Thermoplastic marking compositions

The Dow Chemical Company

Thermoplastic marker compositions

The present invention relates to thermoplastic markime compositions. The present invention particularly relates to thermoplastic markers of a composition comprising a binder further comprising at least one homogeneous polymer.

Thermoplastic markers of the formulation comprising inorganic fillers bonded with a polymeric binder are known in the art.

Published PCT Patent Application WO 9623845 describes a thermoplastic adhesive composition suitable for use as a road marking agent comprising silane modified petroleum resin containing 0.05 to 1.0 weight percent silane functionality, extender oil and / or a softener, pigment and filler. It is stated that the adhesive composition provides improved adhesion of glass beads to road surfaces for improved durability.

Netherlands published patent application NL7907550 describes a reflective road marking agent applied by applying the standard marking composition as a hot melt to the road surface and then applying a reflective agent containing a thermoplastic agent to the still warm marking composition. The reflective material preferably contains glass pearls, prismatic or lens reflectors and is based on substantially the same materials as the road marking composition.

GB 2 059 430 discloses a thermoplastic hot melt road marking composition comprising 7 to 38 weight percent synthetic resin, 1 to 10 weight percent softener, 0 to 10 weight percent elastomer, 1 to 15 weight percent pigment, 0 to 35 weight percent glass beads, 10 to 50 weight percent mineral aggregate, 10 to 50 weight percent extender, and 0 to 5 weight percent stabilizer. The publication states that the composition is easily applied to roads with a screed or extrusion type applicator at 180 to 200 ° C and that it has a long shelf life even when not only 1.5 mm thick. The publication further states that 280 to 500 g / m glass beads may be applied to the molten surface.

Japanese published patent application JP 52058737 describes compositions prepared by mixing (a) 2 to 20 parts by weight of ethylene vinyl acetate copolymer or atactic polypropylene; (b) 60 to 96 parts by weight of a carboxy modified hydrocarbon resin (having an acid value of 0.1 to 25) or an ester modified hydrocarbon resin obtained by reacting the carboxy modified resin with an alcohol; (c) 2 to 20 parts by weight of low molecular weight polyethylene optionally carboxy-modified; and (d) 200 to 700 parts by weight of mineral fillers or pigment, optionally with plasticizers or glass beads. It is stated that the coatings described have improved flexibility and strength and are obtained from compositions with improved fluidity.

British Patent Application GB 1324553 discloses a road marking composition of a hot-applied, thermoplastic superimposed type comprising: (a) aggregate (e.g., crushed marble, dolomite, calcite debris or silica sand), (b) pigment and extender; and (c) a binder consisting of (i) 55 to 90% by weight of polymeric unsaturated resin (ii) 10 up to 45% by weight of hydrocarbon oil softener having an inflammation point (open) greater than or equal to 204 ° C and a viscosity of 0.6 to 1 Pa.s (6-10 Poise) at 25 ° C; and (iii) 0 to 10 by weight of aliphatic monocarboxylic acid having at least 14 carbons, such as steama acid or oleic acid. The post describes the inclusion of glass beads (Ballotini) for making reflective bar markings. The publication describes the use of Ί1Ο2 as a pigment with bleach as an extender, or, instead of TiO₂, a heat stable yellow pigment.

European Patent Application Publication EP 115 434 discloses a hot-melt adhesive composition comprising a copolymer of ethylene and at least one alpha-olefin having from 3 to 10 carbon atoms and a sticky agent. The copolymer has a molecular weight of 1000 to 40000. Alpha-olefin is present in amounts of 2 to 40 weight percent. The case copolymers were prepared using a soluble vanadium catalyst. The post describes the use of adhesives in road markim applications.

Those in the industry would find great advantage in a thermoplastic brand formulation expressing a consistent and low viscosity (as expressed by a melt viscosity at 177 ° C not exceeding 5000 mPa.s) that would have reduced mating and smoking and which would exhibited good low temperature flexibility (as expressed by crushing temperature from -10 to -20 ° C).

Therefore, the present invention provides a thermoplastic marking composition comprising:

(a) 10 to 80% by weight of a binder, further comprising:

(i) from 1 to 99% by weight of at least one homogeneous polymer;

(ii) from 5 to 70% by weight of at least one adhesive enhancer;

(iii) from 0 to 10 percent by weight of polyethylene having suspended acid functional moieties or non-functionalized wax; and (iv) from 0 to 20 percent by weight of plasticizer; and (b) 20 to 90 percent by weight of inorganic filler.

The subject formulations are advantageously applied by spray, ester and extrusion techniques. The subject formulations express improved low-temperature flexibility and low-temperature adhesion and abrasion and express improved smoke and low odor properties at high temperatures. The subject formulations have a wide potential range of application temperatures, especially at temperatures from 150 ° C to 250 ° C, making them suitable for application by various means. The ability of the compositions to be applied at low application temperatures, i.e., temperatures from 150 to 170 ° C, e.g. makes them suitable for an application with extrusion coating techniques; while the ability of the compositions to be applied at high application temperatures, i.e., temperatures from 200 ° C to 250 ° C, makes them suitable for application with spray coating techniques. The subject formulations are preferably resistant to dirt uptake and furthermore preferably exhibit less viscosity variability compared to systems lacking a homogeneous ethylene polymer.

The unique balance of formulation characteristics of the invention enables them to be suitable in a variety of coatings, markings and dyeing applications, including, but not limited to, road markings, traffic signs, highway markings, pedestrian crossings, advertisements and markings for buildings, cycle lanes, tennis courts. playgrounds, marking of tartan substitutes, stop lines and markings of the running course.

These and other embodiments are described in the following detailed description.

Test methods used to characterize a homogeneous ethylene polymer

The density was measured according to ASTM D-792. Prior to the measurement, the samples were solidified at room temperature for 24 hours.

The melting index (I?) Is measured according to ASTM D-123 8, condition 190 ° C / 2.16 kg (formally known as condition (E)).

The molecular weight was determined using gel permeation chromatography (GPC) on a Waters, 150 ° C high temperature chromatography unit equipped with three mixed porous columns (Polymer Laboratories 103, 104, 105 and 106) operating at a system temperature of 140 ° C. The solvent is 1,2,4-trichlorobenzene, from which samples of a 0.3 wt% solution for injection are prepared. The flow rate is 1.0 ml / minute and the injection size is 100 microlitres.

Molecular weight determination is performed using a narrow molecular weight distribution of polymeric standards (Polymer Laboratories) in conjunction with their elution volumes. Polyethylene equivalent molecular weights are determined using appropriate Mark-Houwink coefficients for polyethylene and polystyrene (as described by Williams and

Word in the Journal of Polymer Science, Polymer Letters, Vol. 6, (621) 1968) to derive the following equation:

*

Mp_Ohii_etii_en~ a (Mp_Ohij_sie_ren) b.

In this equation, a = 0.4316 and b = 1.0. Mass of average molecular weight, M_w, is calculated in the usual way by the following formula: M_w = Σ w; Mj, where Wj and Mj are the mass fraction or. the molecular weight of the -ite fraction eluted from the GPC column.

The melt viscosity of the polymer components is determined by the following procedure using a Brookfield Laboratories DVII + viscometer in single-use aluminum sample chambers. The spindle used is the SC-31 hot melt spindle, used to measure viscosities in the range of 10 to 100000 mPa.s (0.1 to 1000 g / cm.second). To cut the samples into pieces small enough to fit into the sample chambers, which are 2.5 cm wide and 13 cm long, use a cutting blade. The sample is placed in a chamber, which is then placed in a Brookfield Thermosel (thermo-cell) and fixed in place with pliers with a bent needle nose. The sample chamber has a notch at the bottom that fits into the bottom of the Brookfield Thermosel so that the chamber cannot rotate when the spindle is inserted and rotates. The sample was warmed to 177 ° C, adding an additional sample until the molten sample was about 2.5 cm below the top of the sample chamber. Lower the viscometric apparatus and dip the spindle into the sample chamber. The descent is continued until the beams on the viscometer are on the Thermosel. Turn on the viscometer and adjust the shear rate leading to a torque reading in the range of 30 to 60%. The readings are taken every minute for about 15 minutes and / or until the values ​​have stabilized and a final reading is recorded.

The adhesives of the invention comprise at least one homogeneous ethylene / α-olefin interpolymer which is an ethylene interpolymer and at least one C3-C20 α-olefin. The term interpolymer is used herein to refer to a higher-order copolymer or terpolymer or polymer. In order to make the interpolymer, at least one other comonomer is said to be polymerized with ethylene.

By the term homogeneous, we mean that any comonomer is randomly distributed within a given interpolymer molecule, and essentially within that interpolymer all interpolymer molecules have the same ethylene / comonomer ratio. The melting peak of homogeneous linear and essentially linear ethylene polymers, as obtained by differential scanning calorimetry, will expand by decreasing the density and / or by reducing the numerical average molecular weight. However, unlike heterogeneous polymers, when the homogeneous polymer has a melting peak higher than 115 ° C (as in the case of polymers with a density greater than 0.940 g / cm³), additionally has no distinctive lower temperature melting peak.

The homogeneous ethylene / α-olefin interpolymers useful in the invention are characterized in that they have a narrow molecular weight distribution (M_w/ M_n). For homogeneous ethylene / α-olefins useful in the practice of the present invention, M_w/ M_n from 1.5 to 2.5, preferably 1.8 to 2.2, most preferably about 2.0.

Homogeneously branched linear ethylene / α-olefin interpolymers can be prepared using polymerisation processes (e.g. as described by Elston in US Patent No. 3,645,992) that provide homogeneous distribution of short chain branching. Elston used soluble vanadium catalyst systems in its polymerization process to produce such polymers. Others, such as Mitsui Petrochemical Company and Εχχοη Chemical Company, have used so-called single-site catalyst systems to produce polymers with a homogeneous linear structure. U.S. Pat. No. 4,937,299 to Ewen et al. and U.S. Pat. No. 5,218,071, Tsutsui et al. describe the preparation of homogeneous linear ethylene polymers using hafnium-based catalyst systems. Homogeneous linear ethylene / α-olefin interpolymers are currently available from Mitsui Petrochemical Company under the trade name Tafmer and at Εχχοη Chemical Company under the trade name Exact.

Essentially linear ethylene / α-olefin interpolymers are available from The Dow Chemical Company as Affmity ™ polyolefin plastomers. Essentially linear ethylene /? -Olefin interpolymers can be prepared according to the techniques described in U.S. Pat. No. 5,272,236 to U.S. Pat. No. 5,278,272 and U.S. Pat. No. 5,665,800.

Particularly preferred homogeneous ethylene / α-olefin polymers are ultra-low molecular weight polymers that can be fabricated according to published PCT patent application WO 97/26287, which is equivalent to US patent application serial no. No. 08 / 784,683, filed Jan. 22, 1997.

At least one homogeneous polymer will be an ethylene interpolymer with at least one comonomer selected from the group consisting of C3-C20 α-olefins, unconjugated dienes and cycloalkenes. Examples for C₃-C₂o α-olefins include propylene, isobutylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-heptene and 1-octene. Priority C₃-C₂₀ α-olefins include C₄-C₂o α-olefms such as 1-butene, 1-hexene, 4-methyl-1-pentene, 1-heptene and 1-octene, more preferably 1-hexene and 1-octene. Examples of cycloalkenes include cyclopentene, cyclohexene and cyclooctene. Non-conjugated dienes, suitable as comonomers, in particular in the manufacture of ethylene /? -Olefin / diene terpolymers, are typically unconjugated dienes having from 6 to 15 carbon atoms. Representative examples of suitable non-conjugated dienes include:

(a) straight acyclic dienes such as 1,4-hexadiene, 1,5-heptadiene and 1,6-octadiene;

(b) branched acyclic dienes such as 5-methyl-1,4-hexadiene; 3,7-dimethyl-1,6-octadiene and 3,7-dimethyl-1,7-octadiene;

(c) single ring alicyclic dienes such as 4-vinylcyclohexene, 1-allyl-4-isopropylidene cyclohexane, 3-allylcyclopentene, 4-allylcyclohexene and 1-isopropenyl-4-butenylcyclohexene;

(d) multi-ring alicyclic fused and bridged ring dienes such as dicyclopentanediene, alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbomenes such as 5-methylene-2-norbomen, 5-methylene-6-methyl-2-norbomen, 5-methylene-6, 6-dimethyl-2-norbomen, 5-propenyl-2-norbomen, 5- (3-cyclopentenyl) -2-norbomen, 5-ethylidene-2-norbomen and 5-cyclohexylidene-2-norbomen.

One preferred conjugated diene is piperylene. Preferred dienes are selected from the group consisting of 1,4-hexadiene, dicyclopentadiene, 5-ethylidene-2-norbomen, 5-methylene2-norbomen, 7-methyl-1,6-octadiene, piperylene and 4-vinylcyclohexene.

The molecular weight of the ethylene / α-olefin interpolymer will be selected based on the desired attributes of the thermoplastic marker properties of the formulation. It is well known that the molecular weight of the polymer correlates with the viscosity of the polymer melt. Typically, the ethylene / α-olefin interpolymer has a melt viscosity at 177 ° C of at least 500 mPa.s, preferably at least 1500 mPa.s (15 grams / cm.sec), more preferably at least 2500 mPa.s (25 grams / cm.seconds). and most preferably at least 3000 mPa.s (30 grams / cm.second). Similarly, the ethylene / α-olefin interpolymer will have a typical melt viscosity at 177 ° C of not more than 14000 mPa.s (140 grams / cm.second), preferably not more than 9000 mPa.s (90 grams / cm.seconds), more preferably Not more than 7500 mPa.s (75 grams / cm.seconds), and most preferably not more than 5000 mPa.s (50 grams / cm.seconds).

When the ethylene / α-olefin interpolymer has an ultra-low molecular weight, a numerical average molecular weight of less than 11000, it leads the ethylene / α-olefin interpolymer to a low polymer viscosity and formulation, but characterized by a crystallization temperature peak higher than that of the corresponding materials with a higher molecular weight but with the same density. In applications of pressure sensitive adhesive, an increase in the peak of crystallization temperature leads to increased thermal resistance. Low molecular weight ethylene / α-olefin interpolymers are more fully described below.

The density of the ethylene / α-olefin interpolymer will also be selected based on the desired properties of the adhesive formulation. Typically, however, it will have an ethylene /? -Olefin interpolymer

-3 3 density of at least 0.855 g / cm, preferably at least 0.860 g / cm and more preferably at least 0.870 g / cm³. Typically, the ethylene /? Olefin interpolymer will have a density of not more than • 3 o

0,965 g / cm, preferably not greater than 0,920 g / cm, more preferably not more than · in · 3

0.890 g / cm and even more preferably not more than 0.880 g / cm and most preferably not greater than 0.875 g / cm³.

The ethylene / α-olefin interpolymer will be present in the binder component of the thermoplastic marker composition of the invention in an amount greater than 1, preferably greater than 5, and more preferably greater than 10% by weight. The ethylene /? -Olefin interpolymer will typically be present in the binder component of the thermoplastic marker composition of the invention in an amount of not more than 99, preferably not more than 90, and most preferably not more than 80% by weight. In particularly preferred embodiments, the ethylene /? -Olefin interpolymer will be present in the binder component in an amount of 25 to 50 weight percent.

The first polymer can be suitably prepared using a single-site metallocene or a forced geometry metal complex. Forced geometry catalysts are described in U.S. Pat. No. 545,403, filed July 3, 1990 (EP-A-416,815), US Serial Number. 702,475, filed May 20, 1991 (EP-A-514,828); as in US-A5,470,993, 5,374,696, 5,231,106, 5,055,438, 5,057,475, 5,096,867, 5,064,802 and 5,132,380. In US application, serial no. 720,041, filed 24. June 1991 (EP-A514,828), describes and protects certain boron derivatives of forced-geometry precursors and the process for their preparation. US-A 5,453,410 describes as suitable catalysts for olefin polymerization combinations of cationic catalysts with forced geometry with alumoxane.

Suitable activation cocatalysts and activation techniques have been previously described with respect to various metal complexes in the following references: EP-A-277,003, US-A5,153,157, US-A-5,064,802, EP-A-468,651 (equivalent to US Serial No. 07 / 547,718), EP-A-520,732 (US Serial No 07 / 876,268 equivalent), WO 95/00683 (US Serial No 08 / 82,201 equivalent) and EP-A-520,732 (US Serial No 07 / 884,966 equivalent). filed May 1, 1992.

Catalysts found to be particularly suitable for the preparation of substantially linear ethylene / α-olefin interpolymers include e.g. the catalysts described in the examples below, such as activated by trispentafluorophenylborane and triisobutylaluminum modified methylalumoxane co-catalysts.

Molar ratio of metal complex used: Activation cocatalyst ranges from 1: 1000 to 2: 1, more preferably from 1: 5 to 1.5: 1, most preferably from 1: 2 to 1: 1. In the preferred case in which the metal complex is activated by trispentafluorophenylborane and methylalumoxane is modified by triisobutylaluminum, the molar ratio of titanium: boron: aluminum is typically from 1:10:50 to 1: 0.5: 0.1, most typically from 1: 3: 5.

A carrier, in particular silicon dioxide, aluminum oxide or polymer (especially poly (tetrafluoroethylene) or polyolefine) may be used and it is desirable to use it when using catalysts in the gas phase polymerization process. Preferably, the carrier is used in an amount that provides a catalyst (by metal) mass ratio: carrier of 1: 100 000 to 1:10, more preferably 1:50 000 to 1:20, and most preferably 1:10 000 to 1 : 30. In most polymerization reactions, the catalyst to molar ratio to polymerizable compounds of 10 ': 1 to 10' is used¹: 1, more preferably 10 '⁹: l to 10⁵.T.

In all cases, the individual components, as well as the recovered catalyst components, must be protected from oxygen and moisture. It is therefore necessary to prepare and recover the catalyst components and catalysts in an atmosphere free of oxygen and moisture. Preferably, the reactions are therefore carried out in the presence of a dry inert gas such as, for example, nitrogen.

The polymerization can be carried out as a batch or continuous polymerization process, whereby a continuous polymerization process is required to prepare substantially linear polymers. In a continuous process, ethylene, comonomer and optionally solvent and diene are continuously fed to the reaction zone and the polymer product is continuously removed.

In general, the first polymer can be polymerized under conditions for polymerization reactions of the Ziegler-Natta or Kaminsky-Sinn type, i.e., the reactor pressures range from atmospheric pressure to 350 MPa (3500 atmospheres). The reactor temperature should be greater than 80 ° C, typically 100 ° C to 250 ° C and preferably 100 ° C to 150 ° C, with temperatures at the higher end of the range, with temperatures higher than 100 ° C favoring the formation of polymers with lower molecular weight.

Together with the reactor temperature, the molecular weight of the polymer affects the molar ratio of hydrogen: ethylene, with higher levels of hydrogen leading to polymers with lower molecular weight. When it has the desired polymer I₂ 1 g / 10 min, the molar ratio will be hydrogen: ethylene characterized by OT When it has the desired polymer I₂ 1000 g / 10 min, the molar ratio of hydrogen: ethylene will be from 0.45: 1 to 0.7: 1. The upper limit of the hydrogen / ethylene molar ratio is 2.2 to 2.5: 1.

In general, the polymerization process is carried out with a differential pressure of ethylene of 70 to 7000 kPa (10 to 1000 psi), most preferably 30 to 300 kPa (40 to 60 psi). The polymerization is generally conducted at a temperature of from 80 to 250 ° C, preferably from 90 to 170 ° C and most preferably from above 95 ° C to 140 ° C.

In most polymerization reactions, the catalyst molar ratio is used: polymerizable compounds of 10 *¹²: l to 10 '¹: 1, more preferably 10 '⁹: 1 to 10 '⁵: 1. Solution polymerization conditions are required for the corresponding reaction components of the solvent. Preferred solvents include mineral oils and various hydrocarbons which are liquid at reaction temperatures.

Illustrative examples of useful solvents include alkanes such as pentane, isopentane, hexane, heptane, octane and nonane, as well as alkane mixtures including kerosene and isopar-Ε ™, available from Εχχοη Chemicals Inc., cycloalkanes such as cyclopentane and cyclohexane and aromatics such as benzene, toluene, xylene, ethylbenzene and diethylbenzene.

The solvent will be present in an amount sufficient to prevent phase separation in the reactor. Because the solvent functions to absorb heat, less solvent leads to a less adiabatic reactor. Solvent ratio. Ethylene (mass base) will typically be 2.5: 1 to 12: 1, above which the catalyst efficiency will suffer. The most typical solvent-ethylene (weight basis) ratio is in the range of 5: 1 to 10: 1.

The ethylene / α-olefin interpolymer can alternatively be prepared in the gas phase polymerization process using catalysts as described above which are applied to an inert carrier such as silica. The ethylene /? -Olefin interpolymer can be further fabricated in suspension polymerization using catalysts as described above which are applied to an inert carrier such as silica. A practical limitation is that suspension polymerizations occur in liquid diluents in which the polymer product is substantially insoluble. Preferably, the diluent for suspension polymerization is one or more hydrocarbons having less than 5 carbon atoms. If desired, saturated hydrocarbons such as ethane, propane or butane may be used as a diluent in whole or in part. Similarly, the α-olefin monomer or a mixture of different α-olefin monomers can be used as a diluent in its entirety or as part of it. The most preferred diluent comprises at least a majority of the α-olefin monomer (s) to be polymerized.

As used herein, the term adhesive enhancer means any of the compositions described below that are useful in giving the adhesive a hot melt adhesive composition. ASTMD D-1878-6 IT defines adhesiveness as a property of a material that enables it to form a bond of measurable strength immediately upon contact with another surface

The binder component of the thermoplastic markime composition of the invention will comprise at least 5% by weight of the adhesive, typically at least 10% by weight, and more preferably at least 20% by weight. Similarly, the binder component of the thermoplastic markime composition of the invention will comprise no more than 70% by weight of the adhesive, preferably not more than 60% by weight of the adhesive, and more preferably not more than 50% by weight of the adhesive. In general, adhesive enhancing resins useful in the binder components of thermoplastic markim compositions of the invention include resins derived from renewable sources, such as resin derivatives, which include tree resin, tallow oil, rubber resin, resin esters, natural and synthetic terpenes and their derivatives. The aliphatic, aromatic or mixed aliphatic-aromatic petroleum-based adhesive enhancers are also useful as a binder component of thermoplastic markim compositions of the invention. Representative examples of useful hydrocarbon resins include α-methylstyrene resins, branched and unbranched C5 resins, C9 resins, Cio resins as well as styrene and hydrogenated modifications thereof.

The adhesive enhancement resins range from being liquid at 37 ° C to having a ring and ball point of softening point of about 135 ° C. Solid resins for increasing the stickiness with a softening point greater than about 100 ° C, more preferably with a softening point greater than about 130 ° C, are particularly useful for improving the cohesive strength of the binder component of thermoplastic markings of the compositions of the present invention, especially when used only a single homogeneous ethylene / aolefin interpolymer.

For the binder component of thermoplastic markim compositions of the invention, a preferred aliphatic adhesive resin is preferred. However, resins are also useful for increasing adhesiveness with increased aromatic character, especially when another adhesive enhancer or a common compatible softener is used.

Softener is broadly defined as a typical organic composition that can be added to thermoplastic materials, gums and other resins to enhance extrudability, flexibility, workability or elongation. In preferred embodiments of the invention, a plasticizer is added to the binder component of the thermoplastic markimage composition in amounts of up to 20% by weight, preferably less than 15% by weight and more preferably less than 10% by weight of the binder component of the thermoplastic markimage composition. While the use of a plasticizer is optional, when used, it is typically added to the binder component in an amount of at least one percent by weight, preferably at least 3 percent by weight.

The plasticizer may be either liquid or solid at room temperature. Examples of liquid softeners include hydrocarbon oils, polybutene and liquid elastomers. Softener oils are primarily hydrocarbon oils having a low aromatic content and which are paraffinic or naphthenic in character. The softening oils are preferably poorly volatile, transparent and have as little color and odor as possible. The use of softeners in the present invention also contemplates the use of olefin oligomers, low molecular weight polymers, vegetable oils and their derivatives, and similar softening fluids.

When a solid softener is used, it will preferably have a softening point above 60 ° C. It is believed that by combining a homogeneous ethylene / α-olefin interpolymer with a suitable adhesive-enhancing resin and a solid softener such as cyclohexane dimethane dibenzoate plasticizer, the thermoplastic branded compositions formed can be applied at temperatures below 120 ° C, preferably below 100 ° C. Although the example compound is 1,4-cyclohexane dimethanol dibenzoate, commercially available from Velsicol under the trade name Benzoflex ™ 352, any solid softener that can subsequently be recrystallized in the resulting thermoplastic composition can be used. Other plasticizers that may be suitable for this purpose are described in EP 0422 108 BI and EP 0 410 412 BI, both attributed to HB Fuller Company.

Waxes can be advantageously used in the binder component of thermoplastic markings of the compositions of the present invention, especially when the thermoplastic markings composition is desired to be relatively non-sticky after cooling and curing, such as e.g. for various applications of book packing and binding, as well as foam in seals. Waxes useful in the binder component of the thermoplastic markers of the compositions of the present invention include paraffin waxes, microcrystalline waxes, Fischer-Tropsch, polyethylene and polyethylene byproducts, where M_w less than 3000. The wax is present in the binder component in an amount of less than 10% by weight, preferably less than 8% by weight. While optional, wax, when used, is typically added in an amount of at least 1 weight percent, preferably at least 3 weight percent.

Ethylene / α-olefin interpolymers of ultra-low molecular weight, prepared using forced-geometry catalysts and which may be called homogeneous waxes, are also suitable. Such homogeneous waxes as well as procedures for preparing such homogeneous waxes are given in the examples below. Homogeneous waxes will have, in contrast to paraffin waxes and crystalline ethylene homopolymeric or interpolymeric waxes, M_w/ M_n from 1.5 to 2.5, preferably 1.8 to 2.2.

Homogeneous waxes will be either ethylene homopolymers or interpolymers of ethylene and C₃-C₂o α-olefin. A homogeneous wax will have a numerical average molecular weight of less than 6000, preferably less than 5000. Such homogeneous waxes will typically have a numerical average molecular weight of at least 800, preferably at least 1300.

Homogeneous waxes lead to low polymer viscosity and formulation, but they are characterized by crystallization temperature peaks higher than the crystallization peaks of the corresponding high molecular weight materials with the same density. In applications of polymer binders, an increase in the peak of crystallization temperature leads to an increase in thermal resistance, an improved creep resistance, and an improved shear adhesion failure temperature.

In addition to, or instead of, non-functionalized wax, the binder furmulation will optionally comprise polyethylene having suspended acid functional moieties. In the practice of the present invention, any unsaturated organic compound containing at least one ethylene unsaturation (e.g. at least one double bond), at least one carbonyl group (C = O) can be used and which will cleave to polyethylene. Representatives of compounds containing at least one carbonyl group are carboxylic acids, anhydrides, esters and their salts, both metal and non-metal. Preferably, the organic compound contains ethylene unsaturation conjugated to a carbonyl group. Representative compounds include maleic, fumamo, acrylic, methacrylic, itaconic, crotonic, methyl crotonic and cinnamic acids and their anhydrous, ester and salt derivatives, if any. Maleic anhydride is a preferred unsaturated organic compound containing at least one ethylene unsaturation and at least one carbonyl group.

The content of unsaturated organic compound in acid-functionalized polyethylene is at least 0.01% by weight and preferably at least 0.05% by weight based on the combined weight of the polymer and the organic compounds. The maximum amount of unsaturated organic compound content may vary as appropriate, but typically does not exceed 10% by weight, preferably does not exceed 5% by weight, and more preferably does not exceed 2% by weight.

The unsaturated organic compound may be grafted onto polyethylene by any known technique such as those disclosed in U.S. Pat. No. 3,236,917 and U.S. Pat. No. 5,194,509. E.g. in patent '917, the polymer is introduced into a two-roll mixer and mixed at 60 ° C. The unsaturated organic compound is then added together with the free radical initiator such as e.g. benzoyl peroxide and components are stirred at 30 ° C until vaccination is complete. In the patent '509, the process is similar except that the reaction temperature is higher, e.g. 210 to 300 ° C, and the free radical initiator is not used or is being used in reduced concentration.

An alternative and preferred vaccination method is set forth in U.S. Pat. No. 4,950,541 using a twin-screw devolatization extruder as a mixing apparatus. The polyethylene and unsaturated organic compounds are mixed and reacted in the presence of the free radical initiator inside the extruder at the temperatures at which the reactants are melted. Preferably, the unsaturated organic compound is injected into a zone within the extruder which is maintained under pressure.

Acid-functionalized polyethylene is present in the binder component in an amount of less than 10% by weight, preferably less than 8% by weight. While acid-functionalized polyethylene is optional, when used it is typically added in an amount of at least 1 percent by weight, preferably at least 3 percent by weight.

In the practice of the present invention, any polyethylene which may be acid-functionalized will be suitable. However, the preferred class of polyethylene is the class of ultra-low molecular weight ethylene / α-olefin interpolymers prepared using a forced geometry catalyst. Such polyethylene will have M_w/ M_n from 1.5 to 2.5, preferably from

1.8 to 2.2.

The polyethylene will preferably have, before acid-functionalization, a numerical average molecular weight of less than 6000, preferably less than 5000, and will typically have a numerical average molecular weight of at least 800, preferably at least 1300, as determined by gel permeation chromatography.

As is well known in the art, various other components can be added to modify the stickiness, color or odor of a thermoplastic markime composition. Formulations may also include additives such as antioxidants (e.g., impeded phenols (e.g., Irganox ™ 1010, Irganox ™ 1076) phosphites (e.g., Irgafos ™ 168)), antiblock additives, pigments and fillers. It is generally preferred that the additives be relatively inert and have minor effects on the properties contributed by the homogeneous linear or substantially linear interpolymer, adhesive enhancer, and softener.

In addition to the binder component, the thermoplastic mark compositions of the invention will further comprise at least one organic filler. Fillers useful in the formulations include sand (quartz), dolomite or talc, carbon black or graphite, calcium carbonate, fly ash, cement powder, clay, feltspar, nepheline, quartz or glass, calcined silica, aluminum oxide, magnesium oxide, zinc oxide, barium sulfate, aluminum silicate, calcium silicate, titanium dioxide, titanates, glass beads, chalk and pigments.

Preferred sand (quartz), dolomite or talc, glass microspheres, pigments and mixtures thereof are preferred.

The filler will be added to the thermoplastic markim composition in an amount of from 40 to 90% by weight, preferably from 50 to 90% by weight. In particularly preferred embodiments, the filler will comprise a combination of the following: 0 to 60% by weight of sand, 0 to 100% by weight of dolomite or talc, 0 to 50% by weight of glass microspheres and 1 to 20% by weight of pigment.

When a thermoplastic coating composition is desired to have reflective properties, a reflective inorganic filler will be used. One particularly preferred reflective inorganic filler is glass microspheres. When a reflective inorganic filler is used, it is typically added to the thermoplastic coating composition in an amount of at least 5% by weight, preferably at least 10% by weight and more preferably at least 20% by weight. A reflective inorganic material is added to the thermoplastic coating composition in an amount of not more than 70, preferably not more than 50% by weight and most preferably not more than 40% by weight.

Certain inorganic fillers will typically be used in order to reduce the cost of the formulation. One suitable extender filler is dolomite clay. When used, dolomite pickup is added in an amount of at least 10% by weight, more preferably at least 20% by weight and most preferably at least 30% by weight of the thermoplastic coating composition. The dolomite filler will typically be added in an amount of not more than 80% by weight, more preferably not more than 75% by weight, and most preferably not more than 70% by weight of the thermoplastic coating composition.

Thermoplastic brand compositions according to the invention are advantageous because they can be easily molded by applying them to the various techniques used in the industry. The present invention is e.g. enabled the development of a single formulation that can be applied with the use of extrusion, screed or spray techniques.

The thermoplastic mark compositions of the invention will preferably express adhesion as measured according to the techniques given in Example 2, at least 1.0 N / mm², preferably 1.2 N / mm, more preferably at least 1.3 N / mm, and most preferably at least

1.5 N / mm².

The thermoplastic mark compositions of the invention will preferably express luminescence as measured according to the techniques given in Example 2, at least 70, preferably at least 75, more preferably at least 76, and most preferably at least 78.

The thermoplastic mark compositions of the invention further express good low-temperature abrasion resistance. The subject formulations exhibit improved low temperature flexibility and low temperature adhesion and express improved smoke and low odor properties at high temperatures. The subject formulations express a wide potential range of application temperatures, especially at temperatures from 150 ° C to 250 ° C, which make them suitable for application by various means. E.g. the ability of the compositions to be applied at low application temperatures, i.e., temperatures of about 150 to 170 ° C, makes them suitable for application with extrusion coating techniques; while the ability of the compositions to be applied at higher application temperatures, i.e., temperatures from 200 ° C to 250 ° C, makes them suitable for application with spray coating techniques. The subject formulations are preferably resistant to dirt uptake and furthermore preferably exhibit less viscosity variability compared to systems lacking a homogeneous ethylene polymer.

The subject formulations can be applied conveniently by spraying, screeding and extrusion techniques. In addition, the subject formulations can be provided as preformed strips, which are laid on the surface and bound thereto by heating, e.g., with a gas flame, optionally at some pressure, such as e.g. by rolling.

Examples of applications for thermoplastic markime compositions of the invention are road markings with hot melt extrusion, road markings with hot melt spray, road markings with manual hot melt application; bicycle lanes marked with colored hot melt applied by spray or extrusion; marking of simulation / training roads for driving on an ice surface; preformed extruded traffic signs (such as arrows, letters, etc.) and tapes (such as traffic safety, information, decoration, etc.) (also called pre-signs or hot smelters); marking flexible and soft sports / playing surfaces such as tartan (e.g. in marking tennis courts, outdoor and indoor sports floors, etc.); safety markings on ships, oil rigs, etc .; and reflective traffic safety coatings for tunnels, concrete, metals, glass beads, or other reflective / self-shining pigments.

In one preferred application, the subject thermoplastic markime compositions will be used for convex road markings. The convex road markings are formed by extruding the markime composition onto the surface, applying reflective particles such as glass beads to the extruded marking and by projecting the extruded marking to create channels or other ridges. Such protrusions are desirable because they provide improved drainage of water and improve reflective properties at night, especially in rainy weather. The thermoplastic mark compositions of the invention are useful in convex road marking applications as they provide the necessary degree of flexibility, adhesion and abrasion even under low temperature conditions.

The following examples are given to illustrate typical embodiments of the invention and are not intended to serve as a limitation of its scope.

Preparation of homogeneous ethylene polymers

Homogeneous ethylene polymers are prepared according to the process of published PCT patent application WO 97/26287, which is equivalent to US patent application serial no. No. 08 / 784,683, filed Jan. 22, 1997.

The process for preparing polymer A is given as follows:

The process for the preparation of ultra-low molecular weight ethylene polymers is as follows.

Preparation of the catalyst

Part 1: Preparation of TiCl₃(DME) i5

The apparatus (indicated by R1) was closed with a lid and purged with nitrogen; The apparatus consists of a 10 1 glass kettle with a flush valve mounted on the bottom, with a 5-door head, polyethylene gasket, clamp and mixing components (bearing, axle and blade). The necks are fitted as follows: the mixing components are mounted on the central door and the outer necks have a reflux condenser fitted at the top with gas outlet / inlet and solvent inlet, thermocouple and stopper. Dry, deoxygenated dimethoxyethane (DME) was added to the flask (approximately 5 L). 700 g of TiCl were weighed in a desiccator₃ in equilizers a powder hopper; The funnel was closed, removed from the desiccator and mounted on the reaction kettle in place of the stopper. After about 10 minutes, TiCl was added with stirring₃. Once the addition was complete, we rinsed the remaining TiCl₃ extra DME was used in the flask. The funnel was replaced with a stopper and the mixture heated to reflux. The color changed from purple to light blue. The mixture was heated for about 5 hours, cooled to room temperature, allowed the solid to settle and the supernatant decanted from the solid. TiCl₃(DME)₁₅ we left in Rl as a light blue solid.

Part 2: Preparation [(Me₄C5) SiMe2N-t-Bu] MgCl] 2

The apparatus (called R-2) was adjusted as described for R1 except that the size of the flask was 30 1. The head was equipped with 7 necks, a mixer in the central neck, and the outer necks contained a condenser that had a top inlet / nitrogen outlet, vacuum adapter and reagent addition tube, thermocouple and stopper. The flask was filled with 4.5 1 toluene, 1.14 kg (Me₄C5H) SiMe₂NH-t-Bu and 3.46 kg 2 M i-PrMgCl in

Et₂A. The mixture was then warmed and allowed to evaporate in the trap to -78 ° C. After 4 hours, the temperature of the mixture reached 75 ° C. Finally, the heater was turned off and DME was added to the hot mixed solution, resulting in the formation of a white solid. The solution was allowed to cool to room temperature, the material was allowed to settle and the supernatant decanted from the solid. [(Me4C₅) SiMe2N-t-Bu] [MgCl] 2 was left in R-2 as a gray-white solid.

Part 3: Preparation [(r |⁵-Me4C5) siMe2N-t-Bu] TiMe2

The material in Rl and R-2 was suspended in DME (3 1 DME in Rl and 5 1 in R-2). The contents of Rl were transferred to R-2 using a transfer tube connected to the floor valve 10 1 of the flask and one of the upper openings in the 30 1 flask. The remaining material in R1 was washed using additional DME. The mixture rapidly darkened to a deep red / brown color and the temperature in R-2 increased from 21 ° C to 32 ° C. After 20 minutes, 160 ml of CH2Cl2 was added through the addition funnel, resulting in a change in color to green / brown. This was followed by the addition of 3.46 kg of 3 M MeMgCl in THF, resulting in an increase in temperature from 22 ° C to 52 ° C. The mixture was stirred for 30 minutes and then 6 l of solvent was removed in vacuo. Isopar ™ E hydrocarbon (6 1) was added to the flask. This vacuum / solvent cycle was repeated, removing 4 1 solvents and adding 5 1 Isopar ™ E hydrocarbons. An additional 1.2 1 solvent was removed in the final vacuum step. The material was allowed to settle overnight, then decanted into another 30 1 glass kettle (R-3). The solvent in R-3 was removed in vacuo to leave a brown solid which was re-extracted with Isopar E; This material was transferred to a storage cylinder. The analysis showed that the solution (17.23 1) was 0.1534 M in titanium; this equals 2,644 moles [(r |⁵-Me4C5) SiMe2N-t-Bu] TiMe2. The remaining solid in R-2 was further extracted with Isopar ™ E hydrocarbon, the solution was transferred to R-3, then dried under vacuum and re-extracted with Isopar ™ E hydrocarbon. This solution was transferred to a storage bottle. The analysis showed a concentration of 0.1403 M titanium and a volume of 4.3 1 (0.6032 mol [(r |⁵-Me4C5) SiMe₂Nt-Bu] TiMe2). That the total yield of 3.2469 moles [(q⁵-Me4C5) SiMe2N-t-Bu] TiMe₂, or 1063 g. That's a 72 percent yield, entirely based on titanium added as TiCl₃.

Polymerization

Polymer A was prepared according to the following procedure and using the reaction conditions listed in Table 1.

Ethylene and hydrogen were combined into one stream before being introduced into a dilution mixture, a mixture of Cg-Cio saturated hydrocarbons, e.g. Isopar-AE hydrocarbon mixture (available from Εχχοη Chemical Company) and comonomer. The comonomer was 1-octane. The reactor feed mixture was continuously injected into the reactor.

The metal complex and the cocatalysts were combined into one stream and also continuously injected into the reactor. The cocatalysts were tris (pentafluorophenyl) borane, available as three wt. percentage solution in Isopar ™ E mixed hydrocarbon from Boulder Scientific. Aluminum was provided in the form of a solution of modified methylalumoxane (MMAO type 3A) in heptane, available as 2 wt. percent aluminum concentration of Akzo Nobel Chemical Inc.

We allowed sufficient holding time for the metal complex and the cocatalyst to react before being introduced into the polymerization reactor. A constant reactor pressure of about 3.3 MPa was maintained in each polymerization reactor. The ethylene content of the reactor was maintained at each of the polymerizations, after reaching a stable state, under the conditions listed in Table 1.

After polymerization, the reactor outlet stream was introduced into the separator, where the molten polymer separated from the unreacted comonomer (s), unreacted ethylene, unreacted hydrogen and the dilution mixture stream. The molten polymer was then chopped or pelleted and, after cooling in a water bath or pelletizer, solid pellets were collected. Table 1 describes the polymerization conditions and properties of the resulting polymer A polymer.

Polymer A was stabilized with 2000 ppm of phenol-impeded Irganox ™ 1010 available from Ciba-Geigy.

Table one

Polymer A

<td>Ethylene total intake (kg / hr)</td><td> 0,91</td>

<td>Fresh ethylene intake (kg / hr)</td><td> 0,91</td>

<td>Total comonomer intake (kg / hr)</td><td> 1,04</td>

<td>Fresh Comonomer intake (kg / hr)</td><td> 1,04</td>

<td>Comonomer ratio: olefm (mole percent)</td><td> 12,5</td>

<td>Hydrogen ratio: eth ylene (molar percentage)</td><td> 0,49</td>

<td>Ethylene Thinner Ratio (Mass Base)</td><td> 11,1</td>

<td>Concentration of catalyst metal (ppm)</td><td> 4</td>

<td>Catalytic Flow Rate (kg / hr)</td><td> 0,14</td>

<td>Co-catalyst concentration (ppm)</td><td> 88</td>

<td>Co-catalyst flow rate (kg / hr)</td><td> 0,21</td>

<td>Aluminum Concentration (ppm)</td><td> 9,8</td>

<td>Aluminum flow rate</td><td> 0,20</td>

<td>Reactor temperature (° C)</td><td> 110</td>

<td>Ethylene concentration in reactor outlet stream (percentage by mass)</td><td> 1,69</td>

<td>Polymer density (g / cm)</td><td> 0,873</td>

<td>Viscosity of polymer melt at 177 ° C (mPa.s</td><td> 4300</td>

<td>(grams / (cm. seconds))</td><td> (43)</td>

Example one

The following components were heated to 180 ° C in a standard mixer in the amounts listed in Table 1 (A) and mixed at low speed to avoid introduction of air bubbles into the melt. Polymer A is essentially a linear ethylene / 1-octene copolymer with a density of 0.873 g / cm³ and a melt viscosity of 4300 mPa.s (43 g / cm.second) at 177 ° C, available from The Dow Chemical Company. The adhesive enhancer is C5 Escorez 1102-M resin available from Εχχοη Chemical Company at a density of 0.970 g / cm³ and a viscosity of 7500 mPa.s (75 g / cm.second) at 140 ° C. The mineral oil is Midioway 68, available at Statoil, with a density of 0.870 g / cm and a viscosity of 71 χ 10 '⁶ m²/ s (70 centistokes) at 40 ° C. Wax is Polyace 573, with maleic anhydride grafted wax, available at Allied Signal and with a maximum viscosity of 600 mPa.s (6 grams / cm.second) at 140 ° C and a hardness of 3 to 6 dmm at 25 ° C, Mettler impact tip 104 to 107⁰C and not more than 0,06% of free maleic anhydride. TiO₂, rutile, A-ll; and TiO₂, anatas R-011 are available from Kronos Titan A / S. Dolomite is available as a Microdol M-200 made by Micro Minerals and available from Nonvegian Tale AS. The sand is available as sodium ev-feldspar. Glass reflector balls are available from Swarco Vestglas as Class A-OV balls.

Table one (A)

<td>Component</td><td>Quantity (percentage by weight)</td>

<td>Adhesive enhancer</td><td> 10</td>

<td>Polymer A</td><td> 8</td>

<td>Mineral oil</td><td> 2,5</td>

<td>Wax</td><td> 1</td>

<td>TiO₂, rutile</td><td> 1,7</td>

<td>TiO₂, anatas</td><td> 1,7</td>

<td>Dolomite</td><td> 30,1</td>

<td>Sand</td><td> 25</td>

<td>Glass balls</td><td> 20</td>

Example two (spray thermoplastic marker compositions):

The following compositions are prepared in the manner given above with respect to Example 1. Polymer B, available from The Dow Chemical Company, is essentially a linear ethylene / 1-octene melt copolymer at 177 ° C 2700 mPa.s (27 g /cm.second) and a density of 0.892 g / cm³.

Thermoplastic markime compositions were evaluated for viscosity, needle penetration, luminescence, color, and adhesion.

Viscosity was measured using standard techniques, e.g. using a Brookfield viscometer DV-l + type RVT at 200 ° C with spindle no. 28 at 20 rpm. per min or Viscotech rheometer, where viscosity measurements were performed at 200 ° C and using a P 20 ETC spindle.

Needle penetration was measured according to the prEN 1871 Annex J. test method, a thermoplastic method for the test of bite.

Luminescence and color coordinates were measured according to the prEN test method 1871, Annex E, a thermoplastic method for testing the trichromatic x, y coordinates and the luminescence factor β. The color coordinates preferably fell within the shape defined in Figure 1.

Adhesion was measured according to the WMB 502: 1993 test method - thermoplastic road marking materials, determination of elongation, except that the test was performed on concrete instead of Marshall test specimens.

The observed properties are given in the following table two:

Table two

<td></td><td>Target</td><td>Sample 1</td><td>Sample 2</td>

<td>Viscosity at 200 ° C (mPa.s</td><td> 3000-5000</td><td> 4350</td><td> 5175</td>

<td>(grams / cm. second))</td><td> (30-50)</td><td> (43,5)</td><td> (51,75)</td>

<td>Needle Penetration (s / 10 mm)</td><td> 5-120</td><td> 34,5</td><td> 62</td>

<td>Luminescence</td><td> 76 ± 1</td><td> 77,5</td><td> 78,7</td>

<td>Color Coordinates (x / y)</td><td>Figure 1</td><td> 0,324/0,344</td><td> 0,325/0,343</td>

<td>Adhesion (N / mm)</td><td>greater than 1,3</td><td> 1,42</td><td> 0,99</td>

As shown in Table two, the formulations of sample 1 satisfy each of the target criteria, which makes it preferable to the formulation of case 2.

Example three (extrusion thermoplastic marker compositions):

The following compositions were prepared in the manner given above with respect to example one. Polymer B, available from The Dow Chemical Company, is essentially a linear ethylene / octene copolymer with a melt viscosity at 177 ° C of 2700 mPa.s (27 g / cm.second) and a density of 0.892 g / cm³.

Thermoplastic markime compositions were evaluated for viscosity, needle penetration, luminescence, color, and adhesion according to the procedures given for example two.

The observed properties are given in the following table three:

Table three

<td></td><td>Target</td><td>Sample 3</td><td>Sample 4</td>

<td>Viscosity at 200 ° C (mPa.s</td><td> 6000-9000</td><td> 4850</td><td> 6450</td>

<td>(grams / cm. second))</td><td> (60-90)</td><td> (48,5)</td><td> (64,5)</td>

<td>Needle Penetration (s / 10 mm)</td><td> 5-45</td><td> 33</td><td> 55</td>

<td>Luminescence</td><td> 76 ± 1</td><td> 78,4</td><td> 78,6</td>

<td>Color Coordinates (x / y)</td><td>Figure 1</td><td> 0,324/0,343</td><td> 0,324/0,343</td>

<td>Adhesion (N / mm)</td><td>greater than 1,3</td><td> 1,42</td><td> 0,99</td>

Example four

The following compositions have been prepared in the manner given above with reference to example one.

The polymers used in the binder formulations are those given in the following table four, each substantially linear ethylene / 1-octene copolymer available from The Dow Chemical Company.

Table four

<td></td><td>Density (g / cm³)</td><td>Viscosity of melt at 177 ° C (mPa.s (grams / cm.second))</td>

<td>Polymer A</td><td> 0,873</td><td> 4300 (43)</td>

<td>Polymer B</td><td> 0,892</td><td> 2700 (27)</td>

<td>Polymer C (Comparative)</td><td> 0,870</td><td> 1000* (10)</td>

<td>Polymer D</td><td> 0,880</td><td> 5000 (50)</td>

<td>Polymer E (Comparative)</td><td> 0,880</td><td> 1000* (10)</td>

<td>Polymer F</td><td> 0,890</td><td> 1000 (10)</td>

* The values ​​quoted are melting indices (I₂) in units of g / 10 minutes, as opposed to the viscosity of the melt.

Thermoplastic markime compositions were evaluated for viscosity, needle penetration, luminescence, color, and adhesion according to the procedures given for example two.

The observed properties are given in the following table five:

Table five

<td></td><td>Viscosity at 200 ° C (mPa.s (grams / cm. second))</td><td>Penetration needles (s / 10 mm)</td><td>Lumine- the scene</td><td>Colored coordinates (x / y)</td><td>Adhesion (N / mm²)</td>

<td>rri v Target</td><td> 4000-6000 (40-60)</td><td> 5-45</td><td> 76±1</td><td></td><td>less than 1.3</td>

<td>Sample 6 (Polymer B)</td><td> 5350 (53,5)</td><td> 56</td><td> 78,1</td><td> 0,323/0,341</td><td> 1,71</td>

<td>Sample 7 (Comparative) (Polymer C)</td><td> 10770 (107,7)</td><td> 0</td><td> 77,8</td><td> 0,324/0,343</td><td> 0,83</td>

<td>Sample 8 (Polymer A)</td><td> 7350 (73,5)</td><td> 0</td><td> 77,7</td><td> 0,324/0,343</td><td> 0,84</td>

<td>Sample 9 (Polymer D)</td><td> 7275 (727,5)</td><td> 5,5</td><td> 77,6</td><td> 0,324/0,343</td><td> 0,93</td>

<td>Sample 10 (Comparative) (Polymer E)</td><td> 10050 (100,5)</td><td> 6</td><td> 77,4</td><td> 0,326/0,344</td><td> 0,88</td>

<td>Sample 11 (Polymer F)</td><td> 4025 (40,25)</td><td> 48,5</td><td> 78,0</td><td> 0,325/0,344</td><td> 1,26</td>

Example five

In a preferred embodiment of the invention, the thermoplastic marking composition will meet the specifications given in the following table six.

Table six

<td></td><td colspan="4">Product</td>

<td>Specifications</td><td>versatile</td><td>spray an artificial substance</td><td>profiled</td><td>ed. um. substance</td>

<td>Viscosity at 200 ° C (mPa.s (grams / cm. second))</td><td> 4000-7000 (40-70)</td><td> 2000-5000 (20-50)</td><td> 10000-14000 (100-140)</td><td> 4000-9000 (40-90)</td>

<td>Needle Penetration (s / 10 mm)</td><td> 5-120</td><td> 5-120</td><td> &gt;60*</td><td> 5-120</td>

<td>Luminescence</td><td colspan="4"> &gt;75</td>

<td>Color coordinates (x, y)</td><td colspan="4">Figure 1</td>

<td>Adhesion (N / mm)</td><td colspan="4"> &gt;1,3</td>

* measured at 30 ° C.

The formulation, identified as versatile, has been formulated to be suitable for application with extrusion, screed or spray techniques. The formulation, identified as a spray plastic, is designed to express the preferred properties in spray applications. The formulation, identified as profiled, is designed to express preferred properties in extrusion applications. Formulation identified as shifts. um. the substance is similar to a versatile formulation, except that a different plasticizer is used.

The formulations were prepared in the manner given above with respect to example one. All tests were performed using the measurement techniques listed above with respect to example two. The formulations are given in the following tables seven to ten. The measured formulation data are given in Table Eleven.

Table seven: Versatile

<td>Supplier</td><td>Trade name</td><td>Component</td><td>Fat%</td>

<td>The Dow Chemical Co.</td><td></td><td>Polymer A as described above</td><td> 8,00</td>

<td>Εχχοη Chemical</td><td>Escorez 1102-RM</td><td>C5 resin</td><td> 10,50</td>

<td>Esso (Chemical Chemical)</td><td>Primol 542</td><td>Paraffin oil</td><td> 2,50</td>

<td>Allied Signal</td><td>Polyace 573</td><td>Wax</td><td> 1,00</td>

<td>The Chemicane Foundation Police SA (Poland)</td><td>Tytanpol R001</td><td>Titanium dioxide rutile</td><td> 6,00</td>

<td>Norwegian Tale</td><td>Microdol M-200</td><td>Dolomite 1</td><td> 15,00</td>

<td>Starbruken AB</td><td>A-40</td><td>Dolomite 2</td><td> 27,00</td>

<td>Swarco Vestglas</td><td>300-800 mm</td><td>Intremix glass beads</td><td> 30,00</td>

<td>The whole formulation</td><td colspan="3"> 100,00</td>

Table eight: Spray plastic

<td>Supplier</td><td>Trade name</td><td>Component</td><td>Fat%</td>

<td>The Dow Chemical Co.</td><td></td><td>Polymer A</td><td> 9,50</td>

<td>Εχχοη Chemical</td><td>Escorez 1102-RM</td><td>C₅ resin</td><td> 11,50</td>

<td>Esso (Chemical Chemical)</td><td>Primol 542</td><td>Paraffin oil</td><td> 3,00</td>

<td>Allied Signal</td><td>Polyace 573</td><td>Wax 1</td><td> 1,00</td>

<td>Huls</td><td>Vestowax C-80</td><td>Wax 2</td><td> 1,00</td>

<td>The Chemicane Foundation Police SA (Poland)</td><td>Tytanpol R001</td><td>Titanium dioxide rutile</td><td> 5,00</td>

<td>Norvvegian Tale</td><td>Microdol M-200</td><td>Dolomite 1</td><td> 10,00</td>

<td>Starbruken AB</td><td>A-40</td><td>Dolomite 2</td><td> 59,00</td>

<td>The whole formulation</td><td colspan="3"> 100,00</td>

Table nine: Extrusion for profiled lines

<td>Supplier</td><td>Trade name</td><td>Component</td><td>Fat%</td>

<td>The Dow Chemical Co.</td><td></td><td>Polymer A</td><td> 8,00</td>

<td>Εχχοη Chemical</td><td>Escorez 1102-RM</td><td>C5 resin</td><td> 8,00</td>

<td>Esso (Chemical Chemical)</td><td>Primol 542</td><td>Paraffin oil</td><td> 2,50</td>

<td>Allied Signal</td><td>Polyace 573</td><td>Wax 1</td><td> 0,50</td>

<td>Hiils</td><td>Vestowax C-80</td><td>Wax 2</td><td> 1,00</td>

<td>Miljstek</td><td>Finsikt</td><td>Glass fiber</td><td> 1,00</td>

<td>The Chemicane Foundation Police SA (Poland)</td><td>Tytanpol R001</td><td>Titanium dioxide rutile</td><td> 6,00</td>

<td>Kronos Titan</td><td>Kronos 1002</td><td>Titanium dioxide anatas</td><td> 3,70</td>

<td>Nonvegian Tale</td><td>Microdol M-200</td><td>Dolomite 1</td><td> 15,00</td>

<td>Starbruken AB</td><td>A-40</td><td>Dolomite 2</td><td> 24,30</td>

<td>Swarco Vestglas</td><td>300-800 mm</td><td>Intremix glass beads</td><td> 30,00</td>

<td>The whole formulation</td><td colspan="3"> 100,00</td>

Table ten: Versatile with exchanges. catering means

<td>Supplier</td><td>Trade name</td><td>Component</td><td>Fat%</td>

<td>The Dow Chemical Co.</td><td></td><td>Polymer A</td><td> 8,50</td>

<td>Εχχοη Chemical</td><td>Escorez 1102-RM</td><td>C 5 resin</td><td> 8,50</td>

<td>BP Chemicals Ltd.</td><td>Hyvis 30</td><td>Polybutene</td><td> 4,00</td>

<td>Huls</td><td>Vestowax C-80</td><td>Wax</td><td> 1,00</td>

<td>The Chemicane Foundation Police SA (Poland)</td><td>Tytanpol R001</td><td>Titanium dioxide rutile</td><td> 5,00</td>

<td>Norwegian Tale</td><td>Microdol M-200</td><td>Dolomite 1</td><td> 15,00</td>

<td>Starbruken AB</td><td>A-40</td><td>Dolomite 2</td><td> 28,00</td>

<td>Swarco Vestglas</td><td>300-800 mm</td><td>Intremix glass beads</td><td> 30,00</td>

<td>The whole formulation</td><td colspan="3"> 100,00</td>

Table eleven: Properties of thermoplastic coating compositions

<td></td><td colspan="4">Product</td>

<td>Specifications</td><td>versatile</td><td>spray an artificial substance</td><td>profiled</td><td>ed. um. substance</td>

<td>Viscosity at 200 ° C (mPa.s (grams / cm. second))</td><td> 6275 (62,75)</td><td> 4525 (45,25)</td><td> 12400 (124)</td><td> 7475 (74,75)</td>

<td>Needle Penetration (s / lOmm)</td><td> 74</td><td> 94</td><td> 6</td><td> 53</td>

<td>Luminescence</td><td> 84,5</td><td> 83,8</td><td> 80,8</td><td> 78,9</td>

<td>Color coordinates (x, y)</td><td> 0,322/0,342</td><td> 0,323/0,343</td><td> 0,324/0,343</td><td> 0,324/0,343</td>

<td>Adhesion (N / mm²)</td><td> 1,7</td><td> 2,0</td><td> *</td><td> 1,1**</td>

No results because epoxy does not harden Material breaks; it did not separate from the surface

The present invention has been described and illustrated above in the examples. Various modifications within the spirit and scope of the invention will be apparent to those skilled in the art. Therefore, the scope of the invention may be limited only by the following claims.