet Pigment 0.03 0.03 0.03 0.03 0.03 0.03
Cycloaliphatic hydrocarbon resin 15.00 10.00 7.50 15.00 15.00 15.00
Rosin Ester resin - 5.00 7.50 - - -
Copolymers of ethylene and vinyl acetate - - - - 2.00 2.00
Silicon coated glass beads 30.00 30.00 30.00 30.00 30.00 30.00
Total 100.00 100.00 100.00 100.00 100.00 100.00
Parameter
Flowability
(Ability to flow the material at 140-160 °C) Poor Poor Good Good Very Good Excellent
Application at 140-160 °C on Concrete Panel Not Applicable Not Applicable Not Smooth & Defect free Film not adhering to surface with pinhole Smooth & Defect free Smooth & Defect free
Further line of action Because of poor flow adding rosin ester to enhance the flow of material Because of poor flow removing thixtropy extender i.e. Magnesium silicate based Extender and selecting binder % to enhance the flow of material Flow found slightly better though not up to the mark therefore removing rosin ester and continuing with hydrocarbon resin only and selecting flow additive i.e. paraffinic oil with wax Flow found better &
wettability of material as well though application
was inferior on panel therefore adding
copolymers of ethylene and vinyl acetate & selecting flow
additive i.e. paraffinic oil with wax Flow found very good though flow was not good as conventional road markings. In order to achieve good flow selecting flow additive in select levels was done i.e. paraffinic oil with wax

Formulation (Example 1 and Example 2) comprising of Magnesium silicate based extender with Cycloaliphatic hydrocarbon resin (15%) or Cycloaliphatic hydrocarbon resin with Rosin Ester resin 10 and 5% wt. respectively provide poor Flowability (not being able to flow the material at 140-160 °C and thus were not considered for application on concrete panel.

Magnesium silicate based extender free Formulation Examples 3 and Example 4 both are having good flowability, however, Application at 140-160 °C on Concrete Panel was not Smooth & Defect free (Example 3) or film generated by Formulation Example 4 do not adhere to surface with pinhole.

Surprisingly, addition of 2% wt. copolymers of ethylene and vinyl acetate into the formulation provides formulation with very good flowability (Example 5) and excellent flowability (Example 6). Application of these two formulations (Example 5 and 6) at 140-160 °C on concrete panel provides smooth & defect free coating.

Evaluation of Dirt Pick Up resistance

Process:
1. Heat and form a round mold of the road marking paint material.
2. Place the mold in a container filled with carbon black powder and shake it 50 times.
3. Remove the mold from the container and tap it on a paper to check dirt absorption.
4. Note down the results of the dirt pickup.
5. Use a white cloth to remove the carbon black powder from the surface of the mold.
6. Inspect the appearance of the mold after cleaning.
7. Repeat the process for multiple samples to ensure consistency.
8. Compare the results to determine the effectiveness of the road marking paint in resisting dirt pickup.
9. Record any changes in appearance or performance of the paint material.

All the formulation from Examples 3-6 were subjected to test for Dirt Pick Up resistance. Formulation Examples 3 and 4 showed good dirt pick up resistance. The formulation of Example 5 and 6 showed dirt pick up resistance similar to (Example 5 very good) or better than (Example 6 excellent) the conventional HMRM coating.

Evaluation of Adhesion of the coating formulation by Chipping

"Testing Method for Checking Adhesion of Thermoplastic Road Marking Paint by Chipping requires:
Thermoplastic road marking paint, Concrete panel, Hammer and Chisel and the procedure includes the following steps:

Prepare the concrete panel by cleaning it thoroughly and allowing it to dry completely.
Apply the thermoplastic road marking paint on the concrete panel to the desired thickness according to the manufacturer's instructions.
Allow the paint to cure overnight or for the recommended period of time.
Once the paint has cured, hold the chisel at a 45-degree angle to the painted surface.
Strike the chisel firmly with the hammer to chip away a small section of the paint film.
Observe the chipping of the paint film and note the results.
Repeat the chipping process at different locations on the painted surface to ensure consistent adhesion throughout.

If the paint chips easily and forms large flakes, the adhesion is poor.
If the paint chips moderately and forms small flakes, the adhesion is moderate.
If the paint does not chip and remains firmly adhered to the concrete panel, the adhesion is good.

Results: Interestingly, it was observed that all the formulations Examples 3, 4, 5 and 6 do not chip and remain firmly adhered to the concrete panel after striking the chisel kept at a 45-degree angle to the painted surface, firmly with the hammer and thus pass the adhesion test.

Cold Crack Test: To evaluate the stability of the coating in response to the weather condition preferably extreme weather condition Cold Crack Test was performed following the method below:

"Prepare concrete panels of the desired size and thickness for testing.
Apply a uniform layer of the thermoplastic road marking paint (hot-melt road marking HMRM) onto the concrete panels according to the specified thickness requirements.
Allow the applied paint to dry overnight to ensure it has properly cured.
Place the painted concrete panels in a freezer set at -15°C for 16 hours to simulate cold weather conditions.
After the freezing period, inspect the panels from a distance of 1 ft to check for any visible cracks in the paint. Note down any observations.
Transfer the panels to a temperature-controlled environment set at 30°C for 8 hours to simulate warm weather conditions.
Repeat the cycles of freezing and heating for additional rounds to further test the resilience of the thermoplastic paint against cold cracking.
Record any instances of cracking or damage to the paint after each cycle of temperature change.
Evaluate the performance of the thermoplastic road marking paint based on the results of the cold crack testing."

Example No. 3 4 5 6 Conventional Thermoplastic HMRM Coating @200 °C
Standard
Whiteness Index
(On spectrometer) ASTM E313-15 75.68 77 76 77 70
Yellowing Index
(On spectrometer) ASTM E313-15 0.0345 0.02 0.02 0.02 0.05
Luminance
(On luminance meter) ASTM D36/BS 3262 78-80 80 81 84 80
Shore D hardness @30°C ASTM D2240 50-54 51-53 50-52 55-54 54-57
Shore D hardness (Panel kept at 60°C for 30 mins) ASTM D2240 08-10 08-10 08-10 15-16 18-19
Adhesion
(By Chipping) Internal Method PASSES PASSES PASSES PASSES PASSES
Dirt Pick Up Scale
(5 - Excellent
0- Poor) Internal Method Good Good Very Good Excellent Very Good
Cold Crack Test
(16 hours at -15 °C followed by 8 hrs at 30°C) Internal Method 3 Passes 3 Passes 3 Passes 4 Passes 4 Passes
Softening Point ASTM D 36 95 °C 98 °C 99 °C 102 °C 105 °C

The results of the cold crack testing reveals that Examples 3, 4 and 5 formulations undergo three pass whereby Example 6 formulation undergoes 4 passes, which is equivalent to Conventional Thermoplastic HMRM Coating @200 °C.
The other characteristic properties including Whiteness Index (On spectrometer), Yellowing Index (On spectrometer), Luminance (On luminance meter), Shore D hardness @30°C, Shore D hardness (Panel kept at 60°C for 30 mins), Dirt Pick Up (5-Excellent) and Softening Point are either equivalent or better in comparison to the Conventional Thermoplastic HMRM Coating @200 °C.

Advantageously, it is thus possible by way of the present invention to provide for said hot melt thermoplastic marking formulation/composition suitable for low temperature applications and a method thereof to allow application on surfaces by consumption of less energy required for melting such paints for marking. The key added advantages of said formulation/composition being one or more of applicability at lower temperature, showing excellent whiteness and less yellowness effect, showing excellent adhesion on bituminous and concrete surface with primer, passing cold crack cycles, good dirt pick up resistance.
,CLAIMS:We Claim:

1. Hot melt thermoplastic paint marking formulation comprising synergistic combination of ingredients at select levels of cycloaliphatic hydrocarbon resin and derivatives thereof, together with copolymers of ethylene and vinyl acetate, polyamide and polyethylene homopolymer wax, silicon coated glass beads, and aggregates.
2. The hot melt thermoplastic paint marking formulation as claimed in claim 1 wherein said ingredients incorporated in wt.% levels includes 10 to 30 weight % of said cycloaliphatic hydrocarbon resin, from 1 to 5 weight % of said ethylene and vinyl acetate as flexibiliser, from 0.8 to 8 weight % of said polyamide and polyethylene homopolymer wax as leveling and softening additive, from 18 to 50 weight % of an aggregate, and from 25 to 45 weight % of said silicon coated glass bead, and,
also includes, pigments 5 to 15 weight % of white pigments including titanium di-oxide, and, hydro treated heavy paraffinic oil in levels of 0.5 to 1 by weight % as flow additive.
3. The hot melt thermoplastic paint marking formulation as claimed in claims 1 or 2 which when heated to upto only 140 °C ~ 160 °C much lower than 200 ?C achieves flow for application on surfaces/roads and is thus applicable at lower temperature saving fuel energy and low heating time also imparting improved whiteness and less yellowness effect, improved adhesion on bituminous and concrete surface coated with primer even when free of epoxy adhesive, and also passes cold crack cycles, and shows good dirt pick up resistance.
4. The hot melt thermoplastic paint marking formulation as claimed in claims 1-3 wherein said cycloaliphatic hydrocarbon resin and derivatives thereof have molecular wt. in the range of 500 to 2500, softening point in the range of 90–110 deg C, glass transition temperature in the range of 40–60 deg C and includes unsaturated aliphatic olefins and diolefins derived of naphtha and on aliphatic hydrogenated resin and tricyclic monocarboxylic acids esterified with Pentaerythritol or derivatives thereof, with flexibiliser including copolymers of ethylene and vinyl acetate, leveling and softening additive including combination of Ethylene Bis Stearamide and linear low density polyethylene wax oil, silicon coated glass beads which is solid spherical glass beads have sphericity more than 70 %, and combination of aggregates including calcium magnesium carbonate or silicates and/ or combination with sand.

5. A process for manufacturing the hot melt thermoplastic paint marking formulation as claimed in claims 1-4 comprising the steps of providing a synergistic combination of ingredients at select levels of cycloaliphatic hydrocarbon resin and derivatives thereof, together with copolymers of ethylene and vinyl acetate, polyamide and polyethylene homopolymer wax, silicon coated glass beads, and aggregates, and processing by blending the same to obtain therefrom said hot melt thermoplastic paint marking formulation.
6. The process for manufacturing the hot melt thermoplastic paint marking formulation as claimed in claim 5 including the sub-steps of
a. Filling required quantity of hydro treated heavy paraffinic oil into liquid feed tank as per batch size;
b. Charging ~50% of powder material extenders including calcium magnesium carbonate and mixing started for 10-15 sec;
c. Charging the remaining quantity of powder material aggregates including silica, marble sand, optionally magnesium silicate based extender and copolymers of ethylene and vinyl acetate and continuing mixing for 180 sec;
d. Starting the Tulip Mill 1,2,3,4 and spray system for liquid heavy paraffinic oil;
e. Automatically stopping the mixer after 180 sec;
f. Switching off the Tulip Mill 1,2,3,4;
g. Charging the remaining raw materials as per formulation including TiO2, ultramarine violet cycloaliphatic hydrocarbon resin, copolymers of ethylene and vinyl acetate and silicon coated glass beads towards total batch size of 1200 Kg;
h. Mixing again for 120 seconds and completing the batch;
i. Opening bottom door of mixer and starting the rotor for 10-15 sec. to transfer all processed material into hopper and obtaining hot melt thermoplastic paint marking formulation.

Dated the 28th day of March, 2024 Anjan Sen
Of Anjan Sen and Associates
(Applicants Agent)
IN/PA-199