WO2001042349A1 - Marquage reflectorise et procede de production et d'application d'une composition renfermant ledit marquage reflectorise - Google Patents

Marquage reflectorise et procede de production et d'application d'une composition renfermant ledit marquage reflectorise Download PDF

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Publication number
WO2001042349A1
WO2001042349A1 PCT/DK2000/000684 DK0000684W WO0142349A1 WO 2001042349 A1 WO2001042349 A1 WO 2001042349A1 DK 0000684 W DK0000684 W DK 0000684W WO 0142349 A1 WO0142349 A1 WO 0142349A1
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WO
WIPO (PCT)
Prior art keywords
beads
road marking
marking composition
composition according
surface tension
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Application number
PCT/DK2000/000684
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English (en)
Inventor
Hans Abildgaard Thomsen
Original Assignee
Abildgaard Roadvision Aps
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Publication date
Application filed by Abildgaard Roadvision Aps filed Critical Abildgaard Roadvision Aps
Priority to AU18524/01A priority Critical patent/AU1852401A/en
Publication of WO2001042349A1 publication Critical patent/WO2001042349A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/004—Reflecting paints; Signal paints
    • E—FIXED CONSTRUCTIONS
    • E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
    • E01F—ADDITIONAL WORK, SUCH AS EQUIPPING ROADS OR THE CONSTRUCTION OF PLATFORMS, HELICOPTER LANDING STAGES, SIGNS, SNOW FENCES, OR THE LIKE
    • E01F9/00—Arrangement of road signs or traffic signals; Arrangements for enforcing caution
    • E01F9/50—Road surface markings; Kerbs or road edgings, specially adapted for alerting road users
    • E01F9/506—Road surface markings; Kerbs or road edgings, specially adapted for alerting road users characterised by the road surface marking material, e.g. comprising additives for improving friction or reflectivity; Methods of forming, installing or applying markings in, on or to road surfaces
    • E01F9/524—Reflecting elements specially adapted for incorporation in or application to road surface markings

Definitions

  • the present invention relates to a reflective road marking composition
  • a reflective road marking composition comprising a thermoplastic binder and a filler m the form of beads.
  • the invention also relates to a method of producing and applying a reflective road marking composition, a method of treating the beads for use m the composition, and the treated beads.
  • Reflective road marking compositions are well known m the art.
  • a solution or a dispersion very often comprising a polymeric or polymenseable material, it is also a known technique to incorporate glass beads to the road marking m order to improve the light reflecting properties .
  • the present invention is principally concerned with the surface properties of beads, which are to be incorporated into a thermoplastic binder and which contact the polymeric material forming the matrix while that material is m the liquid or molten state.
  • the material which is to form the matrix may be m the form of e.g. a melt, a solution or a dispersion and it may be polymeric or polyme ⁇ sable .
  • Beads may be incorporated into synthetic polymeric material for a variety of purposes, for example as fillers m thermoplastic materials and m thermosettmg resins m order to modify the properties of the material or to facilitate moulding, and m order to give light reflective properties to road markings.
  • fillers m thermoplastic materials and m thermosettmg resins m order to modify the properties of the material or to facilitate moulding, and m order to give light reflective properties to road markings.
  • filler m thermoplastics and thermosettmg materials it is often desirable that the beads should be evenly distributed throughout the final product m order to give uniformity of properties, and this implies that the beads should be uniformly distributed m the liquid material from which the product is moulded or other ways prepared.
  • the glass beads does not affect the cohesive strengths of the cooled thermoplastic or thermosettmg materials compared to the pure polymeric material, and this implies a strong bonding between the surface of the glass beads and the respective polymeric material to which the glass beads are incorporated.
  • 0 567 765 A2 describes light reflecting granulated thermoplastic bodies having very small glass beads partly embedded into its surface for use in road marking.
  • European Patent No. 0 586 341 Al describes an equipment for simultaneous applying road marking material and glass beads.
  • US Patent No. 3,746,425 describes a road marking where the voids between large uniform sized glass beads are filled with small also uniform sized glass beads.
  • US Patent No. 4,301,050 describes a thermoplastic road marking, wherein glass beads eventually are incorporated. The road marking material is characterised that is has a particular heat resistance. All the road markings compositions described the above patent publications have certain disadvantages.
  • the glass beads which are partly embedded the surface are easily peeled out of the marking if the intrusion depth of the glass beads is less than 50 of its diameter and especially if the marking is exposed to studded tyres or heavy traffic intensity. Furthermore the encapsulated beads works as break initiators resulting m an accelerated erosion of the total marking during the course of time.
  • the glass beads are removed from the surface of a marking, they are leaving many small craters which are filled with dark highway film resulting m an undesired discolou ⁇ sation of the marking causing both reduced night and day visibility.
  • US Patent No. 3,556,637 describes a light reflection spherical lens or aggregates of e.g. glass for use road marking material.
  • the spherical aggregates are coated with a transparent binder e.g. a mixture of a fluorated elastomer, methylisobutyl ketone, xylol and polyethylmethacrylate, wherein uncoated glass beads are partial embedded.
  • a road marking comprising such aggregates with embedded glass beads have the same disadvantages as the known road markings described above, namely that the glass beads easily slip out of the road marking leaving small craters which may causing both reduced night and day visibility.
  • US Patent No. 4,305,863 describes a thermoplastic polyurethane resin composition comprising ammosilane or epoxysilane, wherein microspherical ammosilane or epoxysilane coated glass beads may be incorporated.
  • the coating on the glass beads serves as coupling agents to the resin.
  • order to serve as a coupling agent it is necessary to use a resm containing a similar silane which render the resulting product to be very expensive.
  • US Patent No. 4,713,295 provides a method of improving the wettability properties of glass beads for use road marking paints order to improve the bonding of the glass beads to the marking paint and thereby achieve prolong the light reflecting properties when the paint is exposed to weathering and wear, describes coated glass beads for use m polyme ⁇ seable road marking paints, especially as drop-on beads, but also as coated beads incorporated the paint.
  • the method comprises two step comprises a first step of coating the glass beads with a silane an organic solvent providing the surface of the glass beads with hydrophobic properties and a second step of coating the glass beads with a fluorocarbon compound an organic solvent providing the surface of the glass beads with both hydrophobic and oleophobic properties. This two-step method of coating glass beads is very inconvenient, expensive and require use of organic solvents .
  • the object of the present invention is to provide a road marking composition with incorporated beads, which beads have a good bonding strengths to the road marking composition.
  • a second object is to provide a road marking composition with incorporated beads, which road marking composition when applied on a road, has prolonged light reflecting properties when the marking is exposed to weathering and wear.
  • a third object is to provide a method of producing and applying a reflective road marking composition with partly embedded beads on a road, which method is simple and cheap and provides a marking on the road which has good and durable reflecting properties.
  • a fourth object is to provide a method of treating beads for use m a reflective road marking composition, which method is simple, fast and relatively cheap.
  • Yet a fifth object is to provide a method of treating beads for use m a reflective road marking composition, which method does not require the use of organic solvents
  • the reflective road marking composition according to the invention may basically be any type of polymer based road marking composition wherein beads, preferably beads coated with a cohesive coating material having a surface tension closer to the surface tension of the thermoplastic binder than the surface tension of the beads, is incorporated.
  • the reflective road marking composition according to the invention comprises a binder on polymer basis and incorporated beads, the beads being coated with a cohesive coating material having a surface tension closer to the surface tension of the polymeric matrix than the surface tension of the beads and wherein the binder before hardening or curing is a solution, a dispersion, two-component or thermoplastic.
  • the binder for use m the thermoplastic road marking according to the present invention may be any type of thermoplastic binder normally used m road marking compositions.
  • Useful thermoplastic binders are e.g. described US patent 4,301,050 and US patent 4,305,863.
  • the thermoplastic binder contains at least 50% by weight of binder of a hydrocarbon resm, a ketone res or a malemate resm.
  • the thermoplastic binder preferably also contains modifying polymers and other rheological modifiers such as mineral oil, antioxidant, lubricants/plasticizer and other components, which are added order to improve the rheological properties of the resm for the particular use.
  • rheological modifiers are generally known m the art.
  • the resm provides the thermoplastic binder with adhesive properties for adhesion to the filler and the surface on which the thermoplastic road marking is applied.
  • the modifying polymers are selected between SBS or SIS block co-polymers, amorphous polyolefmes
  • polypropylenes, polybutadienes ethylenevmylacetate (EVA) or mixture thereof, and they are preferably added m the amount of op to about 40 % by weight, more preferably from 30 to 40 c by weight of the binder.
  • the modifying polymers improve the cohesive strengths and the low-temperature properties of the binder.
  • Mineral oil preferably of the naphtenic or parafmic type may be added m an amount of up to about 15 % by weight, more preferably from 5 to 15 - by weight of the binder.
  • the mineral oil compatibilise the resm and the polymers.
  • Heat stable antioxidants may preferably be added to the mixture m small amounts m order to prevent yellowing of the thermoplastic mixture in the molten state.
  • Lubricants/plasticizers may be added m an amount of up to about 10 o by weight, preferably m an amount from 5 to 7 weight percent of the binder.
  • the lubricants/plasticizers reduce the application temperature and thereby reducing the preparation time.
  • Lubricants/plasticizers are also responsible for the ability of the road marking to wet the surface on which it is applied.
  • thermoplastic road marking composition consist of 18 to 25, preferably about 20 o by weight thermoplastic binder, and 75 to 82, preferably about 80 % by weight of light or transparent and durable filler.
  • the filler of the thermoplastic road marking according to the invention comprises at least about 13 °, preferably about 25 % by weight of coated beads.
  • the filler preferably comprise quartz, light granite, calcined flint and/or Danopal .
  • These filler components preferably have gra sizes from 0.074 to 2.0 mm, determined according to BS 3262 : 1976 m order to induce light reflective properties, skid resistance and resistance to wear.
  • the filler may preferably comprise one or more of calcium sulphate, talc, calcium metasilicate, quartz powder, Danopal powder, calcined flint powder, clay, mica, calcium silicate glass fibres, pigments dyes.
  • These filler components preferably have gram sizes less than 0.074 mm, determined according to BS 3262 : 1976 and may be added m order to improve the overall rheological properties of the thermoplastic road marking, and to prevent segregation of and to colour the road marking.
  • a preferred pigment dye for white thermoplastic road marking is titanium dioxide (rutile or anatas) , zinc oxide, magnesium oxide or mixture thereof, preferably m the amount of 4 to 10 weight percent of the filler, but the invention is not limited to this range.
  • thermoplastic road marking according to the invention may be provided with other colour than white, i.e. yellow, blue or red.
  • the type and content of the pigment dye is selected according to the specific purpose for the road marking. A person skilled m the art, will know how to select a pigment dye which is suitable for its purpose .
  • the beads used in the present invention may be of any suitably type including polymer based beads and glass beads.
  • the mam requirement is that the beads is stable to heat applied under the preparation, mixing and application of the road marking, preferably the beads should be stable when subjected to a heat above at least 200 °C for a period of about 20 minutes.
  • Beads prepared from polymers should preferably be able to withstand the pressure applied from normal traffic without breaking or crushing.
  • the most preferred type of beads is glass beads.
  • the beads should at least have an average size of 0.1 mm.
  • the size of the beads is measured according to the British standard BS 6088 A981.
  • the beads serves as reflecting agent m the road marking composition according to the invention.
  • Glass beads used as reflecting agent generally have a size m the range from 0.1 to 0.8 mm, but for special purposes larger beads may be used.
  • non-spherical glass particles m the bead fraction are not preferred, as their ability to reflect light is rather poor, but beads with a sphericallity larger than about 70 ° is preferred. More preferred is beads with a sphericallity larger than about 80 %. Spherical beads with a sphericallity larger than about 90 0 are particularly preferred. The sphericallity is measured by counting under microscope also according to BS 6088A981.
  • Glass having a refraction index of 1.44 to 2.02 is preferred. More preferred is glass having a refraction index of 1.45 to 1.65. Especially preferred is glass having a refraction index of 1.48 to 1.55. Glass with a refraction index larger than 1.60 is very often, dependent on the Abbe number of the glass, less durable than glass m the said range and is therefore more susceptible to traffic wear.
  • the beads preferably have a size between 0.1 and 3.0 mm measured as described above. More preferred the beads have a size between 0.1 and 2.0 mm. Even more preferably the beads have a size between 0.1 and 0.8 mm.
  • the beads m the thermoplastic binder according to the invention is coated with a cohesive coating material having a surface tension closer to the surface tension of the thermoplastic binder than the surface tension of the beads .
  • the coating material has a surface tension measured according to DIN 53364 Se ⁇ e B m a range of +/- 15 mN/m of the surface tension of the thermoplastic binder. More preferred the surface tension of the coating material is 2 to 10 mN/m larger than the surface tension of the thermoplastic binder.
  • the surface tension of the coating material may also be measured by visual means.
  • the visual means designated "the water droplet method" for easurend surface tension includes treating an object glass for microscopy with a dispersion comprismg the coating material.
  • the treated object glass is dried with a hair dryer (Braun type 4- 479) for 20 seconds and heated to 140 °C for 5 minutes on a heating surface and left to cool to room temperature. 4 separate droplets of destilled water are put on the coated glass surface and the average size of the droplets diameter is determined.
  • the surface tension, expressed m the size of the diameter of a water droplet, of the coating material is 1 mm larger than the surface tension of the thermoplastic binder measured according to the above visually method.
  • the coating material forms a proper uniform, cohesive layer on the surface of the beads which is significant reducing the surface tension of the beads.
  • the coating material forms a strong bonding to the resm of the thermoplastic binder.
  • the coating material on the beads comprises at least 80 % by weight of polyvmyl compound.
  • Preferred polyvmyl compounds is polyvmyls polyvmyl acetate, polyvmyl alcohol, polyvmyl amines, polyvmyl butyral, polyvmyl pyrrolidon, polyvmyl chloride and co-polymers thereof.
  • the coating material may comprise one or more types of polyvmyl compounds or other suitable polymers.
  • the coating material preferably comprises 80 % by weight or more of polyvmyl acetate, which may be able to crosslink e.g. by applying heat. After coating the polyvmyl acetate is preferably at least partly cross- linked.
  • coating materials which are commercial available, for example "Bostik 730 from Bostik DK, Sikabond 540 from Sika DK, Gludan G515 from Gludan DK or Cascol 3337 or Cascol 3339 from Casco DK", to name a few types.
  • This preferred coating material is very cohesive and resistant to heat, and it is not melting, stripped of the beads or soluted m the binder of the road marking while heating and preparing the thermoplastic road marking according to the invention.
  • the coating material may preferably comprises small amounts e.g. up to about 6.0 _, preferably between 2.0 and 5.0 by weight of emulsifying agents which makes the coating partial water resistant.
  • the emulsifying agent is very often polyvmyl alcohol, which also work as a cross- linking agent under the influence of a catalyst which may also be added to the coating material.
  • the reflective road marking composition according to the invention comprises beads coated with a coating composition comprising a suitable amount of emulsifying agents
  • the part of coated beads, which sticks out from the road marking are cleaned by moisture and traffic, leaving them very reflective, meanwhile the part of the coated beads partial embedded in and inside the road marking remains unaffected until the traffic wear makes the embedded beads rises on the markings surface.
  • thermoplastic binder and the coating on the coated beads according to the invention are bonded to each other by adhesive forces, and the strong bonding is responsible for a durable density of beads on the surface of the road marking. This causes a significant increase of the light reflective properties.
  • the coating material comprises one or more of following additives: Cationic or non-ionic surfactants up to 1 %, preferably 0.25 % by weight, an antioxidant as Irganox 1010 from Ciba-Geigy up to 0.5 " , preferably 0.2 _ by weight, a white pigment as titan dioxide (rutile type) up to 10 % preferably 5 % by weight, an phosphorescent
  • (afterglowing) pigment as Lumilux SN from Riedel-de Haen up to 30 % by weight, a luminescent pigment as Lumogen F from BASF up to 0.01 -s by weight and UV absorbers as Fe; ⁇ 3 up to 0.1 % by weight.
  • the coating is preferably applied in one single step and preferably it forms a proper layer e.g. a layer having an average thickness of at least 0.1 ⁇ , preferably at least
  • Coatings in the preferred thickness may preferably have incorporated pigments which improves the functional properties of the road marking further without reducing the bonding strengths between the coated beads and the thermoplastic road marking.
  • the coating on the beads is applied in one single step and includes one single layer. Thereby the cost of production is very reduced.
  • the coating is applied without being dissolved or diluted m an organic solvent.
  • the coating is relatively transparent, which gives the fresh-laid road marking a satisfactory reflection.
  • traffic and moisture during the course of time removes the coating from the parts of the beads which sticks out from the road marking, the reflection significantly increases.
  • the beads of the invention are incorporated into thermoplastic binders in order to maintain a satisfactory reflection during the course of time.
  • traffic wear and weathering removes the upper layer of the road marking including some of the beads, new beads are exposed to the surface.
  • the larger amount of beads added to the composition the larger becomes the reflection of the marking.
  • the uncoated beads of the prior art are mostly physically entrapped m the composition, the beads works as break initiators. Therefore the higher the amount of beads prior art compositions is, the faster is the erosion of the total marking.
  • the beads according to the invention are preferably uniformly distributed m the composition and is thereby physically entrapped m the polymer matrix when it cool down after applying the road marking. Therefore the reflection is uniform during the course of time.
  • a preferred amount of beads m the thermoplastic binder is between 10 % and 60 % by weight of the composition. More preferably between 20 and 40 % by weight.
  • the reflective road marking composition according to the invention may be prepared by coating the beads with the coating material and mixing the components of the reflective road marking composition using ordinary methods known m the art.
  • a preferred method preparing a reflective road marking composition according to the invention comprises the step of preparing a pre-mix for forming a thermoplastic road marking or a pre-fab for forming prefabricated symbols.
  • Pre-mix is a mixture of predetermined amounts of binder and filler which is held into meltable plasticbags at room temperature.
  • thermoplastic road marking is formed from the pre-mix by heating the pre-mix inclusive the plastic bag while stirring a chamber until the binder melts and the mixture becomes liquid and uniform. This resulting thermoplastic road marking is applied on the road by e.g. an extruder.
  • Pre-fab is thermoplastic road marking which has been applied on a non-tacky surface m lanes in a thickness of approx. 3 mm. After cooling down these lanes is cutted into different uses symbols as e.g. triangles and arrows.
  • the pre-fab is mounted on a dry road surface by placing the solid symbol on the road and heat it by e.g. a gas et until the symbol melts. After cooling down, the symbol is well bonded to the road surface.
  • a preferred method is as follows: Predetermined amount of binder including resm and a predetermined amount of filler including coated beads and for example light quartz are mixed optionally with a polymers, mineral oil, antioxidant, lubricant, plasticizer pigment dyes and other components. The mixture is held into meltable plastic bags.
  • the pre-mix including the plastic bag is placed m a suitable tank and is heated to obtain a homogeneous mixture. Normally the mixture will be heated under stirring until the temperature reaches approx . 200 °C, and after approx. 20 minutes stirring at about 200 °C the mixture is molten, homogeneous and ready for the application.
  • the coating on the beads is subjected to high temperature under the mixing procedure when beads and binder is mixed, the cohesive strength will often increase .
  • the hot mixture or reflective road marking composition is applied on a suitable substrate.
  • the reflective road marking composition including the pre-mix for forming the thermoplastic road marking or the pre-fab for forming the prefabricated symbols may be manufactured and applied as known m the art except the usual beads are replaced or partly replaced with the said coated beads according to the invention.
  • the invention also relates to a "drop on" method of producing and applying a reflective road marking composition on a road.
  • This method comprises the step of l) applying a pre-mix road marking composition comprising a thermoplastic binder and preferably beads on a road m a thickness of at least 0,3 mm, preferably at least 1 mm. 11) spreading beads coated with a cohesive coating material having a surface tension closer to the surface tension of the pre-mix composition than the surface tension of the beads.
  • the beads being spread onto the road marking material while the road material is m a molten state.
  • the pre-mix road composition is a reflective road marking composition according to the invention.
  • beads are sprinkled over the melt, whereby the beads are embedded 50 to 75 of their diameter into the melt m order to improve the retro reflective properties of the road marking. After cooling down, the road marking is ready for traffic or for the manufacturing of the prefabricated symbols.
  • the invention also relates to a method of treating beads for use m a reflective road marking composition.
  • This method comprises the step of 1) providing a partial water resistant, acidic dispersion of a coating mate: lal comprising one or more polyvmyl compound, the polyvmyl compound preferably being selected between polyvmyl acetate, polyvmyl alcohol, polyvmyl amines, polyvmyl butyral, polyvmyl pyrrolidon, mixtures and co-polymers thereof,
  • the coating may preferably be dried by removing the water m a hot air current or under reduced pressure until the beads no longer sticks to one another.
  • the coated beads may preferably be sieved through a vibratory screen and eventually formed agglomerates of coated beads may be passed through a soft double roller to loosen the agglomerates .
  • the coated beads may be stored under dry condition until use of the beads.
  • the method of treating beads according to the invention is simple (one coating is sufficient) and without any environmental hazardous consequences to coat the beads. Further more, the coated beads provides a strong bonding to a thermoplastic road marking when incorporated or embedded m a such thermoplastic road marking.
  • the treated beads according to the invention bears a coating which is reducing the surface tension difference between the normal road marking material and the bead.
  • the mixture was stirred further 1 minute to ensure a complete coating of all the glass beads. Still while stirring the water was removed from the mixture by a hair dryer (Braun type 4- 579). When the temperature of the mixture reaches approx. 80 °C, the polyvmylacetate sticked to the surface of the glass beads. The coated glass beads were then sieved to sort out eventually formed agglomerates of coated glass beads. The agglomerates were easily crushed by passing them through a soft double roller. After cooling down, the polyvmylacetate coated glass beads were transferred to suitable plastic bags and stored under dry condition.
  • the thickness in ⁇ m (T) of the coating is arithmetical determined setting the mass in kg of diluted dispersion named M, the specific surface (S) of the glass beads, Potters-Ballotini Class A, to 3.8 iA/kg, the water content of the undiluted dispersion to 50 % by weight, the density ( ⁇ ) of the coating to 1100 kg/m 3 and the degree of dilution, the polyvinyl acetate dispersion content of the diluted dispersion, named F by following formula :
  • object glasses with the dimension 76*26*1 mm were coated with two droplets of fresh maid 50 % water diluted polyvmyl acetate dispersion of the type Sikabond 540.
  • the dispersion was distributed on the object glass by help of a cotton bud.
  • the samples were dried with a hair dryer, Braun type 4-579, for approx. 20 seconds.
  • the coated object glasses were stored at room temperature until next day.
  • the coated object glasses were then heated on a heating surface for 5 minutes to respectively 60, 80, 100, 120 and 140 °C and afterwards cooled to room temperature.
  • One of the coated glasses was kept unheated.
  • object glasses for microscopy with the dimensions of 76 * 26 * 1 mm were coated with 2 droplets fresh maid 50 O water diluted polyvmyl acetate dispersion of the types Sikabond 540, Cascol 3337, Danalim B3 and Bostik 730. Two object glasses were coated with each dispersion. The dispersion was distributed on the object glass by help of a cotton bud. The tested dispersions were all of the type D3 according to DS/EN 204.
  • a masterbatch of the water diluted dispersion was prepared as follows: Predetermined amount of the polyvmyl acetate dispersion of the named types was while stirring at room temperature added the predetermined amount of postal water.
  • object glasses were coated with pigmented 50 % water diluted dispersion of the types Sikabond 540, Cascol 3337, Danalim B3 and Bostik 730.
  • the pigment was rutile titan dioxide, Bayertitan RKB3, was added to the water diluted dispersion m the amount of 2.5 and 5 s by weight.
  • rutile titan dioxide Bayertitan RKB3
  • All these coated surfaces were heated to 140 °C for 5 minutes and afterwards cooled to room temperature.
  • thermoplastic road marking of the type Hv 195 from Nordisk Vejmarkermg DK was while stirring, heated to 190 °C . After reaching the process temperature, the molten road marking material was stirred for further 20 minutes to ensure a homogenous blend. The molten road marking was poured on a non-sticky surface and cooled to room temperature .
  • Coated glass room temperature: 9 mm Coated glass (60 °C, 5 mm. ) : 9 mm Coated glass (80 °C, 5 mm.) : 9 mm Coated glass (100 °C, 5 mm. 8 mm Coated glass (120 °C, 5 mm. 7 mm Coated glass (140 °C, 5 mm. 7 mm Coated glass ( Pigmented, 140 °C , 5 mm : 7 mm Road marking Hv 195 , Nordisk Ve markermg 6 mm
  • titan dioxide m the tested concentrations does not affect the surface tension of the coating material and v) the surface tension of the coated object glass, which is heated to 140 °C, comprising whitening pigment or not, is much closer to the surface tension of the roadmarkmg than uncoated object glass.
  • an object glass was treated with a diluted polyvinyl acetate dispersion, Sikabond 540, as described in example 2.
  • the treated glass sheet was heated to 140 °C for 5 minutes and afterwards cooled to room temperature.
  • a thermoplastic roadmarking, Hv 195 from Nordisk Ve markering, DK was applied on a non-sticky surface and afterwards cooled to room temperature.
  • a drop of formamide, of which the surface tension is known under experimental conditions (58.2 mN/m) was placed onto the prepared surfaces, one at a time.
  • the surface tension of the prepared surfaces were evaluated by measuring the angle theta between the surface of the drop and the respective prepared surface using the equation of Young and Dupre quoted in * Physical Chemistry of Surfaces" (second edition) by Arthur W. Adamson (Department of Chemistry, University of Southern California, Los Angeles, Calif.), published by w Interscience Publishers”. The measurements were affected at 20 °C.
  • the surface tension measured by the above described method for the polyvinyl acetate treated surface and the thermoplastic roadmarking were 42.5 mN/m and 36.4, respectively.
  • Two glass discs with a diameter of 20 mm and a thickness of 3 mm were treated with a diluted polyvinyl acetate dispersion, Sikabond 540, as described in example 2.
  • the treated discs were heated to 140 °C on a heating surface for 5 minutes and afterwards cooled to room temperature.
  • a disc of thermoplastic roadmarking of the type Hv 195 from Nordisk Vejmarkermg with a diameter of approx. 2.2 mm and a thickness of approx. 4 mm was placed on the coating side of one of the treated glass discs. This system was heated to 190 °C on the heating platform. When the thermoplastic was molten, tne other treated glass disc was placed on the thermoplastic with the coating towards the thermoplastic.
  • this sandwich was removed from the heating surface and cooled to room temperature.
  • the excess of thermoplastic sticking out from the glass discs was removed by help of a hot knife.
  • the glass discs were supplied with two nuts using Araldit as binder between the steel and the glass.
  • the sandwich was placed m a tensiometer.
  • the tensile strength or cohesion at 25 °C of the system was measured to 6.2 MPa.
  • the speed of the tensiometer was 1 mm/s.
  • the fracture was obtained mside the thermoplastic.
  • the corresponding reference with untreated glass discs gave a cohesion of 0.7 MPa and the fracture was obtained between the glass and the thermoplastic.
  • thermoplastic road marking Other physical properties of the last-named modified thermoplastic road marking as whiteness, durability, resistance to wear, adhesion and especially the cohesion would be promoted compared to the corresponding unmodified thermoplastic road marking because the coating of the invention induces a better contact between the glass beads and the thermoplastic matrix.
  • thermoplastic roadmarking Premix of the type Hv 195 from Nordisk Vejmarkermg DK for forming thermoplastic roadmarking was heated while stirring to the process temperature at approx. 200 °C . After reaching the process temperature, the mixture was stirred further 20 minutes to ensure a homogeneous blend.
  • the molten thermoplastic was applied on an asphalt concrete as a plane traffic lane marking with dimension of 0.10 m width, approx. 10 m length of each sample and 3 mm m thickness.
  • polyvmylacetate coated glass beads were sprinkled over the molten thermoplastic m an amount of approx. 500 g/m 2 , so that the individual glass bead was partially embedded m the thermoplastic.
  • thermoplastic marking sprinkled with 500 g/m 2 untreated glass beads, Class A according to BS 6088 : 1981 from Potters-Ballotmi.
  • the measurements were carried out by using an apparatus under the trade mark LTL 800 Retrometer (geometry 1.24°/2.29°, equivalent to measurement distance of 30 m) to measuring the specific luminance R L m mCd/m 2 Lx from DELTA Lys & Optik, Hjortekaersvej 99, DK-2800 Lyngby.
  • the test results are indicated m the following Table III. This situ test was initiated 2 X May 1997. The average daily returns (ADT) on the tested samples was m 1997 approx. 2000. TABLE IV
  • the test was carried out as follows according to the proposal of the German Delegation of WG2 - TC226 regarding qualification tests for road marking materials on the turntable (RPA) .
  • thermoplastic Immediately after applying the thermoplastic on the bitumenous surface, polyvmylacetate coated glass beads type A were sprinkled over the molten thermoplastic m the amount of 350 g/m 2 , so that the individual glass bead was partially embedded m the thermoplastic. It was checked, that the amount of drop-on material did not differ more than 10 % from the preferred quantity. 3 test specimens were used for the turntable test. 1 test specimen was necessary to establish the drying time, and finally, 1 test specimen was set aside m case of a damaged one had to be replaced.
  • the test was conducted under the following conditions: The turntable was equipped with 4 new tyres customary m trade, like Michelm XDX, 195/70 VR 14. The load on wheels was 3000 N and a tyre air pressure on 2.2 bar. The support angle was 0 ° and the steering (oblique) angle was ⁇ 1 °. The daily driving cycle was 3 hours of specimens at disk speed of approx. 10 km/h, followed by roll-over of the specimens at a speed of 60 km/h, until 0.2 million roll-overs were carried out, whereby the turning direction was changed every hour. The test temperature was 5 to 10 °C .
  • test value arithmetical mean value

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Civil Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Architecture (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Road Signs Or Road Markings (AREA)
  • Road Repair (AREA)

Abstract

L'invention concerne un marquage réflectorisé et son procédé de production consistant à incorporer des billes dans un liant sur une base polymère et à appliquer un matière de revêtement collante présentant une tension de surface plus proche de celle de la matrice polymérique que de celle des billes.
PCT/DK2000/000684 1999-12-10 2000-12-08 Marquage reflectorise et procede de production et d'application d'une composition renfermant ledit marquage reflectorise WO2001042349A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU18524/01A AU1852401A (en) 1999-12-10 2000-12-08 A reflective road marking and a method of producing and applying a reflective road marking composition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DKPA199901770 1999-12-10
DKPA199901770 1999-12-10

Publications (1)

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WO2001042349A1 true WO2001042349A1 (fr) 2001-06-14

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013043178A1 (fr) 2011-09-22 2013-03-28 Flint Trading, Inc. Composites thermoplastiques préformés à rétro-réflexion élevée antidérapants pour application à des pistes d'atterrissage
KR101255239B1 (ko) 2012-06-28 2013-04-16 주식회사이화정공 도로의 차선 표시용 융착식 도료 조성물
US20140011911A1 (en) * 2010-11-30 2014-01-09 3M Innovative Properties Company Pavement marking composition
WO2016051354A1 (fr) 2014-09-30 2016-04-07 Tubitak Améliorations des propriétés de surface des billes de verre qui sont utilisées en tant que matériau rétroréfléchissant dans les marquages de chaussée, par revêtement à l'aide d'argile naturelle
EP3056475A1 (fr) * 2015-02-11 2016-08-17 LKF Materials A/S Composition, marquage et kit de pièces permettant de former un marquage, tel qu'un marquage routier
WO2018093293A1 (fr) 2016-11-16 2018-05-24 Александр Вячеславович ФИЛИППОВ Signalisation routière horizontale
US11332261B2 (en) 2011-09-22 2022-05-17 Robert W Greer Anti-skid high retroreflectivity preformed thermoplastic composites for runway applications

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2879171A (en) * 1955-11-18 1959-03-24 W P Fuller & Co Paint for highway marking and the like
US3253146A (en) * 1962-08-16 1966-05-24 Prismo Safety Corp Fluorescent marker pigment for roadways
US4301050A (en) * 1979-06-07 1981-11-17 Atom Chemical Paint Co., Ltd. Road marking composition
US4305863A (en) * 1979-06-15 1981-12-15 Dainippon Ink & Chemicals, Inc. Glass bead-filled resin composition
EP0056771A1 (fr) * 1981-01-19 1982-07-28 Potters Ballotini S.A. Procédé pour la réalisation de marquages routiers rétroréfléchissants et moyens pour leur mise en oeuvre
EP0124946A2 (fr) * 1983-05-09 1984-11-14 Moses Bollag Procédé pour réaliser ou calquer un marquage horizontal des routes et marquage horizontal de routes ainsi obtenu
US4609587A (en) * 1984-11-30 1986-09-02 Potters Industries, Inc. Retroreflective materials and use
US5128203A (en) * 1988-02-19 1992-07-07 Glaverbel Marking comprising glass beads in a matrix
WO1997023423A1 (fr) * 1995-12-22 1997-07-03 Norsk Hydro Asa Perles spheriques pour applications relatives a la reflexion de la lumiere, et procede de preparation
US5811480A (en) * 1995-06-28 1998-09-22 Bayer Aktiengesellschaft Size composition, sized glass fibers and use thereof
US5928716A (en) * 1996-04-12 1999-07-27 Stimsonite Corporation Method for marking a roadway surface

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2879171A (en) * 1955-11-18 1959-03-24 W P Fuller & Co Paint for highway marking and the like
US3253146A (en) * 1962-08-16 1966-05-24 Prismo Safety Corp Fluorescent marker pigment for roadways
US4301050A (en) * 1979-06-07 1981-11-17 Atom Chemical Paint Co., Ltd. Road marking composition
US4305863A (en) * 1979-06-15 1981-12-15 Dainippon Ink & Chemicals, Inc. Glass bead-filled resin composition
EP0056771A1 (fr) * 1981-01-19 1982-07-28 Potters Ballotini S.A. Procédé pour la réalisation de marquages routiers rétroréfléchissants et moyens pour leur mise en oeuvre
EP0124946A2 (fr) * 1983-05-09 1984-11-14 Moses Bollag Procédé pour réaliser ou calquer un marquage horizontal des routes et marquage horizontal de routes ainsi obtenu
US4609587A (en) * 1984-11-30 1986-09-02 Potters Industries, Inc. Retroreflective materials and use
US5128203A (en) * 1988-02-19 1992-07-07 Glaverbel Marking comprising glass beads in a matrix
US5811480A (en) * 1995-06-28 1998-09-22 Bayer Aktiengesellschaft Size composition, sized glass fibers and use thereof
WO1997023423A1 (fr) * 1995-12-22 1997-07-03 Norsk Hydro Asa Perles spheriques pour applications relatives a la reflexion de la lumiere, et procede de preparation
US5928716A (en) * 1996-04-12 1999-07-27 Stimsonite Corporation Method for marking a roadway surface

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140011911A1 (en) * 2010-11-30 2014-01-09 3M Innovative Properties Company Pavement marking composition
US10753053B2 (en) * 2010-11-30 2020-08-25 3M Innovative Properties Company Pavement marking composition
WO2013043178A1 (fr) 2011-09-22 2013-03-28 Flint Trading, Inc. Composites thermoplastiques préformés à rétro-réflexion élevée antidérapants pour application à des pistes d'atterrissage
EP2758601A4 (fr) * 2011-09-22 2015-08-05 Flint Trading Inc Composites thermoplastiques préformés à rétro-réflexion élevée antidérapants pour application à des pistes d'atterrissage
US11332261B2 (en) 2011-09-22 2022-05-17 Robert W Greer Anti-skid high retroreflectivity preformed thermoplastic composites for runway applications
KR101255239B1 (ko) 2012-06-28 2013-04-16 주식회사이화정공 도로의 차선 표시용 융착식 도료 조성물
WO2016051354A1 (fr) 2014-09-30 2016-04-07 Tubitak Améliorations des propriétés de surface des billes de verre qui sont utilisées en tant que matériau rétroréfléchissant dans les marquages de chaussée, par revêtement à l'aide d'argile naturelle
RU2661511C1 (ru) * 2014-09-30 2018-07-17 Тюбитак Усовершенствование поверхностных свойств стеклошариков, используемых в качестве световозвращающего материала для дорожной разметки, путем нанесения покрытия из природной глины
EP3056475A1 (fr) * 2015-02-11 2016-08-17 LKF Materials A/S Composition, marquage et kit de pièces permettant de former un marquage, tel qu'un marquage routier
WO2018093293A1 (fr) 2016-11-16 2018-05-24 Александр Вячеславович ФИЛИППОВ Signalisation routière horizontale

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