Novel stk2025 compositions

Abstract

The main objective of the present invention is to protect novel granular thermoplastic compositions for road signalling that comply with all the aforementioned requirements. The thermoplastic compositions for road signalling are stable, visible, durable, reflective in dry, wet and continuous rain conditions, resistant to wear from vehicle tyres and stable in very cold (-9°C) or very hot (60°C) weather. These temperatures can vary on the same day. These compositions can also be used for flat and convex lines.

Description

[0001] NEW STK2025 COMPOSITIONS

[0002] The Romans distinguished themselves as the foremost road builders in the ancient world, erecting a network of communication routes that remains unparalleled in efficiency even today. This road network, which stretched over 80,000 kilometers, developed concurrently with the territorial expansion of the Roman Empire. From its origins as a city-state, Rome gradually expanded, annexing neighboring territories by constructing roads that linked the conquered regions, thus contributing to the consolidation of its dominion. Therefore, it is clear that the creation of this robust road network was one of the cornerstones of Roman colonization.

[0003] Until the end of the 4th century BC, Roman roads were little more than paths leading to Rome from the various cities of Latium. From that point on, they began to be built according to a set plan, designed in conjunction with the tactical program of expansion. Given their considerable military significance, more complex road construction systems were developed to make them more permanent and better able to withstand different types of traffic. As early as 340 BC, after the conquest of Latium, the Via Latina was built to connect Rome with Capua, which had just been devastated in the Samnite War.

[0004] The basic patterns for traffic signs were established at the 1908 International Highway Congress in Rome. In 1909, nine European governments agreed on the use of four pictorial symbols. The intensive use and growth of traffic signs between 1926 and 1949, in parallel with the growth of the automobile fleet, led to the development of the European traffic sign system.

[0005] All specifications, manuals, standards, and regulations for road signage worldwide, including the INEN standards and regulations for road signage (INEN 004, INEN 1042), have a clear focus on the importance of horizontal road signs, symbols, or pavement markings, which are those that are demarcated (painted or installed) on the road surface or pavement; the most important characteristics of these markings are durability, nighttime retroreflectivity in dry and wet conditions, weather resistance, and slip resistance.

[0006] British patent number 2429978 protects a method for producing a thermoplastic composition for road markings comprising mixing an opaque pigment, a translucent particulate thermoplastic material, and reflective glass beads such that when the thermoplastic material is subsequently melted to bind the composition and the composition is applied as a marking, the glass beads on the visible surface of the markings are not substantially obscured by the opaque pigment. A thermoplastic composition for road markings comprising a mixture of a particulate filler material, a pigment, a translucent thermoplastic material, and reflective glass beads is also described; wherein the pigment adheres to the filler material and the reflective glass beads are generally pigment-free.Consequently, thermoplastic road markings immediately have retro-reflectivity without the need for an additional operation of adding glass beads.

[0007] Patent number W02020 / 068944 protects a road marking composition comprising a binder mixture comprising at least one alkyd ester, at least one wax, at least one ethylene copolymer, and at least one plasticizer; a filler mixture comprising at least one coloring additive, reflective elements, and at least one inert inorganic filler; and bentonite clay, the road marking composition being formed into granules. European patent number EP2504491 protects preformed, pre-joined thermoplastic sections comprising smaller articles; said articles and sections comprising flat upper surfaces and flat lower surfaces that are coplanar with each other, and further comprising an adhesive backing layer on said coplanar lower surfaces.wherein said adhesive backing layer connects and joins said coplanar lower surface to form the unified pre-bonded thermoplastic signage, thereby preventing detachment or separation of said signage during handling, movement and / or transport before or during the application of said pre-bonded signage, and wherein said articles, when appropriately sequenced, coupled and combined, comprise together said sections such that when said sections are also sequenced and coupled, said sections combine to form the thermoplastic signage with a final pattern, wherein said flat upper surfaces include the sequential features necessary to visibly aid the rapid assembly of one or more unified thermoplastic signs.

[0008] According to the World Health Organization (WHO) in its Global Plan for the Second Decade of Action, one of the goals is to reduce road traffic deaths and serious injuries by 50% by 2030. The United Nations General Assembly, in its resolution 74 / 299, declared 2021-2030 the Decade of Action for Road Safety, recognizing that road traffic crashes cause nearly 1.3 million preventable deaths and some 50 million injuries annually. They are the leading cause of death for children and young people worldwide. (PAHO. Paho.org). One of the causes of these senseless deaths is inadequate road signage. The present invention aims to contribute to reducing these statistics and constructing roads with the highest safety standards for drivers. In Ecuador, according to the National Transit Agency (ANT), in 2022 there were 21,739 road accidents, within these accidents the following breakdowns are shown: 19.006 injured and 2,002 dead; 16,015 men, 3,040 women, and 2,684 unidentified; 14,193 in cities and 7,546 on highways; 3,163 during the day and 18,576 at night. Furthermore, according to the CEA (Europe - Spain), "there are provinces such as Teruel and Zaragoza that see a fourfold increase in accidents, exceeding 27% compared to dry days." According to the US Meteorological Society, "the wetter the roads, the greater the danger; in the case of rain, the risk of fatal accidents increases by 34%."

[0009] Lane markings are crucial for demarcating a road to indicate the limits within which a driver must keep their vehicle. These lines can be painted using different technologies that have varying lifespans, visibility, retroreflectivity, and anti-slip properties. Ideally, the lines should be retroreflective in wet and rainy conditions, considering that some parts of the world can experience rain, drizzle, sunshine, and fog all in a single day, both day and night. Furthermore, extremely hot and cold climates also have adverse effects on the paints, so their formulations must be adapted to withstand harsh environments depending on where they are installed.Another factor to consider is the types of materials (asphalt and concrete) used to make the roads, which can interfere with the performance of the paints, mainly in adhesion and therefore their useful life.

[0010] None of the aforementioned patents solve the problem of having a thermoplastic composition for road markings that is durable, stable under extreme temperatures, from very cold (-9°C) to very hot (60°C), and that can fluctuate within a single day. Nor are they designed to function at all latitudes, adhere to all types of asphalt, and withstand the environmental conditions of different regions of the world.

[0011] Thermoplastic paints can be laminated or granular. Laminated or preformed paints are mostly used for symbols, letters, numbers, and other markings that come pre-formed and cut from the factory, ready to be laid on the road and melted with a torch. Granular paints are mainly used for lane markings and must be melted in large boilers and applied with complex machines that form the line, all while working on the road itself. Additionally, when applying granular paints, retroreflective and / or anti-slip elements must be applied to their surface through a "surface seeding" process, unlike laminated paints which already contain them on their surface.

[0012] These granulated thermoplastic compositions for road markings must be visible, retroreflective, durable, and stable in dry, humid, and continuous rainy conditions, as well as cloudy and rainy environments, in tropical areas that receive perpendicular sunlight year-round, at altitudes from sea level up to 5500 meters above sea level, as is the case in many parts of Latin America. Their durability must exceed 2-5 years for thicknesses of 1.5 mm and 3.2 mm respectively, under any traffic level, without suffering wear that obliterates the lines. In areas with low traffic levels, they can even have a useful life of 10-12 years.

[0013] Pavement lines or markings made with granulated thermoplastics can be flat or convex. The latter, also called shaped or profiled, offer visibility and retroreflectivity. Because they have convex bodies protruding from the flat base line, they generate sound and vibration properties that alert drivers that they are derailing or invading a prohibited area, and also warn pedestrians that a vehicle is approaching outside their permitted circulation zone.

[0014] The main objective of this invention is to protect new granular thermoplastic compositions for road signage that meet all the aforementioned requirements.

[0015] Thermoplastic compositions for road markings are stable, visible, durable, and reflective in dry, wet, and continuous rain conditions. They are resistant to wear from car tires and stable in very cold (-9°C) or very hot (60°C) climates. These temperatures can vary throughout the day. They can also be applied to both flat and convex lines.

[0016] A thermoplastic is a type of plastic material that exhibits deformability or flexibility at relatively high temperatures. It melts when heated and hardens upon cooling, reaching a glassy transition state. Below 10°C, it acquires a glass-like structure, becoming brittle and easily broken. These characteristics, which give the material its name, are reversible, meaning it can be heated, molded, and cooled repeatedly. This quality also makes it recyclable.

[0017] The granular thermoplastic paints of the present invention, used in horizontal road markings, have a durability ranging from 2 to 12 years. This longevity is directly related to their thickness and the level on the road where they are applied, being 5 to 10 times more durable than conventional liquid paints. A significant attribute of these coatings is that they maintain their retroreflectivity and / or skid resistance throughout their useful life, since they contain glass microspheres and / or anti-slip elements in the premix, which emerge as the line wears down. These properties are maintained throughout the useful life, which can vary from 2 to 5 years depending on the thickness and the traffic volume (ATV) of the road where they are installed, reaching up to 15 years on roads with low traffic volume.

[0018] Another objective of the present invention is to demonstrate that STK2025 granulated thermoplastic paints, used in horizontal road markings, possess the characteristic of retroreflectivity under dry, humid, or continuously rainy conditions. This technical characteristic of the formulations of the present invention depends on the quantity and type of retroreflective elements, such as glass microspheres and ceramic elements, present in the STK2025. This includes both those applied to the surface of the STK2025 as "surface seeding" and those that form part of the composition mixture used in the manufacture of the STK2025, referred to as "premixed."

[0019] Another additional objective of the present invention is to produce compositions of STK2025 granulated thermoplastic that have photoluminescent properties, allowing their visibility even at night without depending on the incidence of light.

[0020] An additional objective of the present invention is to produce STK2025 compositions of granular thermoplastic STK2025 for use in horizontal road markings, capable of providing anti-slip properties at different IRD (Slip Resistance Index) levels. This will be determined in the formulations of the present invention, taking into account the quantity of anti-slip elements they contain, both in surface application by "surface seeding" and in the initial mixture known as "premix."

[0021] Another additional objective of the present invention is that the compositions of STK2025, with their specific physicochemical characteristics, allow their application for the formation of both flat lines and longitudinal or transverse lines, and these can be flat or convex.

[0022] Furthermore, another objective of this invention is the incorporation of zirconium ceramic powders, uniform granules, and / or spheres, characterized by their high wear resistance. This addition strengthens the paint's wear resistance, extending the service life of the markings even with reduced thickness, especially on roads with high traffic flow.

[0023] Another feature of this invention is the methods, equipment, and manufacturing processes for obtaining a powdery (conventional) granular thermoplastic that is slightly dusty and non-dusty:

[0024] 1) Conventional Method. - Currently, granular thermoplastics for road marking follow the so-called conventional manufacturing process, which includes the following general steps: a. Weighing of raw materials, including powders, oils, granular resins, crystallized resins, powdered pigments, granulated pigments, glass spheres, anti-slip elements, and others. b. Placement in a mixer and start of mixing. The sequence of placement, speed, and mixing times varies depending on the manufacturer; the total mixing volumes per batch of product can range from 0.5 to 20 metric tons. c.The mixing process must achieve complete homogeneity among all the mixed components. This mixture is called a powder mixture because, due to the large quantity of loose powders, during packaging, handling, and use, these powders tend to contaminate (dirty) the work environment. Workers must wear respiratory and eye protection equipment at all times, and spills on the floor or in facilities must be avoided, as 100% cleanup is practically impossible and can lead to unwanted contamination. d. Packaging. It is generally packaged in 20 to 25 kg bags. These bags are usually made of polyethylene or polypropylene, preferably heat-fusible, so they can be melted with the granular powder paint and avoid generating waste (bags). e. Palletizing.The product is assembled onto pallets weighing 1 to 1.35 metric tons and wrapped in thermoformable plastic or stretch film to ensure safe handling during loading and transport, preventing the powdery granular paint from spilling and causing unwanted contamination that would be difficult to clean.Use of powdered granular thermoplastic for road marking: Once the pallets of paint have arrived at the work area, the operators place them bag by bag into kettles that melt the paint at temperatures between 160 and 225°C. This process of loading the powdered granular paint into the kettles generates a high amount of dust in the environment, which flies with the wind, staining the worker's clothing and the surrounding work area. Workers must operate at all times with appropriate respiratory masks and protective glasses. The molten product in a liquid state is transferred to the striping machines for marking, which, through extrusion mechanisms, form the lane division line or the mark or symbol being installed. 2) Production method for semi-powdered granular thermoplastic paint by semi-fusion.- Currently, semi-powdered granular thermoplastics for road marking are not industrially manufactured. The present invention proposes the following processes and machinery for their manufacture: g. Weighing of raw materials, including powders, oils, granular resins, crystallized resins, powdered pigments, granulated pigments, glass spheres, anti-slip elements, and others. h. Placement in a mixer and commencement of mixing. The sequence of placement, speed, and mixing times varies according to each manufacturer, and the total mixing volumes per batch of product can range from 0.5 to 20 metric tons. i. The mixing must achieve complete homogeneity among all the mixed components, and this mixture is called the powder mixture. This mixture does not go directly to packaging but undergoes a process that reduces the amount of loose powder in the product. j.From the mixer, the homogeneously mixed product passes to a specialized piece of equipment, the subject of this invention. This equipment, through a heating process using a heat tunnel also of this invention, with circulating air temperatures ranging from 1 to 330°C, generates a slight melting of the granular thermoplastic mixture. This allows the powders to adhere to the resins, and the reflective and / or anti-slip elements to also adhere to the adhesive and tactile resins. This process reduces free powder by 50 to 60% compared to conventionally manufactured powdered granular thermoplastic. Furthermore, the reflective and / or anti-slip elements also adhere to the resins. As described above, semi-powdery amorphous granules are generated, a differentiated and innovative product type that is also the subject of this invention.With all the above mentioned, the semi-powdered granular thermoplastic will allow for better handling, transport, and use of the granular thermoplastic, reducing environmental contamination levels and lowering respiratory and eye exposure for workers when using it. k. Packaging. The semi-powdered granular thermoplastic is packaged in the same way as conventional powdered granular thermoplastic. l. Palletizing. The semi-powdered granular thermoplastic is palletized in the same way as conventional powdered granular thermoplastic, with the difference that the risks of environmental contamination are significantly reduced due to the lower amount of free dust. m.Use of semi-powdered granular thermoplastic for road marking: Once the pallets of paint arrive at the work area, operators place them bag by bag into kettles that melt the paint at temperatures between 160 and 225°C. This process of loading the semi-powdered granular paint into the kettles generates less dust in the environment, reducing the amount of dust that is blown by the wind and could stain workers' clothing and the surrounding area. Workers must wear appropriate respiratory masks and protective eyewear at all times; however, the risks are significantly reduced since there is 50 to 60% less free dust. The molten, liquid product is then transferred to the striping machines, which, through extrusion mechanisms, form the lane marking or the mark or symbol being installed.The semi-powdered granular thermoplastic allows for better uniformity of all components in each bag due to the reduced amount of loose, small particles. With this type of product, during transport, the formation of coarse particles on the surface and fine particles at the bottom of the bag is avoided. 3) Production method for semi-powdered granular thermoplastic paint by semi-fusion and compression. - Currently, semi-powdered granular thermoplastics for road marking are not industrially manufactured by semi-fusion and compression. The present invention proposes the following process and machinery for its manufacture: n. Weighing of raw materials, including powders, oils, granular resins, crystallized resins, powdered pigments, granulated pigments, glass spheres, anti-slip elements, and others. o. Placement in a mixer and commencement of mixing.The sequence of input speed and mixing times varies depending on the manufacturer, and the total mixing volumes per batch can range from 0.5 to 20 metric tons. The mixing process must achieve complete homogeneity among all the mixed components, and this mixture is called the powder mixture. This mixture does not go directly to packaging but undergoes a process that reduces the amount of loose powder in the product. From the mixer, the homogeneously mixed product passes to a specialized piece of equipment, the subject of this invention, which, through a heating and compression process, compresses the mixture, increases the temperature, and produces uniform cylindrical, spherical, and / or amorphous granules. The semi-melting and compression process causes the powders to adhere to the resins, and the reflective and / or anti-slip elements also adhere to the adhesive and tactile resins.This process allows for a 60-80% reduction in free dust compared to conventionally manufactured granular thermoplastic. Furthermore, reflective and / or anti-slip elements adhere to the resins. As described above, cylindrical, oval, and / or semi-powdery amorphous granules are generated. This new type of product is also the subject of the present invention. With all of the above, the compressed semi-powdery granular thermoplastic will allow for better handling, transport, and use of the granular thermoplastic, reducing environmental contamination levels and lowering respiratory and ocular exposure for workers using it. r. Packaging. The compressed semi-powdery granular thermoplastic is packaged in the same way as conventional powdered granular thermoplastic. s. Palletizing.The compressed semi-powdered granular thermoplastic is palletized in the same way as conventional powdered granular thermoplastic, with the difference that the risks of environmental contamination are significantly reduced due to the lower amount of free dust.Use of compressed semi-powdered granular thermoplastic for road marking: Once the pallets of paint arrive at the work area, operators place them bag by bag into kettles that melt the paint at temperatures between 160 and 225°C. This process of loading the compressed semi-powdered granular paint into the kettles generates less dust in the environment, reducing the amount of dust that is blown by the wind and stains workers' clothing and the surrounding area. Workers must wear appropriate respiratory masks and protective eyewear at all times; however, the risks are significantly reduced since there is between 60 and 80% less free dust. The molten product in a liquid state is transferred to the striping machines for road marking, which, through extrusion mechanisms, form the lane division line or the mark or symbol being installed.The compressed semi-powdered granular thermoplastic allows for better uniformity of all components in each bag. Because it contains less free-floating small particles, the phases of coarse particles on the surface and small particles at the bottom of the bag are not created during transport.4 4) Production method for non-powdered granular thermoplastic paint by melting and granulation. Currently, non-powdered granular thermoplastics for road marking are not industrially manufactured. The present invention proposes the following processes and machinery for their manufacture: u. Weighing of raw materials, including powders, oils, granular resins, crystallized resins, powdered pigments, granulated pigments, glass spheres, anti-slip elements, and others. v. Insertion into a mixer and start of mixing.The sequence of input speed and mixing times varies depending on the manufacturer, and the total mixing volumes per batch can range from 0.5 to 20 metric tons. The mixing process must achieve complete homogeneity among all the mixed components, and this mixture is called the powder mixture. This mixture does not go directly to packaging, but rather undergoes a process that significantly reduces the amount of loose powder throughout the product mass. From the mixer, the homogeneously mixed product passes to a melting unit. This unit uses a heating process with a preheater or boiler and a granulating extruder, the subject of this invention, at temperatures that can vary between 1 and 330°C. This process completely melts the granular thermoplastic mixture, allowing the powders and all the ingredients of the mixture to adhere to each other through the resins.This process allows for a 95-99% reduction in free dust compared to conventionally manufactured granular thermoplastic. As described above, amorphous, oval, spherical, or cylindrical non-dusty granules of varying sizes, ranging from 0.5 to 20 mm along their major axis, are generated. This type of product is also the subject of the present invention. With all of the above, the non-dusty granular thermoplastic will allow for better handling, transport, and use, virtually eliminating environmental contamination levels and significantly reducing respiratory and ocular exposure for workers using it. Packaging. The non-dusty granular thermoplastic is packaged in the same way as conventional powdered granular thermoplastic. Palletizing.Non-powder granular thermoplastic is palletized in the same way as conventional powdered granular thermoplastic, with the difference that the risks of environmental contamination are reduced by more than 95% as there is practically no free dust.

[0025] Use of non-dusty granular thermoplastic for road marking: Once the pallets of paint arrive at the work area, operators place them bag by bag into kettles that melt the paint at temperatures between 160 and 225°C. This process of loading the non-dusty granular paint into the kettles generates virtually no dust in the surrounding area, which could be carried by the wind and does not stain workers' clothing or the surrounding work area. Workers must wear appropriate respiratory masks and protective eyewear at all times; however, the risks are considerably reduced since there is between 95% and 98% less free dust. The liquid product is then transferred to the striping machines, which, through extrusion mechanisms, form the lane marking or the mark or symbol being installed.The non-powdered granular thermoplastic allows for better uniformity of all components in each bag, and because it has virtually no free small particle dust, when in motion by transport, the phases of coarse particles on the surface and small particles at the bottom of the bag are not created.

[0026] Certain terms of the present invention are defined for a better understanding thereof:

[0027] Binders. A binder is defined as a substance used to hold other elements together within a mass. Its main function is to maintain cohesion between pigments, microspheres, retroreflective elements, anti-slip components, and fillers, the latter being responsible for transporting all the aforementioned elements.

[0028] For this invention, the following binders are preferred: modified alkyd resins (soybean oil, linseed oil, safflower oil, tung oil, castor oil), flexible polyamide resins (coconut oil, soybean oil, talc oil, linseed oil, tung oil), flexible polyethylene resins (low-density (LDPE), linear low-density (LLDPE) flexible, high-density (HDPE) flexible, ultra-high-density (UHMWPE) flexible, high-strength (high-strength HDPE) flexible, high-strength (high-strength HDPE) flexible), flexible ethyl vinyl acetate (EVA) resins (low-density flexible, high-density flexible, vinyl acetate copolymer flexible, with variable vinyl acetate content flexible, modified for specific applications flexible), polyethylene waxes (low-density, high-density, ultra-high-density, oxidized, modified with special additives), recycled polyethylene resins (high-density (HDPE) recycled,recycled low-density polyethylene (LDPE), recycled linear low-density polyethylene (LLDPE), recycled ultra-high-density polyethylene (UHMWPE), recycled polypropylene (from recycled homopolymer, from recycled copolymer, impact recycled, modified recycled), recycled PET (polyethylene terephthalate), oxidized polyethylene waxes (low-density, high-density, ultra-high-density, microcrystalline), castor oil waxes (from refined castor oil, from hydrogenated castor oil, from modified castor oil, from virgin castor oil), castor oil, passion fruit oil, castor bean oil, palm oil, corn oil, frying oil, peanut oil, canola oil, avocado oil, soybean oil, epoxidized soybean oil, epoxy binders, synthetic latex, natural latex, styrene-isoprene block copolymers (SIS), styrene-ethylene / butylene-styrene (SEBS), block copolymers of styrene-butadiene (SBS), methyl methacrylate, polyurea,Diisononyl phthalate (DINP), di(isononyl)cyclohexane-1,2-dicarboxylate (DINCH), dioctyl phthalate (DOP), and mixtures thereof.

[0029] Plasticizers. These are selected according to the type of granular thermoplastic paint required, based on soil parameters such as humidity, temperature, and pressure, among other well-known factors determined by the weather conditions. The following plasticizers are selected: Dibutyl phthalate, Dioctyl phthalate, Diethyl phthalate, adipic acid esters, and sebacic acid esters.

[0030] Pigments. Pigments provide color, contrast, and opacity without emitting substances harmful to people or the environment. The most preferred pigments are listed below, but these are not exhaustive: organic and inorganic pigments of different colors and chemical natures, such as: titanium dioxide (white), zinc oxide (white), iron oxide (red, yellow, brown), calcium carbonate (white), clay pigments (various colors), ultramarines (blues, violets), chromium oxide pigments (greens), modified zinc oxide (blue), sienna (ochre), umber (brown), Naples yellow (yellow ochre), treated titanium white (to provide pearlescent or iridescent effects), calcium phosphate pigments (various colors), mica pigments (various colors, also used for pearlescent effects), and carmine pigments (red, obtained from insects).

[0031] The pigments used in the present invention encompass both organic and inorganic compounds. Preferred colors include white, yellow, orange, red, purple, green, blue, black, gray, sand, dark red, violet, turquoise, and magenta. These pigments include organic and inorganic pigments with fluorescent, photoluminescent, and phosphorescent properties, as well as pigments derived from algae, fungi, and plants. Optical brighteners, organic or inorganic substances that enhance the performance of the pigments, are also incorporated.

[0032] Retroreflective elements. These can be glass microspheres or ceramic elements, prismatic elements, used drop-on and / or in premix.

[0033] Glass microspheres. Glass microspheres are integrated into the premix as an essential part of the STK2025 granular paint composition. These elements are responsible for giving it retroreflective properties, maintaining these characteristics throughout the paint's service life, even during progressive wear.

[0034] In the present invention, glass microspheres are used in the premix, ensuring retroreflectivity and nighttime visibility throughout the entire lifespan (2 to 15 years) of the marking, even during gradual wear due to use. These beads are very small, generally between 50 and 2000 micrometers in diameter.

[0035] The glass microspheres used in the present invention are primarily composed of SiO2 (silicon dioxide) and can be manufactured from recycled glass, virgin glass, or a combination of both. Preferably, they are made from silicon dioxide, soda-lime (sodium oxide), and / or borosilicate (calcium oxide). Furthermore, they have refractive indices between 1.5 and 2.4. Increasing the proportion of microspheres with indices between 1.6 and 2.4 results in effective nighttime retroreflectivity levels even under humid and rainy conditions. Conversely, a higher content of microspheres with indices of 1.5 results in retroreflectivity only under dry conditions.

[0036] In addition to the refractive index, the microspheres of the present invention must exhibit a crush strength in the range of 350–400 MPa, with a preference between 250–500 MPa. A roundness of between 70% and 80% is desired, with a preference between 60% and 95%. Furthermore, the particle size or diameter of the microspheres is required to be between 150 and 2800 microns, with a specific preference between 1 and 3000 microns.

[0037] Ceramic elements. In the present invention, retroreflective elements are integrated into the premix, significantly enhancing the retroreflective properties even under humid and rainy conditions. These elements are selected from micronized ceramics. This micronization process involves reducing the size of the ceramic particles to a microscopic scale, resulting in very small, uniformly sized particles.

[0038] The ceramic elements used in the present invention consist of a spherical or amorphous core made of ceramic or polymers, with high refractive index glass spheres bonded to the entire surface. These elements can have refractive indices between 1.7 and 2.4. As the proportion of these ceramic elements is increased, higher levels of nighttime retroreflectivity are achieved under humid and rainy conditions. Furthermore, the particle sizes or diameters selected in the present invention range from 300 to 2500 microns, with a specific preference between 100 and 3000 microns.

[0039] Retroreflectivity. This phenomenon occurs when the light from a vehicle's headlights strikes and reflects back towards the driver, making road signs and symbols visible to the driver. These signs and symbols serve to inform, warn, and restrict traffic on various routes such as runways, highways, streets, airports, ports, and other access points used by vehicles. It is important to note that the level of retroreflectivity varies under dry, humid, or continuously raining conditions. Therefore, the use of different types and proportions of retroreflective materials is essential to achieve effective retroreflectivity in all these conditions.

[0040] Photoluminescence. An event that occurs when a marking absorbs light during the day and emits it at night, making it visible to the driver even in situations where there is no illumination from the vehicle's headlights or streetlights.

[0041] Anti-slip elements. These amorphous elements with angular and pointed edges are applied by drop-on and / or incorporated into the premix. The anti-slip elements provide the property of being "anti-slip" or "anti-skid" when the road marking is wet, preventing the risk of slippage for both vehicles and pedestrians. The effectiveness of this property is evaluated using slip resistance indices, also known as IRD or SRT. In the present invention, various anti-slip elements are used, the most common being alumina, fused alumina or corondun, silica, ground glass, bauxite, and high-strength polymers, either individually or in combination. The hardness of these elements ranges from 4 to 9 on the Mohs scale, and as both the hardness and the concentration in the marking increase, higher slip resistance indices are achieved.The particle sizes of the anti-slip elements range from 50 to 3500 microns, with a preference between 20 and 4000 microns.

[0042] Slip resistance. This is the property that prevents a marking from becoming slippery or sliding when wet. It is measured using slip resistance indices (IRD or SRT).

[0043] High wear-resistant elements. These are generally spherical and / or amorphous elements, powders, or granules with or without angular edges, used in premixed applications. High wear-resistant elements provide greater resistance to wear from vehicle traffic, allowing for reduced thickness and less paint to be used, while maintaining the same relative lifespan compared to paints without these elements.

[0044] The present invention utilizes the most commonly used high-wear-resistant materials, which are zirconium, ceramics, alumina, fused alumina or corondum, silica, high-hardness glass, bauxite, high-strength polymers, and mixtures thereof. The hardness of these materials can range from 5 to 9 Mohs, and the particle size of the high-wear-resistant materials is between 50 and 3500 microns, preferably between 10 and 4000 microns.

[0045] Wear resistance. This is the property of pavement markings to resist wear from tire traffic, withstanding the tangential and torsional forces they generate. It is measured using various methods depending on the standards and region, but generally, all relate an initial weight to a final weight of the sample after it has been subjected to a wear process by abrasion or the passage of tires or wheels.

[0046] Fillers or fillers. Fillers or fillers are inert elements that do not chemically interact with the other components and serve as carriers for binders, pigments, retroreflective elements, and anti-slip elements. Often, the anti-slip and retroreflective elements are also considered fillers.

[0047] The present invention uses: calcium carbonates, magnesium carbonates, bentonites, talc, silica powders, alumina powders, and sand powders. Mixtures thereof are used. The particle sizes of the fillers are between 100 and 1000 microns, preferably between 2 and 2500 microns, not including anti-slip elements, which in many cases are considered fillers.

[0048] The process for manufacturing granular thermoplastics involves a mixing process with a predefined order and timing for adding the different components. During this process, the temperature is carefully controlled to prevent it from rising due to friction and melting the components. In summary, the process is as follows: The binders and plasticizers are slowly mixed until they are homogeneous. Then, the fillers, pigments, retroreflective elements, and anti-slip elements are added so that they integrate uniformly with the binders and plasticizers. Mixing can take between 20 and 60 minutes, depending on the type of mixer and the batch size.

[0049] The material obtained from STK2025 is a powdery granular form, solid at room temperature, and becomes pasty at various temperatures, ranging from 30°C to 70°C. These variations are suitable for different types of granular thermoplastic coatings, depending on roadway parameters, including temperature, pressure, atmospheric conditions, rainfall frequency, ice formation, and drought. It will not deteriorate from sodium chloride, calcium chloride, or other chemical agents used to combat ice formation, nor from chemicals present in waste or spills of fuels and lubricants generated by traffic.

[0050] In its liquid or semi-liquid state, it will not emit toxic fumes nor pose a danger to people handling it or who are present during its application on the roads.

[0051] The viscosity / temperature relationship of the plastic material will remain constant throughout six (6 to 10) reheating cycles.

[0052] To ensure optimal adhesion when applied to roadways, the compounds of the present invention shall be melted and maintained at a controlled temperature, ranging from 100 to 180 degrees Celsius. This temperature must be maintained for a specific period of time, between four (4) and ten (10) hours, without discoloration. Preferred temperatures are between 30°C and 200°C, 50°C and 160°C, 160°C and 250°C, and 180°C and 200°C. The product obtained under this invention will vary depending on specific soil conditions, temperature, pressure, traffic volume, humidity, and dryness.

[0053] When heated between 150°C and 300°C and dispersed using appropriate machinery, the product will not exhibit clotting, hard deposits, or color separation. Furthermore, it will be free of skin, dirt, foreign particles, or other ingredients that may cause bleeding, staining, or discoloration.

[0054] The flash points will be at least 80°C, 120°C, 200°C, 235°C, 280°C, and 300°C when measured using the Cleveland Open Cup method, depending on the type of granular thermoplastic paint desired.

[0055] The products of the present invention shall include a weight percentage of approximately ten, fifteen, twenty, thirty percent of glass microspheres, in addition to thirty to fifty percent (30-50%) of the total weight shall be supplied separately by the combined method.

[0056] The organic binders and pigments shall consist of a mixture of synthetic thermoplastic resins and plasticizers, where at least one, two, three, four, or up to five of these resins shall be solid at room temperature. The total binder and plasticizer content of a thermoplastic compound shall not be less than ten, fifteen, or twenty percent (10%, 15%, 20%) nor more than eighty or ninety percent (80%, 90%) by weight.

[0057] The cooling of the products of the present invention will be practically instantaneous, with a prudent time margin of twenty to thirty (5-30) minutes, avoiding any adhesion, discoloration or displacement under the action of traffic.

[0058] QUALITY TESTS. The following quality tests were carried out, with optimal results that complied with current road regulations. Tests were performed on 200 samples, which were labeled as STK2025.01; STK2025.02; STK2025.03; STK2025.04; STK2025.05; STK2025.06; STK2025.07; STK2025.08; STK2025.09; STK2025.10; STK2025.11; STK2025.12; STK2025.13; STK2025.14; STK2025.15; STK2025.16; STK2025.17; STK2025.18; STK2025.19; STK2025.20. According to ASTM (American Society for Testing and Materials), ASTM D450 - Standard Specification for Coal-Tar Pitch Used in Roofing, Dampproofing, and Waterproofing; The following were applied: ASTM D611 - Standard Test Methods for Aniline Point and Mixed Aniline Point of Petroleum Products and Hydrocarbon Solvents. ASTM D637 - Standard Test Method for Rubber Property—Piles of Carbon Black. ASTM D3383 - Standard Test Methods for Film-Forming Characteristics of Protective Coatings.ASTM D5324 - Standard Guide for Testing Water-Borne Architectural Coatings. Directional light reflectance (RLD).

[0059] The directional light reflectance for the color white and yellow, daytime visibility of the applied line, shall not be less than seventy-five (75) when the measurement is made with standardized light under an angle of forty-five degrees (45°).

[0060] Retroreflection (RF)

[0061] The retroreflection or night visibility will be greater than one hundred and fifty millicandelas per lux and square meter (150 mcd / lux / m²). 2 ) measured with a retroreflectometer operating with an angle of incidence of eighty-six degrees thirty minutes (86° 30) and an angle of divergence of one degree thirty minutes (I o 30).

[0062] Softening point (WP)

[0063] The softening point shall not be less than ninety-five degrees Celsius (95°C), measured by the ball and ring method (ASTM B-28-58-T), using truncated conical rings.

[0064] Heat stability (EC)

[0065] The manufacturer shall indicate the safe temperature, that is, the temperature at which the material can be maintained for a minimum of ten (10) hours in a closed boiler or in the application machine without degradation occurring. This temperature shall not be less than the softening temperature, measured according to the test indicated in the previous point, minus fifty degrees Celsius (50°C).

[0066] The decrease in luminance, using an EEL reflectance spectrophotometer with filters 601, 605, and 609, shall not exceed five (5) units. Light Stability (EL)

[0067] The decrease in light reflectance when a test specimen of the material is subjected to the action of ultraviolet rays for sixteen hours (16h) shall not exceed five (5) units.

[0068] Flow resistance (RF)

[0069] The decrease in height of a thermoplastic cone twelve centimeters (12 cm) in diameter and one hundred plus five millimeters (100 ± 5 mm) in height during forty-eight (48) hours, at forty degrees Celsius (40°C), shall not be greater than twenty percent (20%).

[0070] Impact resistance is measured with a pendulum device, where the thermoplastic must have a resistance of at least 1.1 joules.

[0071] Abrasion resistance (AR)

[0072] Abrasion resistance will be measured using a Taber Abraser apparatus with H-22 calibrated wheels. The material will be applied to a one-eighth-inch thick Monel sheet, and the test specimen will be subjected to water-lubricated abrasion. The weight loss after one hundred (100) revolutions will not exceed half a gram (0.5 g).

[0073] Slip resistance (SR)

[0074] All materials used for road markings must offer a coefficient of skid resistance similar to that of the pavement on which they are placed. In any case, this coefficient must exceed a value of forty-five (45) as measured by the Skide device at the Road Research Laboratory.

[0075] Table of Quality Test Results

[0076] These are the 20 types of STK2025 products that demonstrated stability in their compositions and met ASTM requirements, from a sample of 5650 tests.

[0077] For the presentation in non-powdered granules, a controlled heating process is used to achieve a slight melting and create the granules, which then undergo a cooling process, resulting in a non-powdered granular paint; a pressure compaction process is also used to form granules of different shapes; these processes have been studied and developed by ST.

[0078] This document describes the general procedure for STK2025 products for composing powdered, semi-powdered, or non-powdered granular mixtures. It notes that several procedures exist, with variations in ingredients and temperatures, depending on the specific product required for different types of roads and highways.

[0079] The thermoplastic resins are mixed and heated to a temperature between 140 and 300°C; more preferably between 160°C and 250°C, 180°C and 200°C, 140°C and 165°C, 150°C and 220°C, 180°C and 250°C, or 180°C and 300°C, with a melting point between 150°C and 300°C, depending on the type of resin and the required composition for the ambient conditions. Then, the pigments, plasticizers, anti-slip agents, fillers, ceramic elements, and microspheres are added, and the mixture is thoroughly mixed to ensure a homogeneous composition. The mixture is then cooled to a temperature of 10°C–20°C, preferably 20°C–40°C.

[0080] The compression process for forming granules involves applying mechanical force to a powder mixture to compress it and give it the required shape. For this purpose, the mixture with the aforementioned ingredients is added to a compacting machine, where it must be evenly distributed over the compaction surface. Pressure is controlled by rollers, dies, or hydraulic presses. This pressure compresses the powders and compacts them into granules. The applied pressure must be adjusted according to the characteristics of the final product. Compaction is achieved through cohesive and adhesive forces. The resulting granules are then subjected to drying, cooling, or coating. The different temperatures used in this process are defined as follows: 10°C to 30°C, 30°C to 70°C, 70°C to 100°C, 100°C to 150°C, 150°C to 200°C, and 200°C to 250°C.The pressures used in the production of the granules, according to the environmental parameters where the road / highway is located, are applied in the range of 5 to 50 t / cm. 2 , 5 to 30 t / cm 2 , 5 to 40 t / cm 2 . Between 500 to 5000 kPa, 500 to 1000 kPa, 500 to 2000 kPa, 500 to 3000 kPa, 500 to 4000 kPa.

[0081] The granule formulation, whether powdered, semi-powdered, or non-powdered, is then packaged in plastic bags for transport to the roads where it will be applied. After mixing, rigorous quality control is carried out through laboratory tests. These tests cover various physicochemical properties, such as density and the percentage composition of each component group. In addition, the product's performance properties, which are crucial for its proper functioning on the roads throughout its service life, are evaluated.

[0082] Performance properties evaluated include softening point, hardness, luminance, chromaticity coordinates, wear resistance, impact resistance, flowability, adhesion, and resistance to changes caused by accelerated weathering. Most of these properties are evaluated after holding the product in a molten state at 218°C for 1 hour, 300°C for 1.15 hours, 200°C for half an hour, 150°C for 2 hours, and temperatures between 90 and 200°C for 0.30 to 1.0 hour, with some also being evaluated at 4 and 8 hours.

[0083] In addition, specific quality controls are performed on properties such as retroreflectivity and skid resistance after the granules are installed on the road. These controls can be carried out immediately after installation or even several years later to verify performance throughout the product's lifespan.

[0084] All these tests and controls guarantee the stability of the formulation and ensure that STK2025 paints meet the required performance characteristics.

[0085] Application Method. Granular thermoplastic paints are applied to the surface using melting or fusion equipment until they reach a liquid state. Then, using sophisticated equipment, they are poured onto the asphalt, forming lane markings or other pavement markings. They can be used on flexible (bituminous) pavement or with a primer, which must be applied beforehand when the surface is concrete, stone, cobblestone, or worn bituminous pavement. Once applied, the pavement marking should remain adhered to the surface for its entire lifespan and not peel off, but only wear away with use. This process generally requires large, complex, and expensive equipment.The formulation must have a balance so that when the paint is applied and the spheres and anti-slip elements are placed on top of that hot paint, they do not sink at the application temperature, which is between 150°C and 250°C; it must also ensure that the composition is not too liquid when melted, causing the surface spheres to sink or the edges to deform, nor so thick that it does not adhere.

[0086] The technical characteristics of the final product

[0087] Thickness. When applied to the track, the granular thermoplastic may form lines or symbols between 0.5 and 4.5 mm; 0.8 and 4.8 mm; preferably between 0.5 and 1.3 mm; 0.8 and 1.5 mm; more preferably between 0.4 and 2.2 mm; 0.6 and 2.4 mm; more preferably between 1.5 and 2.5 mm; 2.3 and 3.0 mm; more preferably between 0.2 and 1.5 mm; 0.2 and 1.2 mm; even more preferably between 2.5 and 3.0 mm; 3.0 and 3.2 mm. The thickness variation tolerance is between ±0.2 mm and 0.1 mm; more preferably between ±0.5 mm and 0.6 mm. This thickness should not include the surface-seeded microspheres applied to the track at the time of application. In convex lines, on the prominent bodies that are placed on the flat line, thicknesses of up to 10 mm, 1 mm, and 9 mm can be achieved.

[0088] Microspheres. Glass microspheres are used to embed in road marking paint to improve nighttime visibility. These microspheres are made of glass and contain elements such as TiO2 (titanium dioxide), ZnO (zinc oxide), and / or ZrO2 (zirconium dioxide) in their composition, and must meet certain quality standards.

[0089] It is crucial that the microspheres have a retroreflectivity within the range of 100–700 mcd / m² / lux to 800–900 mcd / m² / lux, with 700–900 mcd / m² / lux being preferable, and between 100 and 1000 mcd / m² / lux being preferable. Furthermore, they must possess a crush resistance between 350–400 MPa and 400–800 MPa, with 250–600 MPa being preferable, although a value between 250 MPa and 500 MPa is preferred.

[0090] The binders used in preference in the present invention include all or several of the following compounds: modified alkyd resins, flexible polyamide resins, flexible polyethylene resins, flexible ethyl vinyl acetate resins, maleic resins, modified steric resins, polyamide resins, bisphenol-A epoxy resins (DGEBA), bisphenol-F epoxy resins, novolac-modified epoxy resins, polyglycidyl epoxy resins, cycloaliphatic epoxy resins, polyamide epoxy resins, unsaturated polyester epoxy resins, polyethylene waxes, oxidized polyethylene waxes, castor oil waxes, castor oil, passion fruit oil, epoxidized soybean oil, DINP, DINCH, DOP. Acrylics such as: Pure acrylics, Styrene acrylics, Vinyl acrylics, Styrene-butadiene acrylics (SBR), Urethane acrylics and Siloxane acrylics;aliphatic poburethanes, aromatic poburethanes, air-based poburethanes, polyester-based poburethanes, pobeter-based poburethanes, sibeone-based poburethanes, and thermoplastic poburethanes (TPU); air-dried alkyds, soybean oil-modified alkyds, linseed oil-modified alkyds, tung oil-modified alkyds, safflower oil-modified alkyds, walnut oil-modified alkyds, tall oil-modified alkyds; vinyl acetate (PVA) polymers; vinyl acetate-ethylene (VAE) copolymers; vinyl acetate and vinyl chloride copolymers (PVAc), vinyl chloride copolymers (PVC), vinyl chloride and vinyl acetate copolymers (VCA), vinyl chloride and ethylene acetate copolymers (EVA), stabilized vinyl chloride polymers (PVDC); condensation sibeone resins; addition sibeone resins (sibeone ethers);Platinum-cured Sibeone resins, peroxide-cured Sibeone resins, UV-cured Sibeone resins, condensation-cured Sibeone resins, and addition-cured Sibeone resins; the aforementioned binders primarily impart the following characteristics to the product: adhesiveness, flexibility, flowability, penetration resistance, resin plasticization, tackiness, impact resistance, and marking resistance. Furthermore, recycled binders are included, contributing to environmental protection by offering a sustainable alternative.

[0091] The pigments used in the present invention for the color white are titanium dioxide, zinc white, titanium white, lead white, and blue pigment selected from: phthalocyanine blue, ultramarine blue, Prussian blue, and cobalt blue; for the color yellow, one or more pigments of yellow tones are selected from: cadmium yellow, chromium yellow, nickel yellow, and barium yellow, and likewise, mixtures of pigments of various colors for each required color of STH2025 thermoplastic. The pigments may be organic or inorganic, synthetic, fluorescent, interference (pearlescent, iridescent, or metallic), and luminescent or non-luminescent, and may also be optical brightening materials. Retroreflectivity.The glass microspheres and ceramic elements for surface seeding are retroreflective elements that provide nighttime retroreflectivity in dry, humid, and continuous rain conditions. The glass microspheres and ceramic elements used in the premix provide retroreflectivity throughout the entire lifespan of the marking, as they emerge when the paint wears away, allowing for retroreflectivity throughout the marking's lifespan in dry, humid, and continuous rain conditions. The glass microspheres used in the present invention for surface seeding and in the premix have diameters between 50 and 2500 microns, with a refractive index of at least 1.5, allowing the marking to have retroreflective properties in dry conditions, measured according to ASTM E1710 and ASTM 7585. Glass microspheres with refractive indices greater than 1.6 up to 2.4 and ceramic elements with refractive indices from 1.6 to 2.5 are also added.Both in surface seeding and in premix, allowing for initial retroreflectivity and throughout the entire useful life under humidity conditions measured according to ASTM E2177 and continuous rain measured according to ASTM E2832. The minimum retroreflectivities sought in a demarcation are: In dry conditions, white and yellow initial retroreflectivity not less than 200 millicandelas and throughout the entire useful life not less than 80 millicandelas; in wet conditions, white and yellow initial retroreflectivity not less than 120 millicandelas and throughout the entire useful life not less than 70 millicandelas; in continuous rain, white and yellow initial retroreflectivity not less than 80 millicandelas and throughout the entire useful life not less than 50 millicandelas.

[0092] Slip resistance. The thermoplastic STK2025 incorporates anti-slip elements in a premix that provides slip resistance ratings when the marking is wet. These ratings can range from 10 to 100 BPN, according to ASTM E303, both in initial measurements taken immediately after application and throughout the marking's lifespan. This innovation utilizes various types of anti-slip elements, which may include alumina, fused alumina, corundum, silica, ground glass, and mixtures thereof.

[0093] Service life. The service life of the products obtained in the present invention, in terms of the durability of the road marking, varies according to the thickness. From 0.8 to 1.5 mm and 2.3 to 3.0 mm, the relative lifespan of the thermoplastic STK2025 is a minimum of 1, 2, 3, and 4 years, respectively, up to 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, and 15 years. Due to the large number of variables involved in the durability of road markings, another functional indicator is that, at a thickness of 2.3 mm, the service life of the thermoplastic should be at least 6 times longer than that of conventional liquid aerosol paints applied at a thickness of 180 microns when dry.

[0094] Other performance characteristics, evaluated in the laboratory, are:

[0095] • Color. The daylight luminance factor Y (%) at a 45 / 0° geometry and D65 illuminant, using a CIE 1931 standard observer, which determines color, must be >45 for white, >30 for yellow, and >25 for other colors. Low-temperature crack resistance. When STK2025 thermoplastic is heated for 240 min ± 5 min to 218 °C ± 2 °C, applied to concrete blocks, and cooled to -20 °C ± 2 °C, in accordance with Section 12 of AASHTO T250, it must not crack.

[0096] • Drying time. When the thermoplastic material STK2025 is applied at a temperature in the range of 205°C ± 8°C or 210°C ± 7°C and a thickness of 3.0 mm to 5.0 mm, the material must be ready for traffic in no more than 5 min when the air temperature is between 6°C ± 1.5°C and 5°C ± 2°C and no more than 20 min when the air temperature is between 30°C ± 4°C and 32°C ± 2°C.

[0097] • Softening point. When the thermoplastic material STK2025 is heated for 240 min ± 5 min to 218°C ± 2°C and tested in accordance with ASTM D36 / D36M, the material shall have a softening point of 100°C ± 30°C.

[0098] • Impact resistance. When the thermoplastic material STK2025 is tested in accordance with ASTM D256 Method A, on a 2.54cm by 2.54cm by 15.24cm unnotched sample, the impact resistance shall be a minimum of 0.8 J.

[0099] • Specific gravity or density. When the thermoplastic material STK2025 is tested in accordance with Section 16 of AASHTO T250, the specific gravity shall not exceed 2.0 g / cm3

[0100] • Indentation resistance. When the thermoplastic material STK2025 is tested in accordance with ASTM D7735, using a Shore A durometer, the indentation resistance must be between 30 and 90. The durometer and the panel must be at 46°C with an applied load of 1 kg. The instrumental measurement must be taken after 15 s.

[0101] • Flowability. When the thermoplastic material STK2025 is tested according to the “cylinder and oven heating test” (ST Internal Test), it must have percentages between 150 and 500%.

[0102] • Marking resistance. When the thermoplastic material STK2025 is tested according to the “hydraulic press tire marking test” (ST internal test), it must have percentages between maximum tire marking indexes of 1 or 2, at 65°C on the scale of 1 to 5.

[0103] • Wear resistance. When the thermoplastic material STK202 is tested according to the “Tabber abrasion resistance test” (Test adapted by ST for thermoplastic paints), it must have maximum wear of 100 mg per 1000 cycles.

[0104] Other performance characteristics, evaluated in the laboratory and in the field, are:

[0105] • Retroreflectivity. When the thermoplastic material STK2025 is applied immediately or throughout its service life, its nighttime retroreflectivity is measured according to ASTM E1710 and ASTM 7585 methods.

[0106] • Slip resistance. When the thermoplastic material STK2025 is applied immediately or throughout its service life, its wet slip resistance is measured according to ASTM E303. • Photoluminescence. When the thermoplastic material STK2025 is applied immediately or throughout its service life, its photoluminescence is measured according to UNE 23035.

[0107] Granular thermoplastics for road marking are typically presented as bags of powdered granular mixture. This presentation is useful but has drawbacks due to the high dust content and the need for careful handling by personnel, as well as the significant dust contamination around the work areas. The present invention develops a non-powdery presentation of STK2025 thermoplastic paint, consisting of granules of different shapes and / or sizes that can be manufactured using various processes studied and developed in this invention.The first granulation process is an incomplete melting of powdered granular thermoplastic, through the application of external heat for this process whose temperatures range according to the characteristics of the product from 20°C to 50°C, 50°C to 120°C, 120°C to 200°C, from 20°C to 200°C, and its subsequent cooling with air and / or water to obtain amorphous granules or other shapes that will be up to 60% dust-free compared to the powdered granular thermoplastic, whose temperatures are selected between 0°C to 30°C, in the case of cooling with water, an air drying process is followed; the second process is granulation with pressure compaction equipment ranging from 5 to 50 t / cm; 2 , 5 to 30 t / cm 2 , 5 to 40 t / cm 2Between 500 to 5000 kPa, 500 to 1000 kPa, 500 to 2000 kPa, 500 to 3000 kPa, 500 to 4000 kPa, with or without external heat input for granulation, obtaining compact cylindrical, oval, round or other shapes of granules depending on the size and model of the mold. These granules can be from 0.1 mm to 20 mm in the longest measurement of the granule, and it is up to 80% dust-free compared to powdery thermoplastic.

[0108] Another objective of the present invention is that STK2025 road marking products are visible, reflective, durable, and stable in rain, fog, hail, or other extreme weather conditions. Their durability ranges from 1 to 10 years, 10 years, 8 to 10 years, 4 to 10 years, and 6 to 10 years, respectively. Despite gradual wear, they retain the safety-enhancing properties of visibility, retroreflectivity, and slip resistance.

[0109] TABLE 1. MINIMUM AND MAXIMUM PARAMETERS OF THE COMPONENTS FOR STK2025 PAINTS

[0110] TABLE 2. MINIMUM AND MAXIMUM PARAMETERS OF THE COMPONENTS FOR THERMOPLASTIC COMPOSITIONS. MOST PREFERRED COMPOSITIONS: TABLE 3. MINIMUM COMPONENT PARAMETERS FOR THERMOPLASTIC COMPOSITIONS. MOST PREFERRED COMPOSITIONS:

[0111] TABLE 4. MAXIMUM COMPONENT PARAMETERS FOR THERMOPLASTIC COMPOSITIONS. MOST PREFERRED COMPOSITIONS:

[0112] Applying all the principles outlined in the preceding paragraphs, and in compliance with all applicable national and international standards, methods, and regulations, we have developed the following novel thermoplastic compositions. These new products meet all the aforementioned parameters and are durable, stable at extreme temperatures, from very cold (-9°C) to very hot (60°C), even with temperature fluctuations within the same day. They are retroreflective in dry, humid, and continuous rain conditions, and even photoluminescent in the absence of vehicular or public lighting. Furthermore, they contain highly wear-resistant elements that increase their lifespan. This also includes the development of a non-powdered granule presentation that improves the handling of STK2025 thermoplastic paint during application, as it prevents dust inhalation by workers who are not using appropriate personal protective equipment.

[0113] GENERAL THERMOPLASTIC COMPOSITIONS

[0114] The following thermoplastic formulations or compositions are merely examples of the product varieties presented in the present invention. All parameters, such as temperature, pressure, pavement quality, topography, and rainfall intensity, among others, must be analyzed to formulate and obtain a product that meets the requirements of both international and national standards. The following formulations are described as examples and should not be considered limitations to the main object of the invention.

[0115] EXAMPLE 1: THERMOPLASTIC COMPOSITIONS EXAMPLE 2. THERMOPLASTIC COMPOSITIONS:

[0116] EXAMPLE 3. THERMOPLASTIC COMPOSITIONS:

[0117] EXAMPLE 4. THERMOPLASTIC COMPOSITIONS:

[0118] EXAMPLE 5. THERMOPLASTIC COMPOSITIONS:

[0119] EXAMPLE 6. THERMOPLASTIC COMPOSITIONS:

[0120] EXAMPLE 7. THERMOPLASTIC COMPOSITIONS:

[0121] EXAMPLE 8. THERMOPLASTIC COMPOSITIONS: EXAMPLE 9. THERMOPLASTIC COMPOSITIONS:

[0122] EXAMPLE 10. THERMOPLASTIC COMPOSITIONS: EXAMPLE 10. THERMOPLASTIC COMPOSITIONS: EXAMPLE 11. THERMOPLASTIC COMPOSITIONS:

[0123] EXAMPLE 12. THERMOPLASTIC COMPOSITIONS:

[0124] EXAMPLE 12. THERMOPLASTIC COMPOSITIONS:

[0125] EXAMPLE 13. THERMOPLASTIC COMPOSITIONS: EXAMPLE 14. THERMOPLASTIC COMPOSITIONS:

[0126] EXAMPLE 14. THERMOPLASTIC COMPOSITIONS:

[0127] EXAMPLE 15. THERMOPLASTIC COMPOSITIONS:

[0128] EXAMPLE 16. THERMOPLASTIC COMPOSITIONS:

[0129] EXAMPLE 16. THERMOPLASTIC COMPOSITIONS:

[0130] EXAMPLE 17. THERMOPLASTIC COMPOSITIONS:

[0131] EXAMPLE 18. THERMOPLASTIC COMPOSITIONS:

[0132] EXAMPLE 19. THERMOPLASTIC COMPOSITIONS:

[0133] EXAMPLE 20. THERMOPLASTIC COMPOSITIONS: EXAMPLE 21. THERMOPLASTIC COMPOSITIONS:

[0134] EXAMPLE 22. THERMOPLASTIC COMPOSITIONS:

[0135] EXAMPLE 23. THERMOPLASTIC COMPOSITIONS:

[0136] EXAMPLE 24. THERMOPLASTIC COMPOSITIONS:

[0137] EXAMPLE 25. THERMOPLASTIC COMPOSITIONS:

[0138] EXAMPLE 26. THERMOPLASTIC COMPOSITIONS:

[0139] EXAMPLE 27. THERMOPLASTIC COMPOSITIONS:

[0140] EXAMPLE 28. THERMOPLASTIC COMPOSITIONS:

[0141] EXAMPLE 29. THERMOPLASTIC COMPOSITIONS:

[0142] EXAMPLE 30. THERMOPLASTIC COMPOSITIONS:

[0143] EXAMPLE 31. THERMOPLASTIC COMPOSITIONS:

[0144] EXAMPLE 32. THERMOPLASTIC COMPOSITIONS:

[0145] EXAMPLE 33. THERMOPLASTIC COMPOSITIONS:

[0146] EXAMPLE 34. THERMOPLASTIC COMPOSITIONS:

[0147] EXAMPLE 34. THERMOPLASTIC COMPOSITIONS:

[0148] EXAMPLE 33. THERMOPLASTIC COMPOSITIONS:

[0149] EXAMPLE 34. THERMOPLASTIC COMPOSITIONS:

[0150] EXAMPLE 35. THERMOPLASTIC COMPOSITIONS:

[0151] EXAMPLE 35. THERMOPLASTIC COMPOSITIONS:

[0152] EXAMPLE 36. THERMOPLASTIC COMPOSITIONS:

[0153] EXAMPLE 36. THERMOPLASTIC COMPOSITIONS:

[0154] EXAMPLE 36. THERMOPLASTIC COMPOSITIONS: EXAMPLE 37. THERMOPLASTIC COMPOSITIONS:

[0155] EXAMPLE 38. THERMOPLASTIC COMPOSITIONS:

[0156] EXAMPLE 39. THERMOPLASTIC COMPOSITIONS:

[0157] EXAMPLE 39. THERMOPLASTIC COMPOSITIONS:

[0158] EXAMPLE 40. THERMOPLASTIC COMPOSITIONS:

[0159] EXAMPLE 41. THERMOPLASTIC COMPOSITIONS:

[0160] EXAMPLE 42. THERMOPLASTIC COMPOSITIONS:

[0161] TABLE 5. MINIMUM AND MAXIMUM PARAMETERS OF COMPONENTS FOR THERMOPLASTIC COMPOSITIONS. PREFERRED ACTIVE SUBSTANCES IN THE DIFFERENT COMPOSITIONS.

[0162] Tests confirm the effectiveness of STK2025 thermoplastic compositions. They meet all international and national standards requirements. The following pages present international and national test results validating the formulations and their effectiveness in testing their retroreflectivity, luminance, impact resistance, low-temperature resistance, indentation resistance, wear resistance, minimum heavy metal content, and component contents.

[0163] These analyses demonstrate that the formulations of the present invention meet their industrial application and effectiveness.

[0164] Table of average results of the temporal evolution of the Chromatic Coordinates of the 15 Samples from ATK2025.01 to ATK2025.20 at different times, where t represents its age. a) t = 0 months; b) t = 1 month; c) t = 6 months; d) t = 12 months; e) t = 18 months; f) t = 24 months; g) t = 30 months; and h) t = 36 months. The results are defined in the following graphs:

[0165] Nighttime visibility on roads in general, and on conventional roads in particular, is the most important characteristic of STK2025 thermoplastic, as it is the only guide that the road user has for their orientation in extreme weather.

[0166] TABLE. TESTS OF EMITTED LUMINANCE ACCORDING TO EXPOSURE TIME, LUX RECEIVED AND PERCENTAGE OF PIGMENT

[0167] Analyzing the data, it is observed that the higher the illuminance to which case (b) is exposed, the greater the level of light emitted. Similarly, a higher percentage of pigment yields better luminance results. The phosphor's luminance values ​​must be translated into terms of human eye visibility, understanding that a value of 0.3 mcd*m 2 It is normally used as the acceptable visibility threshold. This value is 100 times the sensitivity of the human eye in complete darkness.

[0168] However, discussing this value is meaningless in outdoor situations. Firstly, because this limit is established for a light source in a completely dark environment, whereas outdoors it is often not completely dark. Secondly, a road user's eye is never at its most sensitive and cannot fully adapt to darkness due to moonlight, streetlights, other road users, etc.

[0169]

[0170]

[0171]

[0172]

[0173]

[0174]

[0175] All tests demonstrate the novelty, inventiveness, and industrial applicability of STK2025 compositions. They demonstrate compliance with all national and international regulations and even surpass all existing compositions on the market.

[0176] OTHER EVIDENCE:

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[0183]

Claims

CLAIMS 1. STK2025 compositions characterized in that they are formed by: a) Binders b) Pigments c) Microspheres d) Ceramic elements e) Rheological modifier f) Plasticizer g) Anti-slip agent h) Filler 2. Compositions of STK2025 according to claim 1, wherein the binders are CHARACTERIZED in that they are mixed from: rigid resins, elastomeric resins, recycled plastic resins and waxes.

3. Compositions of STK2025 according to claims 1 and 2, wherein the binders, the rigid resins are CHARACTERIZED in that they are selected from: modified maleic alkyd, rosin-ester alkyd resin, penteritritol alkyd resin, C5 hydrocarbon resin, C9 hydrocarbon resin.

4. Compositions of STK2025 according to claims 1 and 2, wherein the binders, the elastomeric resins are CHARACTERIZED in that they are selected from: polyamide elastomer, polyurethane elastomer, ethyl vinyl acetate elastomer, polyethylene elastomer, SIS, SES and SBS synthetic rubbers, natural rubbers.

5. Compositions of STK2025 according to claims 1 and 2, wherein the binders, the recycled plastic resins are CHARACTERIZED in that they are selected from: polyethylene terephthalate (PET), high-density polyethylene (HDPE), low-density polyethylene (LDPE), high-density polypropylene (HDPP), low-density polypropylene (LDPP).

6. Compositions of STK2025 according to claims 1 and 2, wherein the binders, the waxes, are CHARACTERIZED in that they are selected from: oxidized polyethylene wax, polyethylene wax, castor oil wax.

7. Compositions of STK2025 according to claim 1, wherein the pigments are CHARACTERIZED in that they are a combination of: organic pigments, inorganic pigment and UV protective pigment.

8. Compositions of STK2025 according to claims 1 and 7, wherein the pigments are CHARACTERIZED in that they are selected from: titanium dioxide, yellow pigment, blue pigment, red pigment, green pigment, black pigment, optical brightener, titanium dioxide and photoluminescent pigments.

9. Compositions of STK2025 according to claim 1, wherein the microspheres are CHARACTERIZED in that they are a mixture of: a) Dry retroreflective glass microspheres with refractive indices of at least 1.5 to 2.4; and, b) Reflective microspheres in wet and rain conditions, refractive indices between 1.6 and 2.

4. Granulometries: diameters between 150 to 2800 microns and roundness of 60 to 95%.

10. Compositions of STK2025 according to claims 1 and 9, wherein the microspheres are CHARACTERIZED in that they are selected from: refractive index between 1.6 to 2.5; and, granulometries of diameters between 1 to 3000 microns and roundness of 60 to 95%.

11. STK2025 thermoplastic compositions are CHARACTERIZED by having a refractive index between 1.6 and 2.5; and granulometries with diameters between 100 and 3000 microns.

12. Compositions of STK2025 according to claim 1, wherein the rheological modifier is CHARACTERIZED in that it is bentonite whose particle size varies between 0.1 and 200 microns.

13. Compositions of STK2025 according to claim 1, wherein the plasticizers are CHARACTERIZED in that they are selected from: castor oil, castor oil, passion fruit oil, diisononyl phthalate (DINP), dioctyl phthalate (DOP), dioctyl terephthalate (DOTP), epoxidized soybean oil (ESBO), dimethyl phthalate (DMP), DI-2-PROPYLHEPTYL PHTHALATE (DPHP), mineral oil, Di(isononyl)cyclohexane-1,2-dicarboxylate (DINCH).

14. Compositions of STK2025 according to claim 1, wherein the anti-slips are CHARACTERIZED in that they are selected from: Alumina (AL2O3), Fused Alumina (Al2O3), Corondun (Al2O3), Silica (SiO2), Ground Glass (SiO2), from 50 to 3000 microns, hardness from 4 to 9 Mohs.

15. Preformed thermoplastic compositions according to claim 1, wherein the fillers are CHARACTERIZED in that they are selected from: calcium carbonate, magnesium carbonate, of volcanic or marine origin, the particle size of which varies between 0.1 and 200 microns.

16. Preformed thermoplastic compositions according to claims 1 to 15 are CHARACTERIZED in that they are present in the following percentages: titanium dioxide 1.00-15.00; yellow pigment 0.01-3.00; blue pigment 0.01-3.00; red pigment 0.01-3.00; green pigment 0.01-3.00; black pigment 0.01-3.00; optical brightener 0.01-3.00%; rigid resins 4.00-9.00; elastomeric resins 2.00-9.00; recycled plastic resins 0.20-3.00; wax 0.50-3.00; carbonate 2.30-80.00; bentonite 0.10-3.00; plasticizer 0.50-3.00; Dry retroreflective glass microspheres 5.00-45.00; dry and wet retroreflective glass microspheres 0.10-50.00; dry and wet retroreflective ceramic elements 0.10-40.00; anti-slip elements 0.05-20.

00.

17. Preformed thermoplastic compositions according to claims 1 to 16 are CHARACTERIZED in that they are powdery or non-powdery granulated products of various colors and compositions.

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