Indian Patents. 210677:THERMOPLASTIC ROAD MARKING PAINT COMPOSITION

Title of Invention	THERMOPLASTIC ROAD MARKING PAINT COMPOSITION
Abstract	Thermoplastic road marking paint composition comprising polyester resin derived from polyester waste in the range of 20-25% of the total formulation; glass beads in the range of 22% of the total formulation; titanium dioxide as pigment in the range of 10% of the total formulation; calcium carbonate and marble powder as fillers in the range of 43-48 % of the total formulation.

Full Text	FORM 2 THE PATENTS ACT, 1970 (39 of 1970) COMPLETE SPECIFICATION [See section 10; rule 13] "Thermoplastic road marking paint composition" (a) MALSHE VINOD CHINTAMANI (b)l, Staff Quarters, UDCT Campus, Matunga Mumbai - 400 019. Maharashtra, India (c) Indian National The following specification describes the nature of the invention and the manner in which it is to be performed: Related Application: Related application for patent: Related application for "A low cot, better performance and ecofriendly thermosetting powder coating formulation and process thereof with application no. 1114/MUM/2003 for the synthesis of polyester resin from polyester waste is disclosed and reported herein. Technical Field of the invention: The present invention relates to polyester resin based on poly ester waste (PEW) and its preparation which is useful in thermoplastic road marking paints as a binder. This invention further relates to synthesis of the resin based on PEW modified with dimethyl terphthalate (DMT) and / or rosin maleate adduct. Background and Prior Art: Traffic markings have evolved greatly throughout the past decade and continue to -improve to meet environmental and functional requirements for traffic control. The first major recorded event in traffic marking was in 1917 when a center dividing line was painted white in Michigan, USA, to assist drivers to stay in their own lane. The practice was adopted the next year as a standard procedure in Michigan. In 1934, glass beads were introduced to improve the visibility of traffic markings. The first patent for commercial epoxies was issued in 1945 to Devoe and Reynolds. In the early 1950s, the researchers at Prismo Company in Montgomery, PA invented pre-formed heavy-duty striping tapes and by the end of the 1959s thermoplastics were beginning to be used on American roads. In 1958 prismo developed the first successful thermoplastic application machine. Many fascinating developments continued to follow in response to various requirements and challenges posed to the industry. Many terms are used to describe traffic marking systems; line marking paints, traffic paints, striping paints, etc. Although they all serve the same purpose i.e. marking the roads with clear visible lines, they differ profoundly in their composition, properties and durability. Some are even meant to be only temporary, as opposed to those, which last for many years under heavy continuous traffic. Traffic markings are composed of pigments, extenders, specialty chemicals and dispersion medium. The pigment in the formulations is generally titanium dioxide (TiCh) for white marking and yellow (lead chromate-PbCr04) for yellow marking. Minor quantities of tinting colours may be used to obtain the correct hue. Extenders are generally inert inorganic compounds used to give the desired tensile strength and abrasion resistance to traffic markings. Some commonly used extenders are calcium carbonate, calcined clays, silicates, silica, mica, barium sulfate, etc. quantity of extenders is sometimes reduced to preserve the brightness and opacity of traffic marking formulations. Thermoplastic traffic markings are based on resins that melt at elevated temperatures and revert to a solid state on cooling. They dry quickly i.e. as fast as 30 seconds and do not depend on ambient drying conditions for their set. They set just by the drop in temperature to ambient conditions. Thermoplastics can be applied under high humidity conditions as well. In formulating such materials, pigments, fillers, plasticizers, resins (hydrocarbon or alkyd), heat stabilizers, etc are mixed either as dry powders or in molten resins under high shear. For traffic marking, thermoplastics are melted between 180-190° C and can be extruded or spray applied in film thickness ranging from 30-125 mils. Some of the major advantages are: ■ No hazardous solvents. ■ Used on asphalt as well as Portland cement (a primer is required). ■ Highly durable. Will last as much as 10 times longer than conventional traffic paints, costing only 3-4 times more than water-borne paints. Thermoplastic marking are used extensively on roads carrying heavy traffic; longitudinal lines, stop bars, cross walks, etc. The latest generation of thermoplastic is offered in the form of pre-formed tapes that can be used in all types of applications; temporary tapes for construction sites and permanent tapes for medium to high traffic volume areas. They are 100% solids, thus environmentally safe and without any volatile organic compounds (VOC) issues. The durability of these tapes is excellent. Even the temporary tapes have been known to last for 2-2.5 years. Permanent types have lasted up to 4 years. Composed of polymers, pigments and glass beads, thermoplastic reflective tapes have excellent skid resistance, resistance to weather, salt, water and petrochemicals like petrol and oil. Traffic markings have contributed tremendously to pedestrian and vehicular safety since the turn of the century and they continue to evolve with technological advancements in materials and techniques. Over the past decades, water-borne traffic markings have effectively resolved most of the health, safety and performance requirements. Thermoplastics and epoxy systems have also found a niche within the industry as reported in US3,321,329. As these technologies become more cost effective, they may eventually acquire a large market share. The traffic marking industry will undoubtedly continue to concentrate on the performance and safety aspects while taking advantage of the technological advancements in the future years. Thermoplastic road marking is used for special application. In comparison with the usual alkyd based traffic paints, both drying time and lifetime are improved. The binder system is mostly a mixture of resins e.g. rosin ester and C5 dicyclopentadiene resin (15-20 %), white pigment (Ti02, 25 %), filler (CaC03, 45-50 %) and reflective glass beads (25 %). Film thickness is about 2-3 mm when coated normally, 5-7 mm when screen applied into flat recesses. For yellow markings aromatic resins may also be used, but when unstabilized they are more sensitive to oxidation and discolouration. For road markings, paints are used more than thermoplastic materials. The coating thickness is 0.5-mm. These, paints are based on binder systems containing alkyd resins, Chlorinated rubber, and combined with hydrocarbon resins or rosin esters. The main requirements are stability to light and abrasion resistance. Resin characteristics must meet the following standards light stability (UV resistance), neutral and unsaponifiable, resistant against water, diluted acids, alkali and mineral oils, good film forming and wetting properties, good compatibility with synthetic rubber, synthetic copolymers, and other resins which are normally used in the formulation of road marking systems. Good thermal stability must allow heating to temperatures of 200°C. For this area of application, there are a number of commercially available resins, especially low priced binders. The aliphatic C5 resins types are by far the most popular, but other resin types are also used. 1. C5 (DCPD)- modified C9 hydrocarbon resins. 2. Hydrogenated hydrocarbon resins. 3. C4 modified C9 hydrocarbon resins. 4. C9 resins with low indene and high alpha methyl styrene / vinyl toluene content. 5. Terpene phenolic resins. The C5 modified and hydrogenated resins commonly show excellent light stability, a major factor, especially for white road markings. The light stable hydrogenated resins are not normally used because of their relatively high price. Some of the commercial C5 modified resins also show remarkably good UV stability and are also used for white markings, depending on specific requirements. C9 resins show a gradually deteriorating light stability though they are often used in combination with C5 resins or in less sensitive areas. Because of their slight tendency to yellow under the influence of light, indene -coumarone resins are not used at all. C9 resins are primarily used in yellow road markings. For white road markings a higher pigmentation is suggested. The road marking paints are divided into three types mainly: Solvent based traffic paints: They have been by far the most widely used traffic markings. They are easy to apply through conventional methods, fast drying and very durable. They are intimate dispersions of primary pigments, extenders and specialty chemicals in a dispersion medium (like alkyd resin) and fast evaporating solvents. Water-borne traffic paints: Water-borne traffic paints are intimate dispersion of pigments, extenders, specialty chemicals (like biocides, film formers, adhesion providers etc.) in a dispersion medium comprising of emulsion polymers, water and co-solvents. Major disadvantage of water borne paints is that they require more drying time. Thermoplastics traffic marking: Thermoplastic traffic markings are based on resins that melt at elevated temperatures and revert to a solid state on cooling. They dry quickly i.e. as fast as 30 seconds. In formulating such systems, pigments, fillers plasticizers, resins, heat stabilizers etc. are mixed either as dry powders or in molten resins under high shear. For traffic markings, thermoplastics are melted between 177-240° C and are either spiay applied or gravity extruded. Major advantages of Thermoplastics traffic marking are, no hazardous solvents, and high durability on asphalt as well as Portland cement roads. The main contents of road marking paints are pigments, extenders, specialty chemicals and a dispersion medium. Pigments: The pigment in the formulations is generally TiO2 for white markings and chrome yellow (lead chromate-PbCrO4) for yellow. Minor quantities of tinting colors may be used to obtain the correct hue. Extenders: Extenders are generally inorganic compounds used to give the desired tensile strength and abrasion resistance to traffic markings. Some commonly used extenders are calcium carbonate, silicates, silica, mica, barium sulphate etc. extenders are omitted sometimes to preserve the brightness and opacity of traffic marking paints. Retro-reflective glass beads: Glass beads were first used in 1934 when they were used on traffic signs to increase their visibility. Glass beads are used in all types of traffic paints; solvent based, water borne and thermoplastics. They can be either dropped in specified quantities on the wet traffic paints after application or they can be supplied premixed. Glass beads are generally of the size 100 to 150 microns. They shall have resistance to acids, calcium chloride, sodium sulfide and water. These elements shall not have any dulling effect on the glass spheres. The main reason for use of glass beads in road marking paints is the visibility at night. At night when light from headlight falls on the road markings, the glass beads on them reflect back the light. The paint contains almost 20-30% by weight of these glass beads, therefore if top layer goes off there are more glass beads under this layer. Resins: The resins that can be used for road marking paints are as follows: Alkyd resins: Alkyd resins can be used for both solvent based and thermoplastic markings. Alkyd resin based traffic paints are suitable for both asphalt and concrete surfaces. They have excellent resistance to petrochemicals and they can be applied by conventional or airless spray methods. Chlorinated- rubber alkyd resins: They have better toughness and chemical resistance and better overall durability as compared to conventional alkyd based paints. The cure mechanism involves solvent evaporation and oxidation. They are easy to apply. But because of regulatory restrictions on chlorinated rubber they are not used since 1980s. Hydrocarbon resins: Hydrocarbon resins are primarily petroleum-based compounds. Thermoplastics based on hydrocarbon resins lack adequate resistance to petrochemicals (like oil, grease etc.). Alkyd and hydrocarbon resins are not compatible. Any cross contamination in the heating kettle will result in performance problems. Polyester paint: Polyester paints provide unsurpassed durability, which makes this the most cost effective paint for asphalt, when compared on a life-cycle basis with alternative paints and marking materials. Advanced polyester paint technology with the development of VOC compliant formulations by replacing MEKP with a non-hazardous catalyst to achieve a chemical cure poses no threat to either applicators or the environment. They achieve short curing times without sacrificing chemical stability. Acrylic water borne emulsions: Acrylic water borne traffic paint, the polymeric binder is an acrylic emulsion. After the water borne paint is applied, the water begins to evaporate, which causing the emulsion particles to move closer together, resulting in deformation of the spherical particles and hexagonal particles begin to form. In the last stage, the water and coalescent diffuses more or less completely out to produce a continuous film. Vinyl chloride: The vinyl chloride marking film comprises a film, a suitable pressure sensitive adhesive layer on one surface and a suitable releasing sheet on the adhesive layer. Ultraviolet absorbers are incorporated to protect the markings from UV radiation. Application techniques used in road marking are as follows; Surface preparation: Care is taken to ensure that the surface is clean, dry and free of loose material. A simple blower is typically sufficient to remove gravel and dust in most instances. When applying over previously coated areas, special care is required to remove any loose or peeling paint. Other surface conditions, such as areas with large amounts of engine oil build-up or existing epoxy coatings, may require a power washing procedure or abrading the surface before application of the paint. New concrete and asphalt should be aged for a minimum 30 days prior to painting. Weather conditions: Air temperature, surface temperatures, humidity, and weather conditions following the application are extremely important factors in the success of the road marking paint. At lower temperatures or when humidity is extremely high, a significant amount of extra time will be needed for drying. Equipments: Solvent based and water borne traffic paints are applied with conventional air or airless spray equipments. For thermoplastic traffic markings two basic pieces of equipment are needed. 1. A kettle to melt the thermoplastic composition. 2. A screened applicator machine to extrude and deposit the desired film thickness on the pavement. These can be walk-behind, ride-on or truck or van mounted. Stain resistant markings are described in US patent 594833. Water borne road paints in particular have the problem of yellowing, which occurs after application of the paint on the road. A possible cause for this phenomenon is rust formation due to the reaction of iron with the materials in the paint formulation. Incorporating a chelating agent in the water borne road-marking paint solves this problem. The chelating agent is capable of chelating iron ions to form a substantially colourless complex, as per the above patent. US Patent 6036764 describes yellow pigment blend. Traditional traffic paint use lead and hexavalent chrome pigments, which are toxic to plants, animals and humans and are subjected to strict environmental regulation. Conventional organic pigment, when subjected to hot melt heat test decompose and discolor. Therefore a blend comprising; Yellow nickel titanate pigment, Yellow bismuth vanadate and Yellow isoindolinone pigment is formulated. This is a lead and chrome free yellow pigment that can be used in hot melt traffic markings as described in this patent. US patent 6211260 deals with water borne paints which are non pollutive but which dry slowly. One of the important features of road marking paints is the speed at which they dry after application of the paint on the road. This dictates the level of disruption required to road traffic in order to apply them. Since solvent-based paints are polluting, using water borne is more environmentally friendly. But the drying times for water borne paints are dependent on the relative humidity of the atmosphere. Water-resistant traffic markings based on alkyl-based paints are reported in US patent 6228901. Conventional water borne paints tend to be less wear resistant than traditional alkyd based paints. The term wear resistance means the degree of resistance of the traffic markings to detaching from the road surface when the marking is exposed to traffic conditions and to UV radiation. The method of producing a wear resistant traffic marking paint comprises applying on the road surface an aqueous traffic paint, which contains a polymer polymerized from a monomer mixture that includes a range from 80% to 99.9% (all in weight % based on polymer solids) of one or more hydrophobic monomers and drying the layer to form the wear resistant traffic marking. The hydrophobic monomer can be butyl methacrylate, ethyl methacrylate etc. Advantage of this method is that it produces traffic markings that are wear resistant even under exposure to UV radiation from sun. Features of an ideal road marking paint are described hereafter, ■ Reduced environmental impact through formulations having low VOC. ■ Improved balance of coating rheology during application and film formulation to promote substrate wet out and fast cure to free films. ■ Good visibility at night i.e. they should be retro-reflective in nature. ■ Broadened range of weather conditions for coating application. ■ Improved marking performance through increased durability and reflectivity. ■ Quick drying time for resumption of traffic. ■ Improved properties like wear-resistance, stain-resistance, abrasion resistance, skid- resistance, UV resistance etc. The solid waste from polyester plant comprises oligomeric polyesters and a small percentage of titanium dioxide pigment. This material cannot be used for production of fibers, as it would cause considerable loss of its properties due to presence of impurities. Due to the pigment content, it is not possible to consider applications where transparent coatings are desired. A new road marking paint has emerged in the past few years. This is applied in the form of strips of about 5 mm thickness and is applied as an extruded coating at the site. The coating has following requirements. • It should be extrudable at relatively low temperatures of about 150°C. • It should have low application viscosity and good wetting properties. • It should be able to take high pigment loading. • It should have good colour retention in outdoors. • It should have a high melting point, good abrasion resistance and low cost. At present hydrocarbon resins are used for this application and most of these resins are imported. There are only few manufacturers of these products in India and the acceptability of the product is increasing due to long life offered by the product. The consumption is in excess of 15,000 tpy with approximately 30 % resin content. The expected consumption would be about 25,000 tpy by end of 2003. The world market is already very large. Since, at present, this product is based on hydrocarbon resins that are not readily available in such quantities, it is necessary to look at alternate raw materials, which have considerably large manufacturing base. Polyester based on DMT or PTA and ethylene glycol (EG) appears an ideal choice since the installed capacity of the raw materials is very huge. In this invention studies on to the viscosity, molecular weight relationship of the polymer after completely characterizing it is done. The flow properties might be modified by addition of other raw materials to a small extent. These may be neopentyl glycol, dimethyl terephthalate and rosin maleic adduct which considerably influence the performance of the polymer. The present work involves the preparation of polyester resin based on PEW, which would be useful in thermoplastic road marking paints as a binder. Polyester was synthesized based on PEW modified with DMT and rosin maleic adduct. Different paint formulations were prepared and evaluated for their performance at different temperatures to study the influence of composition variables (pigment / binder ratio, resin content, and filler employed) on properties. Thermoplastics type road marking paint is a prime choice for traffic paints. If offers following advantages over solvent-based, waterborne paints and epoxies: ■ Absence of environmentally unfriendly solvents ■ Good water resistance when completely dried ■ Safe for traffic personnel ■ Easy application through the use of current traffic paint equipment Objectives: The objective of this work was to provide polyester resin based on PEW to enhance the opportunities for successful hot-applied thermoplastic pavement marking applications and reduce environmental pollution. It is intended to be beneficial to the public, contractors, application crews, project engineers and inspectors. Summary of the Invention: The present invention relates to polyester resin based on polyester waste (PEW) and its preparation which is useful in thermoplastic road marking paints as a binder. This invention further relates to synthesis of the resin based on PEW modified with DMT and / or rosin maleate adduct. The present invention relates to thermoplastic type road marking paint wherein the said paint comprises; polyester resin in the range of 20-25% of the total formulation; glass beads in the range of 22% of the total formulation; pigment in the range of 10% of the total formulation; filler in the range of 43-48 % of the total formulation. The polyester resin is made of polyester waste (PEW). A source of PEW is selected from polyester fiber, PET bottles used fro mineral water and beverages, film waste and any other waste available from synthetic fiber industry or a textile plant etc. The PEW is glycolised with Neopentyl glycol (NPG) at temperature 180 to 210° C in presence of Zinc acetate catalyst. The polyester resin is prepared by condensing glycolised PEW with DMT or Rosin maleic adduct (RM adduct) which is carried out in presence of catalyst Zinc acetate; heating rapidly to 160° C, from 160-200° C at a rate of 10° C per hour and held at this temperature until the calculated amount of by product (water or methanol) is collected; subjecting reaction mass to polycondensation by gradually heating at temperature ranging 180-210° C under vacuum, to get polyester resin with low acid value. The polyester resin based on DMT is characterized by acid value (mg KOH/g) of 16.3; melting range of 135-139°C; relative viscosity of 1.3024 and number average MW (Mn) 1832. The polyester resin based on rosin maleic adduct is characterized by acid value (mg KOH/g) of 21.0; hydroxyl value (mg KOH/g) of 8.1 ; melting range of 104- 106°C;relative viscosity of 1.2607 and number average MW (Mn) 1685. The paint based on PEW with DMT is characterized by wet abrasion in the range of 1-3- 2.1 g; dry abrasion in the range of 1.1-1.9 g; hardness at 50°C passes; W+ in % after lOOhrs 9.68 - 13.8; W" in % after lOOhrs 8.72-11.24 and flow of paint is poor. The paint based on PEW and RM adduct is characterized by wet abrasion in 1.7 -2.5 g; dry abrasion in the range of 1.5-2.0 g; hardness at 50°C passes; W4 in % after lOOhrs 11.52-13.16; W" in % after 1 OOhrs 9.44 -10.44 and the flow of paint is good. The pigment used is titanium dioxide for white road marking paint or chrome yellow (lead chromate - PbCrO4) for yellow road marking paint. The filler is calcium carbonate and used in the range of 15-20% of the total formulation. The filler is marble powder and used in the range of 28% of the total formulation. A process for preparation of the thermoplastic type road marking paint wherein said process comprises mixing of polyester resin, titanium dioxide, fillers, and glass beads in a mixing vessel; heating to 180-190°C; maintaining at the same temperature for 30minutes with high stirring and pouring the product obtained in special molds with a film thickness of 3-5mm. Detailed Description: The main contents of thermoplastic type road marking paints are binders, pigments, extenders, specialty chemicals and a dispersion medium. Raw materials used are described in the following; Pigments used here are selected from TiO2 for white marking and chrome yellow (lead chromate - PbCrO4) for yellow marking. Extenders are generally inorganic compounds used to give the desired tensile strength and abrasion resistance to traffic markings. Some commonly used extenders are calcium carbonate and marble powder. Retro-reflective glass beads are used in all types of traffic paints; solvent based, water borne, thermoplastic and reflective tapes. They can be either dropped in specified quantities on the wet traffic paints after application or they can be supplied premixed. Glass beads are generally of the size 100 to 150 microns. PEW source used in polyester synthesis is selected from polyester fiber, PET bottles used fro mineral water and beverages, film waste and any other waste available from synthetic fiber industry or a textile plant etc. The monomers used to prepare polyester resin are selected from Neopentyl glycol, Dimethyl terephthalate and Maleic anhydride. All reagents were used without further purifications The prepared polyester resins were characterized for following properties, 1. Colour and appearance. 2. Melting range. 3. Acid value. 4. Hydroxyl value. 5. Number average molecular weight by Gel Permeation Chromatography. The thermoplastic road marking materials were sampled and tested in accordance with the specified methods. Dry and wet abrasion test: For dry and wet abrasion test, disk specimens were employed (80 mm diameter and 3 mm thick). After 24 hrs, samples were abraded using Wet Abrasion Scrub Tester with an abrasive and 1000 g load (ASTM D-4060). The dust produced by the wearing operation was eliminated continuously. When a track is formed as a consequence of wearing, the sample was weighed. After that, the wearing operation was continued along 100 revolutions of the equipment and weighed again. The difference between the two values obtained was expressed as dry wearing. After finishing the previous test, distilled water was added to the track and the operation was continued during 100 more revolutions. The sample was conditioned for water elimination and weighed. The difference in both these weights gave the value for wet wearing. Hardness: Hardness of the paint at temperature between 40-45°C was determined according to ASTM-D 2240. In this case test panels were of 50 mm diameter and 3 mm thick. The panels were kept in an oven for one hour at 40-45°C. Samples were stabilized during one hour at test temperature before the hardness was determination. Water absorption and Water elimination test: For the determination of water absorption and water elimination rates, specimens of 50 mm diameter and 3 mm thick were prepared and weighed to ± 1 g. They were completely submerged in distilled water at room temperature for 100 hrs. Then they were dried with filter paper and weighed after 100 hrs. Absorption values were obtained by the difference in the two weights of the samples. Afterwards, the probes were conditioned at room temperature and exposed to sun for 100 hrs. Water elimination values were obtained by the weight difference. Flow test: The flow of the thermoplastic road marking paint was tested; 500 g of the paint in molten condition (Temperature about 180-200°C) was poured over a test base. After allowing it to settle, the area covered by the paint was measured. The paint is considered to have good / satisfactory flow property if it spared over one feet area. The PEW was characterized by its chemical and physical analysis such as acid value, hydroxyl value, saponification value, melting range. A calculation was done for glycolysis of PEW and synthesis of polyester resins with required acid value. In the second part PEW was glycolyzed by Neopentyl glycol to convert hydroxyl terminated low molecular weight oligomers. The same process was followed for glycolysis, which is described in earlier application number 1114/MUM/2003. The amount of glycol required for glycolysis depended on initial composition of PEW. Standard laboratory esterification equipment was used for the synthesis of polyesters. Glycolyzed PEW, dimethyl terephthalate (DMT) or rosin maleic adduct were taken in the required proportions in three necked quick fit round bottom flask equipped with stirrer, thermometer, Dean and Stark apparatus and nitrogen purge system. Zinc acetate was used as a catalyst (1% on the basis of total amount of dibasic acid). The ingredients were heated rapidly to 160 °C, from 160-200 °C at a rate of 10 °C per hour and held at this temperature until the calculated amount of by product (water or methanol) was collected. Then the reaction was carried forward to polycondensation process by gradually heating at temperature ranging 180-210 C under vacuum, to get polyester resin with low acid value. The completion of polymerization was checked by determining the acid value of the resin. The product was poured in a tray and was completely characterized for its physical and chemical properties like hydroxyl value, acid value, and relative viscosity by standard methods. The reaction conditions and optimized composition of ingredients are as given in Table 1 and 2. Table: 1 Reaction conditions: Resin Code Glycolysis Condensation Polycondensation Eliminated MeOH Qty (ml) Temp Time Temp Time Temp Time PRl PR 2 200 200 3.0 3.0 180 210 3.0 2.5 210 200 1.0 1.0 26.0 7.3 Table: 2 The optimized compositions for polyester. Ingredients PRl PR2 PEW 100 100 NPG 21.47 21.47 DMT 60.55 - RM adduct - 111.7 Note: All values are calculated for 100 g of PEW, PR 1 = Polyester based on DMT, PR 2 = Polyester based on Rosin maleic adduct. Thermoplastic reflecting materials were formulated, containing a binder resin based on PEW and modified with rosin. The modified resin was used in 20, 22 and 25% on total formulation. As a hiding pigment, titanium dioxide (rutile type) was employed to obtain a white colour with high luminosity. Formulation was completed using calcium carbonate and marble powder as fillers, which give good wearing resistance. Sample formulations are indicated in Table 3. Table: 3 Compositions of the Thermoplastic Materials. Materials I (%) II (%) III (%) Polyester (PR1 or PR2) 20 22 25 Glass beads 22 22 22 Titanium dioxide 10 10 10 Calcium carbonate 20 18 15 Marble powder 28 28 28 Mechanical stirrer was used for the thermoplastic preparation rotated at 50-60 rpm to give a smooth consistency to the thermoplastic material to avoid local over heating. For heating, a mineral thermic fluid circulating in the heating jacket (maximum temperature 300°C) around a mixing vessel was employed. Polyester resin PR1, titanium dioxide, fillers, and glass beads were taken in the mixing vessel and heated at 180 -190 °C. Operation at this temperature was maintained for 30 min with high stirring and then the product obtained was poured in special molds with a film thickness of 3 to 5 mm. The sample tests, performed at different temperatures, included wet and dry abrasion, hardness, water absorption and water elimination rate and flow properties of paints. These properties are given in Table 6 and 7. Thermoplastic resin based road marking experiments were conducted using different compositions and embodiments. Thermoplastic road marking with its superior visibility and weather resistant durability, allows drivers to feel confident and secure on the road. Thermoplastic road marking complies with the highest international standards and is ideal for highways and all other paved roads. Superior visibility prevents accidents and it contains high quality glass beads that create an illuminating effect at night, provide lasting daytime visibility and are skid resistant. Thermoplastic road markings are fast setting and dry within minutes, made from durable thermoplastic materials. Thermoplastic road markings retain their texture for more than two years marking their life cycle more cost effective than conventional paint. Reflecting thermoplastics applied on city streets, roads or highways frequently lose their efficiency due to the wearing or the partial detachment of the used materials; the appearance and physical characteristics are modified. The adequate lifetime is a function of different variables, acting individually or as a whole adhesion to the surface where they were applied (asphalt or concrete), resistance to abrasion and weathering (moisture due to rain and dew remaining for a long period of time in contact with thermoplastic marks), high temperature producing deformation or low temperature diminishing elasticity and favoring checking or cracking of the mark. Hydrocarbon thermoplastic, formulated with petroleum-based resins, is a well-proven, durable pavement marking system, resistant to the effects of oil, grease and salt and provides exceptional performance in all applications. Hydrocarbon thermoplastic is used in all types of applications. Its retroreflective performance and durability are only superceded by alkyd thermoplastic materials. For a reference, hydrocarbon resin based on Dicyclopentadiene was chosen. The hydrocarbon resins posed some problematic effects on the road marking paint by the rolling action of tires on the paint thereby removing it completely and exposing the underneath tar road. The main aim of this work was to improve this aspect of the road marking paint. As a result this property can best be improved by replacing the conventional hydrocarbon used in road marking paints with polyester resin as a binder, which is known to have good adhesion on variety of surfaces. The most preferred embodiment was observed to be polyester based on DMT and Rosin maleic adduct which was found to be transparent, glossy, brittle and coloured. The colour could be attributed to side reactions like oxidation and initial colour of PEW. Other properties of polyester including acid value, hydroxyl value, relative viscosity and melting range are listed in Table 5. Table: 5 Properties of prepared polyester resins. Properties PR1 PR 2 Acid value (mg KOH/g) 16.3 21.0 Hydroxyl value (mg KOH/g) - 8.1 Melting range (°C) 135-139 104-106 Relative viscosity 2.3024 1.2607 Number average MW (Mn) 1832 1685 Another embodiment namely by the polyester based on DMT showed high melting range, relative viscosity as compared with Rosin maleic-based polyester. Thermoplastic type road marking paints required low melt viscosity and low melting temperatures (approximately 90 to 100 °C) of binder. This was achieved by replacing DMT with Rosin maleic adduct. The ingredients were melted at 180-190 °C for 30 minutes and extruded on the surface to be marked with a film thickness of 1-5 mm. Volatile solvents were not included in these formulations, so they are ecologically acceptable. Prior to their application, the surface was cleaned. The paint sample tests, performed at different temperatures, included wet and dry abrasion, hardness, water absorption and water elimination rate and flow properties of paints. These properties are given in Table 6. Water absorption and water elimination tests were performed for 100 hrs. This property primarily measures the characteristics of other ingredients like fillers etc present in the formulation. From the Figure 1, it was observed that water absorption was greater in case of formulations with high content of fillers. Also it was higher in case of aromatic polyester i.e. DMT as compared to rosin maleic based polyester which is aliphatic in nature. Similar results were observed for water elimination test for all formulations based on DMT and rosin maleic adduct. The wet abrasion test shows greater wearing values than those obtained in the dry abrasion test. It was observed that formulation based on polyester resin with rosin maleic adduct showed greater wearing values for wet abrasion as compared to that from DMT. A similar trend was observed for dry abrasion. This could be due to greater interstitial voids present in rosin maleic-based polyester and its higher water sensitivity as compared to DMT based polyester. Table: 6 Properties of road marking paint based on polyester with DMT. Properties I II III Wet abrasion in g 2.1 1.8 1.3 Dry abrasion in g 1.9 1.3 1.1 Hardness at 50 °C Passes Passes Passes W+in % after 100 hrs 13.8 13.12 9.68 W" in % after 100 hrs 11.24 10.56 8.72 Flow of paint Poor Poor Poor Where (W+) is Water absorption and (W) is Water elimination. Results of hardness test as a function of temperature are related to the plasticization degree of the resin. This is particularly observed at 50°C, which is considered critical. Above this temperature, hardness diminishes abruptly in practically all of the samples. All these formulations passed the hardness test performed at 50°C. Hardness was performed as per the procedure given in methods of analysis. Table: 7 Properties of road marking paint based on polyester with RM adduct. Properties I II III Wet abrasion in g 2.5 2.2 1.7 Dry abrasion in g 2.0 1.7 1.5 Hardness at 50 °C Passes Passes Passes W+ in % after 100 hrs 13.16 12.00 11.52 W" in % after 100 hrs 10.44 10.00 9.44 Flow of paint Good Good Good In the results of the water absorption and water elimination tests, the increases of weight of the thermoplastic mass during immersion is faster than the water elimination value. Flow test for paints plays a major role in assessing their nature. It was found that formulations with DMT based polyesters showed poor flow. It has been improved by reducing the aromatic content by incorporating rosin maleic adduct instead of DMT. Thus formulations using rosin maleic-based polyesters gave satisfactory flow properties as compared to conventional resins used in thermoplastic road marking paints. It will be readily apparent to one skilled in the art that varying substitutions and modifications may be made to the invention disclosed herein without departing from the scope and spirit of the invention. Thus, it should be understood that although the present invention has been specifically disclosed by preferred embodiments and optional features, modification and variation of the concepts herein disclosed may be resorted to by those skilled in the art, and that such modifications and variations are considered to be falling within the scope of the invention. The following examples are for the purpose of illustration of the invention only and are not intended in any way to limit the scope of the invention. Examples Example 1 Synthesis of PR1 Glycolyzed PEW was prepared by glycolysing 100 g PEW with 21.47 g NPG at 200° C for 3 hour. This glycolised PEW was treated with 60.55 g dimethyl terephthalate (DMT) in three necked quick fit round bottom flask equipped with stirrer, thermometer, Dean and Starck apparatus and nitrogen purge system. Zinc acetate was added as a catalyst (1% on the basis of total amount of dibasic acid). The ingredients were heated rapidly to 160° C, from 160-200° C at a rate of 10° C per hour and held at this temperature until the calculated amount of by product (water or methanol) was collected. Then the reaction was carried forward to polycondensation process by gradually heating at temperature ranging 180-210° C under vacuum, to get polyester resin with low acid value. The completion of polymerization was checked by determining the acid value of the resin. The product was poured in a tray and was completely characterized for its physical and chemical properties like hydroxyl value, acid value, and relative viscosity by standard methods. Example 2 Synthesis of PR 2 Glycolyzed PEW was prepared by glycolysing 100 g PEW with 21.47 g NPG at 200° C for 3 hour. This glycolised PEW was treated with 111.7 g Rosin maleic adduct (RM adduct) in three necked quick fit round bottom flask equipped with stirrer, thermometer, Dean and Starck apparatus and nitrogen purge system. Zinc acetate was added as a catalyst (1% on the basis of total amount of dibasic acid). The ingredients were heated rapidly to 160°C, from 160-200° C at a rate of 10°C per hour and held at this temperature until the calculated amount of by product (water or methanol) was collected. Then the reaction was carried forward to polycondensation process by gradually heating at temperature ranging 180-210° C under vacuum, to get polyester resin with low acid value. The completion of polymerization was checked by determining the acid value of the resin. The product was poured in a tray and was completely characterized for its physical and chemical properties like hydroxyl value, acid value, and relative viscosity by standard methods. Example 3 Thermoplastic paint Polyester resin PR2 (25 g), titanium dioxide (22 g), Calcium carbonate (lOg), Marbel powder (28 g), and glass beads (22g) were taken in the mixing vessel and heated at 180-190° C. Operation at this temperature was maintained for 30 min with high stirring and then the product obtained was poured in special molds with a film thickness of 3 to 5 mm. The sample tests, performed at different temperatures, included wet and dry abrasion, hardness, water absorption and water elimination rate and flow properties of paints. These properties are given in Table 6 and 7. Example 4 Thermoplastic paint Polyester resin PR1 (22 g), titanium dioxide (10 g), Calcium carbonate (15 g), Marble powder (28 g) and glass beads (22g) were taken in the mixing vessel and heated at 180 190° C. Operation at this temperature was maintained for 30 min with high stirring and then the product obtained was poured in special molds with a film thickness of 3 to 5 mm. The sample tests, performed at different temperatures, included wet and dry abrasion, hardness, water absorption and water elimination rate and flow properties of paints. These properties are given in Table 6 and 7. Description of Drawings: Figure 1 describes comparative results for water absorption and elimination test for road marking paints based on polyester with DMT and Polyester resin with rosin maleic adduct. Graph for results obtained for water absorption test is shown by number 9. In this water absorption test, Y axis is shown by 1 which indicates the water absorbed in percentage after 100 hours exposure. X-axis is shown by number 2 which indicates three different formulations with 20, 22 and 25 % of polyester resin based on DMT and rosin- maleic adduct. Number 3 showed by dark black colour column which is for formulation containing polyester resin based on DMT). Number 4 showed by gray column which is for formulation containing polyester resin based on rosin-maleic adduct. Results obtained for water elimination is shown by number 10. Y axis indicates the percentange water elimination after exposure of 100 hours which is shown by number 5, X-axis is shown by number 6 which indicates three different formulations with 20, 22 and 25 % of polyester resin based on DMT and rosin-maleic adduct. Number 7 showed by dark black colour column which is for formulation containing polyester resin based on (DMT). Number 8 showed by gray column which is for formulation containing polyester resin based on rosin-maleic adduct. Polyesters based on PEW show high potential for thermoplastic type road marking paint and durable alkali resistant pigment. Road marking paint using these polyesters show fast drying and other advantages such as excellent adhesion, durability, light reflectivity, water resistance and good weatherability for concrete and asphalt surfaces. These types of paints are especially suitable for highway coating because they are more easily applied than a hot-spray type. This type of traffic paint materials can be applied by a roller or a truck-mounted striper. It's especially strong in durability, low drying time and night reflectivity. While the formulations based on polyesters synthesized from PEW and DMT exhibit poor flow properties than the conventional paints, polyesters prepared from PEW and rosin maleic adduct show very good flow properties as compared to conventional paints. I Claim, 1. Thermoplastic road marking paint composition comprising polyester resin derived from polyester waste in the range of 20-25% of the total formulation; glass beads in the range of 22% of the total formulation; titanium dioxide as pigment in the range of 10% of the total formulation; calcium carbonate and marble powder as fillers in the range of 43-48 % of the total formulation. 2. The paint composition as claimed in claim 1 wherein polyester resin is prepared by glycolising the polyester waste (PEW) with neopentyl glycol (NPG) and condensing the glycolised PEW with dimethyl terephthalate (DMT) or rosin maleic adduct (RM adduct). 3. The paint composition as claimed in claims 1 and 2 wherein said condensation reaction comprises reacting the gycolized PEW with dimethyl terphthalate (DMT) in presence of catalyst zinc acetate by heating rapidly at temperature range of 160-200°C at a rate of 10°C per hour and held at this temperature until the calculated amount of by product (water or methanol) is collected; subjecting reaction mass to polycondensation by gradually heating at temperature ranging 180-210°C under vacuum to get polyester resin with an acid value of approximately 16 to 21. 4. The paint composition as claimed in claim 1 to 2 wherein said condensation reaction comprises reacting the gycolised PEW with rosin maleic adduct is carried out in presence of catalyst zinc acetate by heating rapidly at temperature ranging from 160-200°C at a rate of 10°C per hour and held at this temperature until the calculated amount of by product (water or methanol) is collected; subjecting reaction mass to polycondensation by gradually heating at temperature ranging 180-210°C under vacuum to get polyester resin with an acid value of approximately 16 to 21. 5. The paint composition as claimed in any preceding claims wherein source of PEW is selected from polyester fiber, PET bottles used for mineral water and beverages, film waste and any other waste available from synthetic fiber industry or a textile plant. 6. The paint composition as claimed in claims 1 and 3, wherein the said polyester resin based on DMT is having acid value (mg KOH/g) of 16.3; melting range of 135-139°C; relative viscosity of 1.3024 and number average MW (Mn) 1832. 7. The paint composition as claimed in claim 1 and 4, wherein the said polyester resin based on RM adduct is having acid value (mg KOH/g) of 21.0; hydroxyl value (mg KOH/g) of 8.1 ; melting range of 104-106°C;relative viscosity of 1.2607 and number average MW (Mn) 1685. 8. Thermoplastic road marking paint compositions and the process for preparation as substantially described herein with reference to the foregoing examples 1 to 4.

Full Text

FORM 2
THE PATENTS ACT, 1970
(39 of 1970)
COMPLETE SPECIFICATION
[See section 10; rule 13]
"Thermoplastic road marking paint composition"
(a) MALSHE VINOD CHINTAMANI
(b)l, Staff Quarters, UDCT Campus, Matunga Mumbai - 400 019.
Maharashtra, India (c) Indian National
The following specification describes the nature of the invention and the manner in which it is to be performed:

Related Application:
Related application for patent: Related application for "A low cot, better performance and ecofriendly thermosetting powder coating formulation and process thereof with application no. 1114/MUM/2003 for the synthesis of polyester resin from polyester waste is disclosed and reported herein.
Technical Field of the invention:
The present invention relates to polyester resin based on poly ester waste (PEW) and its preparation which is useful in thermoplastic road marking paints as a binder. This invention further relates to synthesis of the resin based on PEW modified with dimethyl terphthalate (DMT) and / or rosin maleate adduct.
Background and Prior Art:
Traffic markings have evolved greatly throughout the past decade and continue to -improve to meet environmental and functional requirements for traffic control. The first major recorded event in traffic marking was in 1917 when a center dividing line was painted white in Michigan, USA, to assist drivers to stay in their own lane. The practice was adopted the next year as a standard procedure in Michigan. In 1934, glass beads were introduced to improve the visibility of traffic markings. The first patent for commercial epoxies was issued in 1945 to Devoe and Reynolds. In the early 1950s, the researchers at Prismo Company in Montgomery, PA invented pre-formed heavy-duty striping tapes and by the end of the 1959s thermoplastics were beginning to be used on American roads. In 1958 prismo developed the first successful thermoplastic application machine. Many fascinating developments continued to follow in response to various requirements and challenges posed to the industry.
Many terms are used to describe traffic marking systems; line marking paints, traffic paints, striping paints, etc. Although they all serve the same purpose i.e. marking the roads with clear visible lines, they differ profoundly in their composition, properties and durability. Some are even meant to be only temporary, as opposed to those, which last for many years under heavy continuous traffic.

Traffic markings are composed of pigments, extenders, specialty chemicals and dispersion medium. The pigment in the formulations is generally titanium dioxide (TiCh) for white marking and yellow (lead chromate-PbCr04) for yellow marking. Minor quantities of tinting colours may be used to obtain the correct hue. Extenders are generally inert inorganic compounds used to give the desired tensile strength and abrasion resistance to traffic markings. Some commonly used extenders are calcium carbonate, calcined clays, silicates, silica, mica, barium sulfate, etc. quantity of extenders is sometimes reduced to preserve the brightness and opacity of traffic marking formulations.
Thermoplastic traffic markings are based on resins that melt at elevated temperatures and revert to a solid state on cooling. They dry quickly i.e. as fast as 30 seconds and do not depend on ambient drying conditions for their set. They set just by the drop in temperature to ambient conditions. Thermoplastics can be applied under high humidity conditions as well.
In formulating such materials, pigments, fillers, plasticizers, resins (hydrocarbon or alkyd), heat stabilizers, etc are mixed either as dry powders or in molten resins under high shear. For traffic marking, thermoplastics are melted between 180-190° C and can be extruded or spray applied in film thickness ranging from 30-125 mils. Some of the major advantages are:
■ No hazardous solvents.
■ Used on asphalt as well as Portland cement (a primer is required).
■ Highly durable. Will last as much as 10 times longer than conventional traffic paints, costing only 3-4 times more than water-borne paints.
Thermoplastic marking are used extensively on roads carrying heavy traffic; longitudinal lines, stop bars, cross walks, etc. The latest generation of thermoplastic is offered in the form of pre-formed tapes that can be used in all types of applications; temporary tapes for construction sites and permanent tapes for medium to high traffic volume areas. They are 100% solids, thus environmentally safe and without any volatile organic compounds (VOC) issues. The durability of these tapes is excellent. Even the temporary tapes have been known to last for 2-2.5 years. Permanent types have lasted up to 4 years. Composed of polymers, pigments and glass beads, thermoplastic reflective tapes have excellent skid resistance, resistance to weather, salt, water and petrochemicals like petrol and oil.

Traffic markings have contributed tremendously to pedestrian and vehicular safety since the turn of the century and they continue to evolve with technological advancements in materials and techniques. Over the past decades, water-borne traffic markings have effectively resolved most of the health, safety and performance requirements. Thermoplastics and epoxy systems have also found a niche within the industry as reported in US3,321,329. As these technologies become more cost effective, they may eventually acquire a large market share. The traffic marking industry will undoubtedly continue to concentrate on the performance and safety aspects while taking advantage of the technological advancements in the future years.
Thermoplastic road marking is used for special application. In comparison with the usual alkyd based traffic paints, both drying time and lifetime are improved. The binder system is mostly a mixture of resins e.g. rosin ester and C5 dicyclopentadiene resin (15-20 %), white pigment (Ti02, 25 %), filler (CaC03, 45-50 %) and reflective glass beads (25 %). Film thickness is about 2-3 mm when coated normally, 5-7 mm when screen applied into flat recesses. For yellow markings aromatic resins may also be used, but when unstabilized they are more sensitive to oxidation and discolouration.
For road markings, paints are used more than thermoplastic materials. The coating thickness is 0.5-mm. These, paints are based on binder systems containing alkyd resins, Chlorinated rubber, and combined with hydrocarbon resins or rosin esters. The main requirements are stability to light and abrasion resistance. Resin characteristics must meet the following standards light stability (UV resistance), neutral and unsaponifiable, resistant against water, diluted acids, alkali and mineral oils, good film forming and wetting properties, good compatibility with synthetic rubber, synthetic copolymers, and other resins which are normally used in the formulation of road marking systems. Good thermal stability must allow heating to temperatures of 200°C.
For this area of application, there are a number of commercially available resins, especially low priced binders. The aliphatic C5 resins types are by far the most popular, but other resin types are also used.
1. C5 (DCPD)- modified C9 hydrocarbon resins.
2. Hydrogenated hydrocarbon resins.
3. C4 modified C9 hydrocarbon resins.
4. C9 resins with low indene and high alpha methyl styrene / vinyl toluene content.

5. Terpene phenolic resins.
The C5 modified and hydrogenated resins commonly show excellent light stability, a major factor, especially for white road markings. The light stable hydrogenated resins are not normally used because of their relatively high price. Some of the commercial C5 modified resins also show remarkably good UV stability and are also used for white markings, depending on specific requirements. C9 resins show a gradually deteriorating light stability though they are often used in combination with C5 resins or in less sensitive areas. Because of their slight tendency to yellow under the influence of light, indene -coumarone resins are not used at all. C9 resins are primarily used in yellow road markings. For white road markings a higher pigmentation is suggested. The road marking paints are divided into three types mainly:
Solvent based traffic paints:
They have been by far the most widely used traffic markings. They are easy to apply through conventional methods, fast drying and very durable. They are intimate dispersions of primary pigments, extenders and specialty chemicals in a dispersion medium (like alkyd resin) and fast evaporating solvents.
Water-borne traffic paints:
Water-borne traffic paints are intimate dispersion of pigments, extenders, specialty chemicals (like biocides, film formers, adhesion providers etc.) in a dispersion medium comprising of emulsion polymers, water and co-solvents. Major disadvantage of water borne paints is that they require more drying time.
Thermoplastics traffic marking:
Thermoplastic traffic markings are based on resins that melt at elevated temperatures and revert to a solid state on cooling. They dry quickly i.e. as fast as 30 seconds. In formulating such systems, pigments, fillers plasticizers, resins, heat stabilizers etc. are mixed either as dry powders or in molten resins under high shear. For traffic markings, thermoplastics are melted between 177-240° C and are either spiay applied or gravity extruded. Major advantages of Thermoplastics traffic marking are, no hazardous solvents, and high durability on asphalt as well as Portland cement roads.

The main contents of road marking paints are pigments, extenders, specialty chemicals and a dispersion medium.
Pigments:
The pigment in the formulations is generally TiO2 for white markings and chrome yellow (lead chromate-PbCrO4) for yellow. Minor quantities of tinting colors may be used to obtain the correct hue.
Extenders:
Extenders are generally inorganic compounds used to give the desired tensile strength and abrasion resistance to traffic markings. Some commonly used extenders are calcium carbonate, silicates, silica, mica, barium sulphate etc. extenders are omitted sometimes to preserve the brightness and opacity of traffic marking paints.
Retro-reflective glass beads:
Glass beads were first used in 1934 when they were used on traffic signs to increase their visibility. Glass beads are used in all types of traffic paints; solvent based, water borne and thermoplastics. They can be either dropped in specified quantities on the wet traffic paints after application or they can be supplied premixed.
Glass beads are generally of the size 100 to 150 microns. They shall have resistance to acids, calcium chloride, sodium sulfide and water. These elements shall not have any dulling effect on the glass spheres. The main reason for use of glass beads in road marking paints is the visibility at night. At night when light from headlight falls on the road markings, the glass beads on them reflect back the light. The paint contains almost 20-30% by weight of these glass beads, therefore if top layer goes off there are more glass beads under this layer.
Resins:
The resins that can be used for road marking paints are as follows:
Alkyd resins: Alkyd resins can be used for both solvent based and thermoplastic markings. Alkyd resin based traffic paints are suitable for both asphalt and concrete surfaces. They have excellent resistance to petrochemicals and they can be applied by conventional or airless spray methods.

Chlorinated- rubber alkyd resins: They have better toughness and chemical resistance and better overall durability as compared to conventional alkyd based paints. The cure mechanism involves solvent evaporation and oxidation. They are easy to apply. But because of regulatory restrictions on chlorinated rubber they are not used since 1980s.
Hydrocarbon resins: Hydrocarbon resins are primarily petroleum-based compounds. Thermoplastics based on hydrocarbon resins lack adequate resistance to petrochemicals (like oil, grease etc.). Alkyd and hydrocarbon resins are not compatible. Any cross contamination in the heating kettle will result in performance problems.
Polyester paint: Polyester paints provide unsurpassed durability, which makes this the most cost effective paint for asphalt, when compared on a life-cycle basis with alternative paints and marking materials. Advanced polyester paint technology with the development of VOC compliant formulations by replacing MEKP with a non-hazardous catalyst to achieve a chemical cure poses no threat to either applicators or the environment. They achieve short curing times without sacrificing chemical stability.
Acrylic water borne emulsions: Acrylic water borne traffic paint, the polymeric binder is an acrylic emulsion. After the water borne paint is applied, the water begins to evaporate, which causing the emulsion particles to move closer together, resulting in deformation of the spherical particles and hexagonal particles begin to form. In the last stage, the water and coalescent diffuses more or less completely out to produce a continuous film.
Vinyl chloride: The vinyl chloride marking film comprises a film, a suitable pressure sensitive adhesive layer on one surface and a suitable releasing sheet on the adhesive layer. Ultraviolet absorbers are incorporated to protect the markings from UV radiation. Application techniques used in road marking are as follows;
Surface preparation:
Care is taken to ensure that the surface is clean, dry and free of loose material. A simple
blower is typically sufficient to remove gravel and dust in most instances. When applying
over previously coated areas, special care is required to remove any loose or peeling
paint.
Other surface conditions, such as areas with large amounts of engine oil build-up or
existing epoxy coatings, may require a power washing procedure or abrading the surface

before application of the paint. New concrete and asphalt should be aged for a minimum 30 days prior to painting.
Weather conditions:
Air temperature, surface temperatures, humidity, and weather conditions following the application are extremely important factors in the success of the road marking paint. At lower temperatures or when humidity is extremely high, a significant amount of extra time will be needed for drying.
Equipments:
Solvent based and water borne traffic paints are applied with conventional air or airless
spray equipments. For thermoplastic traffic markings two basic pieces of equipment are
needed.
1. A kettle to melt the thermoplastic composition.
2. A screened applicator machine to extrude and deposit the desired film thickness on the pavement. These can be walk-behind, ride-on or truck or van mounted.
Stain resistant markings are described in US patent 594833. Water borne road paints in particular have the problem of yellowing, which occurs after application of the paint on the road. A possible cause for this phenomenon is rust formation due to the reaction of iron with the materials in the paint formulation. Incorporating a chelating agent in the water borne road-marking paint solves this problem. The chelating agent is capable of chelating iron ions to form a substantially colourless complex, as per the above patent.
US Patent 6036764 describes yellow pigment blend. Traditional traffic paint use lead and hexavalent chrome pigments, which are toxic to plants, animals and humans and are subjected to strict environmental regulation. Conventional organic pigment, when subjected to hot melt heat test decompose and discolor. Therefore a blend comprising; Yellow nickel titanate pigment, Yellow bismuth vanadate and Yellow isoindolinone pigment is formulated. This is a lead and chrome free yellow pigment that can be used in hot melt traffic markings as described in this patent.
US patent 6211260 deals with water borne paints which are non pollutive but which dry slowly. One of the important features of road marking paints is the speed at which they dry after application of the paint on the road. This dictates the level of disruption required to road traffic in order to apply them. Since solvent-based paints are polluting, using

water borne is more environmentally friendly. But the drying times for water borne paints are dependent on the relative humidity of the atmosphere.
Water-resistant traffic markings based on alkyl-based paints are reported in US patent 6228901. Conventional water borne paints tend to be less wear resistant than traditional alkyd based paints. The term wear resistance means the degree of resistance of the traffic markings to detaching from the road surface when the marking is exposed to traffic conditions and to UV radiation.
The method of producing a wear resistant traffic marking paint comprises applying on the road surface an aqueous traffic paint, which contains a polymer polymerized from a monomer mixture that includes a range from 80% to 99.9% (all in weight % based on polymer solids) of one or more hydrophobic monomers and drying the layer to form the wear resistant traffic marking. The hydrophobic monomer can be butyl methacrylate, ethyl methacrylate etc. Advantage of this method is that it produces traffic markings that are wear resistant even under exposure to UV radiation from sun. Features of an ideal road marking paint are described hereafter,
■ Reduced environmental impact through formulations having low VOC.
■ Improved balance of coating rheology during application and film formulation to promote substrate wet out and fast cure to free films.
■ Good visibility at night i.e. they should be retro-reflective in nature.
■ Broadened range of weather conditions for coating application.
■ Improved marking performance through increased durability and reflectivity.
■ Quick drying time for resumption of traffic.
■ Improved properties like wear-resistance, stain-resistance, abrasion resistance, skid- resistance, UV resistance etc.
The solid waste from polyester plant comprises oligomeric polyesters and a small percentage of titanium dioxide pigment. This material cannot be used for production of fibers, as it would cause considerable loss of its properties due to presence of impurities. Due to the pigment content, it is not possible to consider applications where transparent coatings are desired.

A new road marking paint has emerged in the past few years. This is applied in the form of strips of about 5 mm thickness and is applied as an extruded coating at the site. The coating has following requirements.
• It should be extrudable at relatively low temperatures of about 150°C.
• It should have low application viscosity and good wetting properties.
• It should be able to take high pigment loading.
• It should have good colour retention in outdoors.
• It should have a high melting point, good abrasion resistance and low cost.
At present hydrocarbon resins are used for this application and most of these resins are imported. There are only few manufacturers of these products in India and the acceptability of the product is increasing due to long life offered by the product. The consumption is in excess of 15,000 tpy with approximately 30 % resin content. The expected consumption would be about 25,000 tpy by end of 2003. The world market is already very large. Since, at present, this product is based on hydrocarbon resins that are not readily available in such quantities, it is necessary to look at alternate raw materials, which have considerably large manufacturing base. Polyester based on DMT or PTA and ethylene glycol (EG) appears an ideal choice since the installed capacity of the raw materials is very huge.
In this invention studies on to the viscosity, molecular weight relationship of the polymer after completely characterizing it is done. The flow properties might be modified by addition of other raw materials to a small extent. These may be neopentyl glycol, dimethyl terephthalate and rosin maleic adduct which considerably influence the performance of the polymer.
The present work involves the preparation of polyester resin based on PEW, which would be useful in thermoplastic road marking paints as a binder. Polyester was synthesized based on PEW modified with DMT and rosin maleic adduct. Different paint formulations were prepared and evaluated for their performance at different temperatures to study the influence of composition variables (pigment / binder ratio, resin content, and filler employed) on properties.
Thermoplastics type road marking paint is a prime choice for traffic paints. If offers following advantages over solvent-based, waterborne paints and epoxies:
■ Absence of environmentally unfriendly solvents
■ Good water resistance when completely dried

■ Safe for traffic personnel
■ Easy application through the use of current traffic paint equipment
Objectives:
The objective of this work was to provide polyester resin based on PEW to enhance the opportunities for successful hot-applied thermoplastic pavement marking applications and reduce environmental pollution. It is intended to be beneficial to the public, contractors, application crews, project engineers and inspectors.
Summary of the Invention:
The present invention relates to polyester resin based on polyester waste (PEW) and its preparation which is useful in thermoplastic road marking paints as a binder. This invention further relates to synthesis of the resin based on PEW modified with DMT and / or rosin maleate adduct. The present invention relates to thermoplastic type road marking paint wherein the said
paint comprises; polyester resin in the range of 20-25% of the total formulation; glass
beads in the range of 22% of the total formulation; pigment in the range of 10% of the
total formulation; filler in the range of 43-48 % of the total formulation.
The polyester resin is made of polyester waste (PEW). A source of PEW is selected from
polyester fiber, PET bottles used fro mineral water and beverages, film waste and any
other waste available from synthetic fiber industry or a textile plant etc.
The PEW is glycolised with Neopentyl glycol (NPG) at temperature 180 to 210° C in
presence of Zinc acetate catalyst.
The polyester resin is prepared by condensing glycolised PEW with DMT or Rosin
maleic adduct (RM adduct) which is carried out in presence of catalyst Zinc acetate;
heating rapidly to 160° C, from 160-200° C at a rate of 10° C per hour and held at this
temperature until the calculated amount of by product (water or methanol) is collected;
subjecting reaction mass to polycondensation by gradually heating at temperature ranging
180-210° C under vacuum, to get polyester resin with low acid value.

The polyester resin based on DMT is characterized by acid value (mg KOH/g) of 16.3;
melting range of 135-139°C; relative viscosity of 1.3024 and number average MW (Mn)
1832.
The polyester resin based on rosin maleic adduct is characterized by acid value (mg
KOH/g) of 21.0; hydroxyl value (mg KOH/g) of 8.1 ; melting range of 104-
106°C;relative viscosity of 1.2607 and number average MW (Mn) 1685.
The paint based on PEW with DMT is characterized by wet abrasion in the range of 1-3-
2.1 g; dry abrasion in the range of 1.1-1.9 g; hardness at 50°C passes; W+ in % after
lOOhrs 9.68 - 13.8; W" in % after lOOhrs 8.72-11.24 and flow of paint is poor.
The paint based on PEW and RM adduct is characterized by wet abrasion in 1.7 -2.5 g;
dry abrasion in the range of 1.5-2.0 g; hardness at 50°C passes; W4 in % after lOOhrs
11.52-13.16; W" in % after 1 OOhrs 9.44 -10.44 and the flow of paint is good.
The pigment used is titanium dioxide for white road marking paint or chrome yellow
(lead chromate - PbCrO4) for yellow road marking paint.
The filler is calcium carbonate and used in the range of 15-20% of the total formulation.
The filler is marble powder and used in the range of 28% of the total formulation.
A process for preparation of the thermoplastic type road marking paint wherein said
process comprises mixing of polyester resin, titanium dioxide, fillers, and glass beads in a
mixing vessel; heating to 180-190°C; maintaining at the same temperature for 30minutes
with high stirring and pouring the product obtained in special molds with a film thickness
of 3-5mm.
Detailed Description:
The main contents of thermoplastic type road marking paints are binders, pigments, extenders, specialty chemicals and a dispersion medium. Raw materials used are described in the following;
Pigments used here are selected from TiO2 for white marking and chrome yellow (lead chromate - PbCrO4) for yellow marking.

Extenders are generally inorganic compounds used to give the desired tensile strength and abrasion resistance to traffic markings. Some commonly used extenders are calcium carbonate and marble powder.
Retro-reflective glass beads are used in all types of traffic paints; solvent based, water borne, thermoplastic and reflective tapes. They can be either dropped in specified quantities on the wet traffic paints after application or they can be supplied premixed. Glass beads are generally of the size 100 to 150 microns.
PEW source used in polyester synthesis is selected from polyester fiber, PET bottles used fro mineral water and beverages, film waste and any other waste available from synthetic fiber industry or a textile plant etc.
The monomers used to prepare polyester resin are selected from Neopentyl glycol, Dimethyl terephthalate and Maleic anhydride. All reagents were used without further purifications
The prepared polyester resins were characterized for following properties,
1. Colour and appearance.
2. Melting range.
3. Acid value.
4. Hydroxyl value.
5. Number average molecular weight by Gel Permeation Chromatography.
The thermoplastic road marking materials were sampled and tested in accordance with the specified methods.
Dry and wet abrasion test: For dry and wet abrasion test, disk specimens were employed (80 mm diameter and 3 mm thick). After 24 hrs, samples were abraded using Wet Abrasion Scrub Tester with an abrasive and 1000 g load (ASTM D-4060). The dust produced by the wearing operation was eliminated continuously. When a track is formed as a consequence of wearing, the sample was weighed. After that, the wearing operation was continued along 100 revolutions of the equipment and weighed again. The difference between the two values obtained was expressed as dry wearing.
After finishing the previous test, distilled water was added to the track and the operation was continued during 100 more revolutions. The sample was conditioned for water

elimination and weighed. The difference in both these weights gave the value for wet wearing.
Hardness: Hardness of the paint at temperature between 40-45°C was determined according to ASTM-D 2240. In this case test panels were of 50 mm diameter and 3 mm thick. The panels were kept in an oven for one hour at 40-45°C. Samples were stabilized during one hour at test temperature before the hardness was determination.
Water absorption and Water elimination test: For the determination of water absorption and water elimination rates, specimens of 50 mm diameter and 3 mm thick were prepared and weighed to ± 1 g. They were completely submerged in distilled water at room temperature for 100 hrs. Then they were dried with filter paper and weighed after 100 hrs. Absorption values were obtained by the difference in the two weights of the samples. Afterwards, the probes were conditioned at room temperature and exposed to sun for 100 hrs. Water elimination values were obtained by the weight difference.
Flow test: The flow of the thermoplastic road marking paint was tested; 500 g of the paint in molten condition (Temperature about 180-200°C) was poured over a test base. After allowing it to settle, the area covered by the paint was measured. The paint is considered to have good / satisfactory flow property if it spared over one feet area.
The PEW was characterized by its chemical and physical analysis such as acid value, hydroxyl value, saponification value, melting range. A calculation was done for glycolysis of PEW and synthesis of polyester resins with required acid value.
In the second part PEW was glycolyzed by Neopentyl glycol to convert hydroxyl terminated low molecular weight oligomers. The same process was followed for glycolysis, which is described in earlier application number 1114/MUM/2003. The amount of glycol required for glycolysis depended on initial composition of PEW.
Standard laboratory esterification equipment was used for the synthesis of polyesters. Glycolyzed PEW, dimethyl terephthalate (DMT) or rosin maleic adduct were taken in the required proportions in three necked quick fit round bottom flask equipped with stirrer,

thermometer, Dean and Stark apparatus and nitrogen purge system. Zinc acetate was used as a catalyst (1% on the basis of total amount of dibasic acid). The ingredients were heated rapidly to 160 °C, from 160-200 °C at a rate of 10 °C per hour and held at this temperature until the calculated amount of by product (water or methanol) was collected. Then the reaction was carried forward to polycondensation process by gradually heating at temperature ranging 180-210 C under vacuum, to get polyester resin with low acid value. The completion of polymerization was checked by determining the acid value of the resin. The product was poured in a tray and was completely characterized for its physical and chemical properties like hydroxyl value, acid value, and relative viscosity by standard methods. The reaction conditions and optimized composition of ingredients are as given in Table 1 and 2.
Table: 1 Reaction conditions:

Resin Code Glycolysis Condensation Polycondensation Eliminated MeOH Qty (ml)

Temp Time Temp Time Temp Time

PRl PR 2 200 200 3.0 3.0 180 210 3.0
2.5 210 200 1.0 1.0 26.0 7.3
Table: 2 The optimized compositions for polyester.

Ingredients PRl PR2
PEW 100 100
NPG 21.47 21.47
DMT 60.55 -
RM adduct - 111.7
Note: All values are calculated for 100 g of PEW, PR 1 = Polyester based on DMT, PR 2 = Polyester based on Rosin maleic adduct.
Thermoplastic reflecting materials were formulated, containing a binder resin based on PEW and modified with rosin. The modified resin was used in 20, 22 and 25% on total formulation. As a hiding pigment, titanium dioxide (rutile type) was employed to obtain a white colour with high luminosity. Formulation was completed using calcium carbonate

and marble powder as fillers, which give good wearing resistance. Sample formulations are indicated in Table 3.
Table: 3 Compositions of the Thermoplastic Materials.

Materials I (%) II (%) III (%)
Polyester (PR1 or PR2) 20 22 25
Glass beads 22 22 22
Titanium dioxide 10 10 10
Calcium carbonate 20 18 15
Marble powder 28 28 28
Mechanical stirrer was used for the thermoplastic preparation rotated at 50-60 rpm to give a smooth consistency to the thermoplastic material to avoid local over heating. For heating, a mineral thermic fluid circulating in the heating jacket (maximum temperature 300°C) around a mixing vessel was employed.
Polyester resin PR1, titanium dioxide, fillers, and glass beads were taken in the mixing vessel and heated at 180 -190 °C. Operation at this temperature was maintained for 30 min with high stirring and then the product obtained was poured in special molds with a film thickness of 3 to 5 mm. The sample tests, performed at different temperatures, included wet and dry abrasion, hardness, water absorption and water elimination rate and flow properties of paints. These properties are given in Table 6 and 7.
Thermoplastic resin based road marking experiments were conducted using different compositions and embodiments. Thermoplastic road marking with its superior visibility and weather resistant durability, allows drivers to feel confident and secure on the road. Thermoplastic road marking complies with the highest international standards and is ideal for highways and all other paved roads. Superior visibility prevents accidents and it contains high quality glass beads that create an illuminating effect at night, provide lasting daytime visibility and are skid resistant.
Thermoplastic road markings are fast setting and dry within minutes, made from durable thermoplastic materials. Thermoplastic road markings retain their texture for more than two years marking their life cycle more cost effective than conventional paint. Reflecting thermoplastics applied on city streets, roads or highways frequently lose their efficiency

due to the wearing or the partial detachment of the used materials; the appearance and physical characteristics are modified.
The adequate lifetime is a function of different variables, acting individually or as a whole adhesion to the surface where they were applied (asphalt or concrete), resistance to abrasion and weathering (moisture due to rain and dew remaining for a long period of time in contact with thermoplastic marks), high temperature producing deformation or low temperature diminishing elasticity and favoring checking or cracking of the mark.
Hydrocarbon thermoplastic, formulated with petroleum-based resins, is a well-proven, durable pavement marking system, resistant to the effects of oil, grease and salt and provides exceptional performance in all applications. Hydrocarbon thermoplastic is used in all types of applications. Its retroreflective performance and durability are only superceded by alkyd thermoplastic materials. For a reference, hydrocarbon resin based on Dicyclopentadiene was chosen. The hydrocarbon resins posed some problematic effects on the road marking paint by the rolling action of tires on the paint thereby removing it completely and exposing the underneath tar road. The main aim of this work was to improve this aspect of the road marking paint. As a result this property can best be improved by replacing the conventional hydrocarbon used in road marking paints with polyester resin as a binder, which is known to have good adhesion on variety of surfaces.
The most preferred embodiment was observed to be polyester based on DMT and Rosin maleic adduct which was found to be transparent, glossy, brittle and coloured. The colour could be attributed to side reactions like oxidation and initial colour of PEW. Other properties of polyester including acid value, hydroxyl value, relative viscosity and melting range are listed in Table 5.
Table: 5 Properties of prepared polyester resins.

Properties PR1 PR 2
Acid value (mg KOH/g) 16.3 21.0
Hydroxyl value (mg KOH/g) - 8.1
Melting range (°C) 135-139 104-106
Relative viscosity 2.3024 1.2607
Number average MW (Mn) 1832 1685

Another embodiment namely by the polyester based on DMT showed high melting range, relative viscosity as compared with Rosin maleic-based polyester. Thermoplastic type road marking paints required low melt viscosity and low melting temperatures (approximately 90 to 100 °C) of binder. This was achieved by replacing DMT with Rosin maleic adduct.
The ingredients were melted at 180-190 °C for 30 minutes and extruded on the surface to be marked with a film thickness of 1-5 mm. Volatile solvents were not included in these formulations, so they are ecologically acceptable. Prior to their application, the surface was cleaned. The paint sample tests, performed at different temperatures, included wet and dry abrasion, hardness, water absorption and water elimination rate and flow properties of paints. These properties are given in Table 6.
Water absorption and water elimination tests were performed for 100 hrs. This property primarily measures the characteristics of other ingredients like fillers etc present in the formulation. From the Figure 1, it was observed that water absorption was greater in case of formulations with high content of fillers. Also it was higher in case of aromatic polyester i.e. DMT as compared to rosin maleic based polyester which is aliphatic in nature. Similar results were observed for water elimination test for all formulations based on DMT and rosin maleic adduct. The wet abrasion test shows greater wearing values than those obtained in the dry abrasion test. It was observed that formulation based on polyester resin with rosin maleic adduct showed greater wearing values for wet abrasion as compared to that from DMT. A similar trend was observed for dry abrasion. This could be due to greater interstitial voids present in rosin maleic-based polyester and its higher water sensitivity as compared to DMT based polyester.
Table: 6 Properties of road marking paint based on polyester with DMT.

Properties I II III
Wet abrasion in g 2.1 1.8 1.3
Dry abrasion in g 1.9 1.3 1.1
Hardness at 50 °C Passes Passes Passes
W+in % after 100 hrs 13.8 13.12 9.68
W" in % after 100 hrs 11.24 10.56 8.72
Flow of paint Poor Poor Poor

Where (W+) is Water absorption and (W) is Water elimination.
Results of hardness test as a function of temperature are related to the plasticization degree of the resin. This is particularly observed at 50°C, which is considered critical. Above this temperature, hardness diminishes abruptly in practically all of the samples. All these formulations passed the hardness test performed at 50°C. Hardness was performed as per the procedure given in methods of analysis.
Table: 7 Properties of road marking paint based on polyester with RM adduct.

Properties I II III
Wet abrasion in g 2.5 2.2 1.7
Dry abrasion in g 2.0 1.7 1.5
Hardness at 50 °C Passes Passes Passes
W+ in % after 100 hrs 13.16 12.00 11.52
W" in % after 100 hrs 10.44 10.00 9.44
Flow of paint Good Good Good
In the results of the water absorption and water elimination tests, the increases of weight of the thermoplastic mass during immersion is faster than the water elimination value.
Flow test for paints plays a major role in assessing their nature. It was found that formulations with DMT based polyesters showed poor flow. It has been improved by reducing the aromatic content by incorporating rosin maleic adduct instead of DMT. Thus formulations using rosin maleic-based polyesters gave satisfactory flow properties as compared to conventional resins used in thermoplastic road marking paints.
It will be readily apparent to one skilled in the art that varying substitutions and modifications may be made to the invention disclosed herein without departing from the scope and spirit of the invention. Thus, it should be understood that although the present invention has been specifically disclosed by preferred embodiments and optional features, modification and variation of the concepts herein disclosed may be resorted to by those skilled in the art, and that such modifications and variations are considered to be falling within the scope of the invention.

The following examples are for the purpose of illustration of the invention only and are not intended in any way to limit the scope of the invention.
Examples
Example 1
Synthesis of PR1
Glycolyzed PEW was prepared by glycolysing 100 g PEW with 21.47 g NPG at 200° C for 3 hour. This glycolised PEW was treated with 60.55 g dimethyl terephthalate (DMT) in three necked quick fit round bottom flask equipped with stirrer, thermometer, Dean and Starck apparatus and nitrogen purge system. Zinc acetate was added as a catalyst (1% on the basis of total amount of dibasic acid). The ingredients were heated rapidly to 160° C, from 160-200° C at a rate of 10° C per hour and held at this temperature until the calculated amount of by product (water or methanol) was collected. Then the reaction was carried forward to polycondensation process by gradually heating at temperature ranging 180-210° C under vacuum, to get polyester resin with low acid value. The completion of polymerization was checked by determining the acid value of the resin. The product was poured in a tray and was completely characterized for its physical and chemical properties like hydroxyl value, acid value, and relative viscosity by standard methods.
Example 2
Synthesis of PR 2
Glycolyzed PEW was prepared by glycolysing 100 g PEW with 21.47 g NPG at 200° C for 3 hour. This glycolised PEW was treated with 111.7 g Rosin maleic adduct (RM adduct) in three necked quick fit round bottom flask equipped with stirrer, thermometer, Dean and Starck apparatus and nitrogen purge system. Zinc acetate was added as a catalyst (1% on the basis of total amount of dibasic acid). The ingredients were heated rapidly to 160°C, from 160-200° C at a rate of 10°C per hour and held at this temperature until the calculated amount of by product (water or methanol) was collected. Then the reaction was carried forward to polycondensation process by gradually heating at temperature ranging 180-210° C under vacuum, to get polyester resin with low acid value.

The completion of polymerization was checked by determining the acid value of the resin. The product was poured in a tray and was completely characterized for its physical and chemical properties like hydroxyl value, acid value, and relative viscosity by standard methods.
Example 3
Thermoplastic paint
Polyester resin PR2 (25 g), titanium dioxide (22 g), Calcium carbonate (lOg), Marbel powder (28 g), and glass beads (22g) were taken in the mixing vessel and heated at 180-190° C. Operation at this temperature was maintained for 30 min with high stirring and then the product obtained was poured in special molds with a film thickness of 3 to 5 mm. The sample tests, performed at different temperatures, included wet and dry abrasion, hardness, water absorption and water elimination rate and flow properties of paints. These properties are given in Table 6 and 7.
Example 4
Thermoplastic paint
Polyester resin PR1 (22 g), titanium dioxide (10 g), Calcium carbonate (15 g), Marble powder (28 g) and glass beads (22g) were taken in the mixing vessel and heated at 180 190° C. Operation at this temperature was maintained for 30 min with high stirring and then the product obtained was poured in special molds with a film thickness of 3 to 5 mm. The sample tests, performed at different temperatures, included wet and dry abrasion, hardness, water absorption and water elimination rate and flow properties of paints. These properties are given in Table 6 and 7.
Description of Drawings:
Figure 1 describes comparative results for water absorption and elimination test for road marking paints based on polyester with DMT and Polyester resin with rosin maleic adduct. Graph for results obtained for water absorption test is shown by number 9. In this water absorption test, Y axis is shown by 1 which indicates the water absorbed in percentage after 100 hours exposure. X-axis is shown by number 2 which indicates three different formulations with 20, 22 and 25 % of polyester resin based on DMT and rosin-

maleic adduct. Number 3 showed by dark black colour column which is for formulation containing polyester resin based on DMT). Number 4 showed by gray column which is for formulation containing polyester resin based on rosin-maleic adduct. Results obtained for water elimination is shown by number 10. Y axis indicates the percentange water elimination after exposure of 100 hours which is shown by number 5, X-axis is shown by number 6 which indicates three different formulations with 20, 22 and 25 % of polyester resin based on DMT and rosin-maleic adduct. Number 7 showed by dark black colour column which is for formulation containing polyester resin based on (DMT). Number 8 showed by gray column which is for formulation containing polyester resin based on rosin-maleic adduct.
Polyesters based on PEW show high potential for thermoplastic type road marking paint and durable alkali resistant pigment. Road marking paint using these polyesters show fast drying and other advantages such as excellent adhesion, durability, light reflectivity, water resistance and good weatherability for concrete and asphalt surfaces. These types of paints are especially suitable for highway coating because they are more easily applied than a hot-spray type. This type of traffic paint materials can be applied by a roller or a truck-mounted striper. It's especially strong in durability, low drying time and night reflectivity. While the formulations based on polyesters synthesized from PEW and DMT exhibit poor flow properties than the conventional paints, polyesters prepared from PEW and rosin maleic adduct show very good flow properties as compared to conventional paints.

I Claim,
1. Thermoplastic road marking paint composition comprising polyester resin derived from polyester waste in the range of 20-25% of the total formulation; glass beads in the range of 22% of the total formulation; titanium dioxide as pigment in the range of 10% of the total formulation; calcium carbonate and marble powder as fillers in the range of 43-48 % of the total formulation.
2. The paint composition as claimed in claim 1 wherein polyester resin is prepared by glycolising the polyester waste (PEW) with neopentyl glycol (NPG) and condensing the glycolised PEW with dimethyl terephthalate (DMT) or rosin maleic adduct (RM adduct).
3. The paint composition as claimed in claims 1 and 2 wherein said condensation reaction comprises reacting the gycolized PEW with dimethyl terphthalate (DMT) in presence of catalyst zinc acetate by heating rapidly at temperature range of 160-200°C at a rate of 10°C per hour and held at this temperature until the calculated amount of by product (water or methanol) is collected; subjecting reaction mass to polycondensation by gradually heating at temperature ranging 180-210°C under vacuum to get polyester resin with an acid value of approximately 16 to 21.
4. The paint composition as claimed in claim 1 to 2 wherein said condensation reaction comprises reacting the gycolised PEW with rosin maleic adduct is carried out in presence of catalyst zinc acetate by heating rapidly at temperature ranging from 160-200°C at a rate of 10°C per hour and held at this temperature until the calculated amount of by product (water or methanol) is collected; subjecting reaction mass to polycondensation by gradually heating at temperature ranging 180-210°C under vacuum to get polyester resin with an acid value of approximately 16 to 21.
5. The paint composition as claimed in any preceding claims wherein source of PEW is selected from polyester fiber, PET bottles used for mineral water and beverages, film waste and any other waste available from synthetic fiber industry or a textile plant.

6. The paint composition as claimed in claims 1 and 3, wherein the said polyester resin based on DMT is having acid value (mg KOH/g) of 16.3; melting range of 135-139°C; relative viscosity of 1.3024 and number average MW (Mn) 1832.
7. The paint composition as claimed in claim 1 and 4, wherein the said polyester resin based on RM adduct is having acid value (mg KOH/g) of 21.0; hydroxyl value (mg KOH/g) of 8.1 ; melting range of 104-106°C;relative viscosity of 1.2607 and number average MW (Mn) 1685.
8. Thermoplastic road marking paint compositions and the process for preparation as substantially described herein with reference to the foregoing examples 1 to 4.

Documents:

1116-mum-2003-abstract(complete)-(21-10-2004).pdf

1116-mum-2003-abstract(granted)-(8-10-2007).pdf

1116-mum-2003-cancelled pages(17-4-2007).pdf

1116-mum-2003-claims(complete)-(21-10-2004).pdf

1116-mum-2003-claims(granted)-(17-4-2007).doc

1116-mum-2003-claims(granted)-(17-4-2007).pdf

1116-mum-2003-claims(granted)-(8-10-2007).pdf

1116-mum-2003-correspondence(17-4-2007).pdf

1116-mum-2003-correspondence(ipo)-(20-9-2006).pdf

1116-mum-2003-correspondence(ipo)-(27-7-2010).pdf

1116-mum-2003-description(complete)-(21-10-2004).pdf

1116-mum-2003-description(granted)-(8-10-2007).pdf

1116-mum-2003-description(provisional)-(21-10-2003).pdf

1116-mum-2003-drawing(21-10-2004).pdf

1116-mum-2003-drawing(provisional)-(21-10-2003).pdf

1116-mum-2003-form 1(17-4-2007).pdf

1116-mum-2003-form 1(21-10-2003).pdf

1116-mum-2003-form 1(24-11-2003).pdf

1116-MUM-2003-FORM 15(28-4-2011).pdf

1116-mum-2003-form 18(29-12-2005).pdf

1116-mum-2003-form 2(complete)-(21-10-2004).pdf

1116-mum-2003-form 2(granted)-(17-4-2007).doc

1116-mum-2003-form 2(granted)-(17-4-2007).pdf

1116-mum-2003-form 2(granted)-(8-10-2007).pdf

1116-mum-2003-form 2(provisional)-(21-10-2003).pdf

1116-mum-2003-form 2(title page)-(complete)-(21-10-2004).pdf

1116-mum-2003-form 2(title page)-(granted)-(8-10-2007).pdf

1116-mum-2003-form 2(title page)-(provisional)-(21-10-2003).pdf

1116-mum-2003-form 26(15-5-2003).pdf

1116-mum-2003-form 3(21-10-2003).pdf

1116-mum-2003-form 5(21-10-2004).pdf

1116-mum-2003-specification(amended)-(17-4-2007).pdf

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Patent Number

210677

Indian Patent Application Number

1116/MUM/2003

PG Journal Number

43/2007

Publication Date

26-Oct-2007

Grant Date

08-Oct-2007

Date of Filing

21-Oct-2003

Name of Patentee

MALSHE VINOD CHINTAMANI

Applicant Address

1, STAFF QUARTERS, UDCT CAMPUS, MATUNGA, MUMBAI 400 019, MAHARASHTRA, INDIA.

Inventors:

#	Inventor's Name	Inventor's Address
1	MALSHE VINOD CHINTAMANI	1, STAFF QUARTERS, UDCT CAMPUS, MATUNGA, MUMBAI 400 019, MAHARASHTRA, INDIA.
2	TAMBOLI HEMANTKUMAR ROHIDAS	1, STAFF QUARTERS, UDCT CAMPUS, MATUNGA, MUMBAI 400 019, MAHARASHTRA, INDIA.

PCT International Classification Number

C09D133/00

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1			NA