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WO1993017188A1 - Bande de marquage routier - Google Patents

Bande de marquage routier Download PDF

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Publication number
WO1993017188A1
WO1993017188A1 PCT/US1993/000062 US9300062W WO9317188A1 WO 1993017188 A1 WO1993017188 A1 WO 1993017188A1 US 9300062 W US9300062 W US 9300062W WO 9317188 A1 WO9317188 A1 WO 9317188A1
Authority
WO
WIPO (PCT)
Prior art keywords
pigment
tape
yellow
top layer
pigment yellow
Prior art date
Application number
PCT/US1993/000062
Other languages
English (en)
Inventor
Eric E. Rice
Elmar P. J. Klameth
Robert L. Keech
Sergio Passarino
Original Assignee
Minnesota Mining And Manufacturing Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Minnesota Mining And Manufacturing Company filed Critical Minnesota Mining And Manufacturing Company
Publication of WO1993017188A1 publication Critical patent/WO1993017188A1/fr

Links

Classifications

    • 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
    • E01F9/576—Traffic lines
    • E01F9/578—Traffic lines consisting of preformed elements, e.g. tapes, block-type elements specially designed or arranged to make up a traffic line
    • 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

Definitions

  • the present invention relates to yellow and orange pavement marking tapes which are substantially free of pigments containing lead, cadmium, or chromium.
  • Colored pavement marking tapes are well known, being used in both long term, “permanent”, and short term, “temporary” applications. Ease of application and customizable adhesive performance have led to the wide acceptance of such tapes for providing lane markings and other graphic information on road surfaces instead of such alternatives as paints.
  • Pavement marking tapes are typically made in desired colors by incorporation of pigments in the top layers thereof. Many colors, including especially yellow and orange, are achieved by incorporation of pigments containing lead, cadmium, and/or chromium. Such pigments can impart vivid, consistent, durable color, thereby enhancing the safety of the marking tapes in which they are used. In recent years, however, compounds including pigments containing lead, cadmium, and/or chromium have been the focus of increased concern over environmental and health risks.
  • a pavement marking tape of the invention comprises a top layer and an optional adhesive layer wherein the top layer is yellow or orange, comprises one or more pigments in a polymeric matrix, and the pigments are substantially free of lead, cadmium, and chromium.
  • the top layer may comprise titanium dioxide, retroreflective elements, and/or anti-skid particles.
  • the tape further comprises a conformance layer disposed between the top layer and the adhesive layer.
  • the tape may further comprise a reinforcing web.
  • Figure 1 is cross-sectional view of an illustrative embodiment of pavement marking tape of the invention.
  • pavement marking tape 10 comprises top layer 12 and optional adhesive layer 18 on the bottom side thereof.
  • Top layer 12 contains optional retroreflective elements 14 and optional anti-skid particles 16.
  • Tape 10 also comprises optional conformance layer 20 and optional reinforcing web 22.
  • Top layer 12 is a polymeric matrix, e.g., of polyvinyl chloride (“PVC") , polyvinyl acetate (“PVA”) , PVC/PVA blends, ethylene/acrylic acid (“EAA”) , ethylene/methacrylic acid (“EMMA”), and EAA/EMAA blends, polyurethane, epoxy resins, melamine resins, or polyamides, that preferably exhibits tough, durable characteristics.
  • Top layer 12 contains colorants to impart desired color thereto and, if desired, retroreflective elements 14 and/or anti-skid particles 16. Polyurethane-based top layers are typically preferred because such top layers are generally more durable than polyvinyl top layers.
  • Polyurethane-based top layers have been used in pavement marking tapes for some time in view of their typically high tensile strength, tear strength, and abrasion resistance.
  • aliphatic polyurethane resins exhibit superior abrasion resistance and color stability.
  • Phenolic modified resins and aromatic urethanes that tend to discolor so as to turn brown may be less suitable than those that tend to turn yellow.
  • Top layer 12 contains an organic pigment or combination of two or more such pigments formulated to impart a desirable yellow or orange color to the pavement marking tape. By selection of particular pigments and adjusting the relative amounts which used, pavement markings may be made in desired colors, e.g., to satisfy applicable government specifications.
  • top layer 12 is substantially free of lead-, cadmium-, and chromium-containing pigments. Preferably, top layer 12 is substantially free of lead, cadmium, and chromium.
  • Illustrative examples of pigments which are suitable colorants for use in the invention include such yellow pigments such as:
  • C.I. Pigment Yellow 55 e.g., IRGALITE Brand Yellow BAF from Ciba-Geigy, a diarylide-p-toluidide
  • C.I. Pigment Yellow 61 e.g., SC from Ciba-Geigy
  • C.I. Pigment Yellow 65 e.g., DA AMAR Brand Yellow YT-820-D from Cookson Pigments Company, a monoazo
  • C.I. Pigment Yellow 74 e.g., DALAMAR Brand Yellow YT-808-D from Cookson, a monoazo
  • C.I. Pigment Yellow 83 (e.g., DIAZO HR Brand from Hoechst)
  • C.I. Pigment Yellow 110 e.g., IRGAZINE Brand Yellow 3RLTN from Ciba-Geigy, a tetrachloroisoindolinone
  • IRGAZINE Brand Yellow 3RLTN from Ciba-Geigy, a tetrachloroisoindolinone
  • C.I. Pigment Yellow 139 (e.g., Y5700 from Mobay)
  • C.I. Pigment Yellow 184 (e.g., 10652 IRGACOLORTM
  • DALAMARTM Yellow YT719 a monoazo from Cookson; such orange pigments as:
  • C.I. Pigment Orange 5 e.g., IRGALITE Brand Red 2GW from Ciba-Geigy, a dinitraniline
  • C.I. Pigment Orange 13 e.g., IRGALITE Brand Orange P from Ciba-Geigy, a diasopyrazolone
  • C.I. Pigment Orange 34 e.g., IRGALITE Brand
  • Orange F2G from Ciba-Geigy, a diasopyrazolone
  • C.I. Orange 65 e.g., IRGAZINTM Orange 5R, a bis-azomethine nickel complex from Ciba-Geigy
  • red and violet pigments which are useful in forming orange top coats
  • C.I. Pigment Red 3 e.g., IRGALITETM Scarlet RNP and IRGALITETM Red PDS4, both toluidene red from
  • C.I. Pigment Red 4 e.g., IRGALITETM Red PRR a chlorinated para red from Ciba-Geigy
  • C.I. Pigment Red 48:3 (e.g., IRGALITETM Red 2YB from Ciba-Geigy) ,
  • C.I. Pigment Red 112 e.g., IRGALITETM Red 3RS, a BON arylamide from Ciba-Geigy
  • IRGALITETM Red 3RS a BON arylamide from Ciba-Geigy
  • C.I. Pigment Red 144 e.g., CROMOPHTALTM Red BRN, an azocondensate from Ciba-Geigy
  • C.I. Pigment Red 166 e.g., CROMOPHTAL Scarlet RN from Ciba-Geigy, a azocondensate
  • Top layer 12 of a pavement marking tape of the invention typically comprise between about 1.0 and about 20 weight percent of such organic pigment(s) .
  • two or more pigments may be used in blends, some available commercially, to achieve desired top coat coloration.
  • HEUCOSINTM G7633 and G7635 blends of C.I. Pigment Yellow 53, 138, and 191, from Cookson have been found to impart desirable yellow color to urethane-based top layers.
  • a blend containing C.I. Pigment Yellow 53 (HEUCOTECHTM HD156) , C.I. Pigment Yellow 61 ( SC) , and C.I. Pigment Yellow 139 (Y5700) in a 50.0:38.1:11.9 weight ratio was found to provide excellent nighttime yellow color in vinyl-based top layers having colorless microspheres.
  • the pigment(s) and polymer are preferably selected to be compatible with one another. They are preferably substantially non-reactive with one another. For instance, an acidic polymer and basic pigment may produce a composition too highly viscous to be easily worked. Furthermore, reaction between pigment(s) and polymer may result in undesirable change in resultant color. For example, C.I. Pigment Yellow 83 has been found to be substantially non-reactive with urethane polymers and is thus preferred for use in pavement markings made of such polymeric matrices.
  • top layer 12 typically contains titanium dioxide pigment which increases the CAP Y of the top layer as well as being useful in blending with yellow or orange pigments to achieve desired color. Also, in embodiments where, as discussed below.
  • top layer 12 typically comprises up to about 30 weight percent of titanium dioxide, with between about 5 and about 30 weight percent being preferred.
  • Rutile titanium dioxide, urethane grade, is typically a suitable grade.
  • Top layer 12 is typically formed by coating a liquid composition of the various components and drying and/or curing the composition to yield top layer 12. Excessive amounts of titanium dioxide and pigment have been observed to undesirably increase the viscosity of the coating composition from which top layer 12 is formed.
  • the pigment is preferably dispersed in the polyol prior to mixing with the isocyanate component. This procedure is useful to reduce the likelihood of undesirable interaction between the pigment and the isocyanate or catalyst components which occurs in some instances, interfering with the reaction kinetics and impairing the color appearance of the resultant top layer.
  • Top layer 12 typically contains retroreflective elements 14 to impart improved nighttime visibility to the marking tape.
  • retroreflective elements 14 are typically scattered throughout top layer 12 and may be partially embedded in top layer 12, protruding from the top surface thereof, and some may be totally embedded therein, becoming exposed as the top layer is progressively eroded away in use.
  • Several suitable methods and formats of distribution of retroreflective elements are disclosed in U.S. Patent Nos. 4,279,534, 4,322,177, 4,369,001, 4,607,978, 4,652,172, and 4,681,480 (all Eigenmann) .
  • top layer 12 may comprise a mixture of microspheres selected from both ranges.
  • other suitable retroreflective elements include so-called cube-corner reflectors, etc.
  • pavement markings of the invention exhibit good daytime color, they may tend to appear somewhat white or washed out at night, particularly at long distances.- corresponding to low observation angles. Accordingly, for some applications it is desirable to incorporate suitably colored microspheres in the marking.
  • U.S. Patent No. 3,294,559 discloses yellow glass beads or microspheres which may be used in marking tapes of the invention.
  • Other suitable colored microspheres will be apparent to those skilled in the art.
  • colorless microspheres provide brighter retroreflection than do colored microspheres.
  • the aforementioned blend of C.I. Pigment Yellow 53, 61, and 139 has been observed to be particular effective at imparting yellow daytime and nighttime color to pavement markings. It is believed that this blend of pigments contains a particularly suited combination of particle sizes to provide good light scattering properties so as to provide effective retroreflection and color.
  • Top layer 12 typically contains anti-skid particles 16 to improve the tire traction on the marking material.
  • Anti-skid particles 16 are typically irregular or angular particles of sand, quartz, corundum, beryllium, silicon carbide, or other abrasive materials.
  • Preferably anti-skid particles 16 exhibit a hardness of at least about 6° on the Mohs Hardness Scale, more preferably at least about 7°.
  • average dimension of of each anti-skid particle is between about 0.1 and about 1.0 millimeters, preferably between about 0.5 and about 0.8 millimeters.
  • the number of anti-skid particles in a given volume of top layer 12 is limited such that not more than 20 percent of the top surface of top layer 12 is covered by such particles, preferably between about 5 and 10 percent. It may be desired to treat retroreflective elements 14 and anti-skid particles 16 with adhesion promoting agents or to incorporate such agents into top layer 12 to improve the bond with the polymeric matrix of top layer 12. Such agents typically have an inorganic moiety which associates with the retroreflective elements or anti-skid particles and an organic moiety which associates or reacts with the polymeric matrix.
  • pavement marking tape 10 will also comprise conformance layer 20 disposed between top layer 12 and adhesive layer 18.
  • a typical conformance layer is made of highly filled acrylonitrile butadiene rubber or nitrile, properly filled (e.g., with mineral fillers) to provide desired physical properties such as suitable tensile strength, elongation, and conformability.
  • suitable materials include chloroprene (e.g.,. NEOPRENETM) • and chlorosulphonated polyethylene (e.g., HYPALONTM) which are.well known for superior weathering and oil resistance.
  • Conformance layer 20 may comprise up to 15 weight percent, typically about 1 to 12 weight percent, of organic or inorganic pigments (e.g., iron oxide, bismuth vanadate, titanium yellow, etc.) to provide better color matching with the top layer.
  • Optional adhesive layer 18, which adheres tape 10 to the pavement surface (not shown) is selected to provide desired adhesion properties.
  • tape 10 may be intended for long term applications and should thus provide high durability.
  • adhesive 18 should provide suitable release characteristics.
  • the adhesive is not applied to the marking tape until the time the tape is being applied to the pavement.
  • colored top layers of the invention may be coated on the back or under side with contact cement just before application to the pavement, upon which contact cement is also typically preapplied. If desired, preformed strips of adhesive may be used to secure adhesive-less tapes of the invention.
  • pavement marking tape 10 further comprises optional reinforcing web 22.
  • a web is incorporated into the tape construction to increase the tensile strength and tear resistance of the tape.
  • Such webs are especially preferred in instances where the tape is intended to be removed after use for a desired term as they facilitate removal of the tape which might otherwise tend to tear or shred upon application of a peel force.
  • reinforcing web 12 is typically disposed at the interface of the adhesive layer and adjacent elements of tape 10 or within the adhesive layer itself.
  • Reinforcing web 22 should be made of a tough, tear resistant material with high tensile strength, e.g., polyester.
  • Web 22 is typically in the form of an open weave or perforated sheet, preferably of multifilament construction, or a fibrous, non-woven web, such that bulk of the layer(s) it is in, e.g., adhesive layer 18 and/or conformance layer 20, will flow through web 22, forming a strong bond thereto so as to reduce the potential for delamination failure. It may be desirable to treat reinforcing web 22 with adhesion promoting agents, or incorporate such agents in the layers to improve the bond therebetween.
  • U.S. Patent No. Re. 31,669 (Eigenmann), Great Britain Patent No. 2,085,056 (Eigenmann), and European Patent Application Publications Nos.
  • pavement marking tapes of the invention will comprise a top layer between about 50 and about 300 microns, typically about 100 microns thick, a conformance layer between about 300 and 1200 microns, typically about 700 microns thick, and an adhesive layer between about 50 and about 300, typically about 100 microns thick.
  • a pavement marking was made with a yellow top layer comprising:
  • the conformance layer was 700 microns in thickness and comprised:
  • Chloroparafin (CLOPARINTM 70, 70% Cl from Caffare) 2.0 Chloroparafin (CLOPARINTM 68, 68% Cl from Caffare) 6.2 Titanium dioxide (Anatase titanium dioxide from Bayer)
  • Amorphous silica (VULCASILTM S from Bayer) 20.0 Calcium silicate (VULCASILTM G from Bayer) 0.4 Antioxidant (ANEX T, a phenyl antioxidant from 30.0 Glass beads (1.5 refractive index, 100 to 200 microns in diameter) 1.0 Yellow pigment 0.03 Orange pigment 0.4 Stearic acid
  • a pavement marking was made with a yellow top layer comprising:
  • the conformance layer was a 700 micron thick layer like that used in Example 1.
  • Example 3 A pavement marking was made with a top layer comprising: Amount Component
  • the yellow pigment which was predispersed in the polyols, reacted with the catalyst reducing the speed of cure. Complete curing was not achieved. It is believed that a continuous production process, with in-line addition of catalyst such as would be commonly be used in commercial production facility, would overcome this problem. Also, the top layer appeared to be slightly transparent and a somewhat reduced retroreflectivity (i.e., about 300 millicandela/lux/meter 2 ) was noted.
  • a pavement marking was made with an orange top layer comprising: Amount Component
  • the conformance layer was 700 microns in thickness, with similar composition as that in Example 1, except 1.0 parts by weight of C.I. Pigment Orange 34 was the only pigment used.
  • Example 5
  • a pavement marking was made with a yellow top layer comprising:
  • Amount Component 2.2 Yellow pigment (Y5700 from Mobay, C.I.
  • Pigment Yellow 139 7.1 Yellow pigment (WSC from Ciba-Geigy,

Landscapes

  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Laminated Bodies (AREA)
  • Road Signs Or Road Markings (AREA)

Abstract

Bande de marquage routier de couleur jaune ou orange et comportant une couche supérieure et, éventuellement, une couche de conformation, une nervure de renforcement et une couche adhésive, la couche de conformation étant disposée entre la couche supérieure et la couche adhésive, et la bande étant pratiquement dépourvue de plomb, de cadmium et de chrome.
PCT/US1993/000062 1992-02-19 1993-01-07 Bande de marquage routier WO1993017188A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US83852192A 1992-02-19 1992-02-19
US07/838,521 1992-02-19

Publications (1)

Publication Number Publication Date
WO1993017188A1 true WO1993017188A1 (fr) 1993-09-02

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Family Applications (1)

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PCT/US1993/000062 WO1993017188A1 (fr) 1992-02-19 1993-01-07 Bande de marquage routier

Country Status (2)

Country Link
AU (1) AU3433993A (fr)
WO (1) WO1993017188A1 (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995008426A1 (fr) * 1993-09-20 1995-03-30 Minnesota Mining And Manufacturing Company Marquage de la chaussee et feuille de base
US5645938A (en) * 1995-09-15 1997-07-08 Minnesota Mining And Manufacturing Company Retroreflective article containing a polyester polyurethane binder layer
WO1998050635A1 (fr) * 1997-05-08 1998-11-12 Minnesota Mining And Manufacturing Company Marquages discrets pour chaussee et leur procede de fabrication
WO1999004096A1 (fr) * 1997-07-16 1999-01-28 Minnesota Mining And Manufacturing Company Articles de signalisation horizontale noirs retroreflechissants
WO2003054071A3 (fr) * 2001-12-20 2003-10-23 Ciba Sc Holding Ag Couche de surface de protection thermique
EP1270820A3 (fr) * 2001-06-29 2003-11-26 Cleanosol Ab Marquage de surfaces de routes
WO2011066355A2 (fr) 2009-11-25 2011-06-03 Flint Trading Inc. Marquage de chaussée thermoplastique préformée et procédé utilisant un agrégat de taille importante pour une résistance au glissement perfectionnée à long terme et une formation d'ornières réduite
CN112240008A (zh) * 2019-07-19 2021-01-19 吉林建筑大学 一种多功能道路标线带及其制备方法和施工方法
US11110695B2 (en) 2012-05-30 2021-09-07 3M Innovative Properties Company Marking tape, method of applying and method of manufacturing the marking tape
EP4223844A4 (fr) * 2020-09-29 2024-05-01 FUJIFILM Corporation Encre jaune pour jet d'encre, procédé d'impression d'image et matière d'impression d'image

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3337483A (en) * 1963-10-23 1967-08-22 Cataphote Corp Traffic marking compositions containing thermoplastic rosinless resinous binder
USRE31669E (en) * 1976-04-15 1984-09-11 Anti-skid, wear- and stress-resisting road marking tape material
EP0304405A1 (fr) * 1987-06-25 1989-02-22 SNOLINE S.p.A. Bande préfabriquée pour signalisation routière temporaire

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3337483A (en) * 1963-10-23 1967-08-22 Cataphote Corp Traffic marking compositions containing thermoplastic rosinless resinous binder
USRE31669E (en) * 1976-04-15 1984-09-11 Anti-skid, wear- and stress-resisting road marking tape material
EP0304405A1 (fr) * 1987-06-25 1989-02-22 SNOLINE S.p.A. Bande préfabriquée pour signalisation routière temporaire

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 0580, Derwent Publications Ltd., London, GB; AN 80-08419C *

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995008426A1 (fr) * 1993-09-20 1995-03-30 Minnesota Mining And Manufacturing Company Marquage de la chaussee et feuille de base
US5645938A (en) * 1995-09-15 1997-07-08 Minnesota Mining And Manufacturing Company Retroreflective article containing a polyester polyurethane binder layer
WO1998050635A1 (fr) * 1997-05-08 1998-11-12 Minnesota Mining And Manufacturing Company Marquages discrets pour chaussee et leur procede de fabrication
WO1999004096A1 (fr) * 1997-07-16 1999-01-28 Minnesota Mining And Manufacturing Company Articles de signalisation horizontale noirs retroreflechissants
US5928761A (en) * 1997-07-16 1999-07-27 Minnesota Mining And Manufacturing Company Retroreflective black pavement marking articles
EP1270820A3 (fr) * 2001-06-29 2003-11-26 Cleanosol Ab Marquage de surfaces de routes
WO2003054071A3 (fr) * 2001-12-20 2003-10-23 Ciba Sc Holding Ag Couche de surface de protection thermique
WO2011066355A2 (fr) 2009-11-25 2011-06-03 Flint Trading Inc. Marquage de chaussée thermoplastique préformée et procédé utilisant un agrégat de taille importante pour une résistance au glissement perfectionnée à long terme et une formation d'ornières réduite
EP2504492A4 (fr) * 2009-11-25 2014-07-09 Flint Trading Inc Marquage de chaussée thermoplastique préformée et procédé utilisant un agrégat de taille importante pour une résistance au glissement perfectionnée à long terme et une formation d'ornières réduite
US11110695B2 (en) 2012-05-30 2021-09-07 3M Innovative Properties Company Marking tape, method of applying and method of manufacturing the marking tape
CN112240008A (zh) * 2019-07-19 2021-01-19 吉林建筑大学 一种多功能道路标线带及其制备方法和施工方法
CN112240008B (zh) * 2019-07-19 2021-11-23 吉林建筑大学 一种多功能道路标线带及其制备方法和施工方法
EP4223844A4 (fr) * 2020-09-29 2024-05-01 FUJIFILM Corporation Encre jaune pour jet d'encre, procédé d'impression d'image et matière d'impression d'image

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Publication number Publication date
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