Thermoplastic marking compositions

Details Thermoplastic marking compositions Thermoplastic marking compositions

2000-06-12

2003-04-22

Wu, David W. (Department: 1713)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

At least one aryl ring which is part of a fused or bridged...

C524S425000, C524S270000, C524S494000, C524S497000, C524S413000, C528S490000, C523S172000

Reexamination Certificate

active

06552110

ABSTRACT:

The subject invention pertains to thermoplastic marking compositions. In particular, the subject invention pertains to thermoplastic marking compositions comprising a binder, which in turn comprise at least one homogeneous polymer.
Thermoplastic marking formulations which comprise inorganic fillers bound by a polymeric binder are known in the art.
PCT Publication WO9623845 discloses a thermoplastic adhesive composition suitable for use as a road-marking, which comprises a silane-modified petroleum resin containing 0.05 to 1.0 weight percent silane functionality, extender oil and/or plasticizer, pigment and filler. The adhesive composition is said to provide improved adhesion of glass beads to road surfaces for improved endurance.
Dutch Patent Publication NL7907550 discloses reflective road markings which are laid by applying a standard hot melt road marking composition to the road surface, then applying a reflector containing a thermoplastic to the still hot marking composition. The reflector material preferably contains glass pearls, prismatic or lens reflectors, and is based on essentially the same materials as the road marking composition.
British Patent Publication GB2059430 discloses a hot melt thermoplastic road marking composition comprising 7 to 38 weight percent synthetic resin, 1 to 10 weight percent plasticizer, 0 to 10 weight percent elastomer, 1 to 15 weight percent pigments, 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 reports that the composition can easily be applied to roads by a screed or extrusion type applicator at 180 to 200° C. and has high durability, even when applied only 1.5 mm thick. The publication further provides that glass beads at 280 to 500 grams/square meter can be applied to the molten surface.
Japanese Patent Publication JP52058737 discloses compositions which are prepared by mixing (a) 2 to 20 parts by weight ethylene-vinyl acetate copolymer or atactic polypropylene; (b) 60 to 96 parts by weight carboxy-modified hydrocarbon resin (with an acid value of 0.1 to 25) or ester-modified hydrocarbon resin obtained by reacting the carboxy-modified resin with alcohol; (c) 2 to 20 parts by weight low molecular weight polyethylene, which is optionally carboxy-modified; and (d) 200 to 700 parts by weight mineral fillers or pigment, optionally with plasticizers or glass beads. The disclosed coatings are said to have improved flexibility, and strength, and are obtained from compositions improved fluidity.
British Patent Publication GB1324553 discloses a road marking composition of a hot-applied, thermoplastic superimposed type comprising: (a) aggregate,(for example, crushed marble, dolomite, calcite spar or silica sand), (b) pigment and extender, and (c) a binder consisting of (i) 55 to 90 weight percent of polymeric unsaturated resin, (ii) 10 to 45 weight percent of a hydrocarbon oil plasticizer, which has a flash point (open) of greater than or equal to 400 degrees F. (204° C.) and a viscosity of 6 to 10 poise at 25 degrees C., and (iii) 0 to 10 weight percent of an aliphatic monocarboxylic acid having at least fourteen carbons, such as stearic acid or oleic acid. The publication discloses the inclusion of Ballotini (glass beads) for making reflective line markings. The publication discloses the use of TiO
2
as the pigment with whiting as the extender, or a heat stable yellow pigment, instead of TiO
2
.
European Patent Publication EP 115,434 describes 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 tackifier. The copolymer has a molecular weight of 1000 to 40,000. The alpha-olefin is present in an amount of from 2 to 40 percent by weight. The copolymers of the examples are prepared using a soluble vanadium catalyst. The publication discloses the use of the adhesives in road marking applications.
Those in industry would find great advantage in a thermoplastic marking formulation which exhibits a consistent and low viscosity (as evidenced by a melt viscosity at 350° F. (177° C.) of no more than 5000 centipoise), which exhibits reduced fuming and smoking, and which exhibits good low temperature flexibility (as evidenced by an embrittlement temperature of −10 to −20° C.).
Accordingly, the subject invention provides a thermoplastic marking composition comprising:
(a) from 10 to 80 weight percent of a binder, which in turn comprises:
(i) from 1 to 99 weight percent of at least one homogeneous polymer;
(ii) from 5 to 70 weight percent of at least one tackifier;
(iii) from 0 to 10 weight percent of a polyethylene which has pendant acid functionality moieties or of a non-functionalized wax; and
(iv) from 0 to 20 weight percent of a plasticizer; and
(b) from 20 to 90 weight percent of an inorganic filler.
The subject formulations are usefully applied via spray, screed, and extrusion techniques. The subject formulations exhibit improved low temperature flexibility and low temperature adhesion and abrasion, and exhibit improved smoke and low odor properties at high temperatures. The subject formulations exhibit a broad potential range of application temperatures, particularly at temperatures of from 150° C. to 250° C., which makes them suitable for application by different means. For instance, the ability of the compositions to be applied at lower application temperatures, that is, temperatures of 150 to 170° C., makes them suitable for application by extrusion coating techniques; while the ability of the compositions to be applied at higher application temperatures, that is, temperatures of 200° C. to 250° C. makes them suitable for application by spray coating techniques. The subject formulations are preferably resistant to dirt pick-up, and further preferably exhibit less viscosity variability relative to systems which lack the homogeneous ethylene polymer.
The unique balance of properties characteristic of the formulations of the invention makes them suitable in a variety of coating, marking, and painting applications, including but not limited to road markings, traffic signs, runway markings, pedestrian crosswalks, building advertisements and markings, bicycle lanes, tennis courts, marking of tartan substitutes, stop lines, and driving course markings.
These and other embodiments are described in the following detailed description.
Test Methods Utilized for Characterizing the Homogeneous Ethylene Polymer
Density is measured in accordance with ASTM D-792. The samples are annealed at ambient conditions for 24 hours before the measurement is taken.
Melt index (I
2
), is measured in accordance with ASTM D-1238, condition 190° C./2.16 kg (formally known as “Condition (E)”).
Molecular weight is determined using gel permeation chromatography (GPC) on a Waters 150° C. high temperature chromatographic unit equipped with three mixed porosity 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 0.3 percent by weight solutions of the samples are prepared for injection. The flow rate is 1.0 mL/minute and the injection size is 100 microliters.
The molecular weight determination is deduced by using narrow molecular weight distribution polystyrene standards (from Polymer Laboratories) in conjunction with their elution volumes. The equivalent polyethylene molecular weights are determined by using appropriate Mark-Houwink coefficients for polyethylene and polystyrene (as described by Williams and Word in Journal of Polymer Science, Polymer Letters, Vol. 6, (621) 1968) to derive the following equation:
M
polyethylene
=a
*(
M
polystyrene
)
b.
In this equation, a=0.4316 and b=1.0. Weight average molecular weight, M
w
, is calculated in the usual manner according to the following formula: M
w
=&Sgr;w
i
*M
i
, where w
i
and M
i
are the weight fraction and molecular weight, respectively, of the ith fraction eluting from the GPC column.
Mel

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