US005665793A

United States Patent 19 11 Patent Number: 5,665,793

Anders 45 Date of Patent: Sep. 9, 1997
54 PHOSPHORESCENT HIGHWAY PAINT 4,172,063 10/1979 O'Brill ........................................ 524/5
COMPOSITION 5,424,006 6/1995 Murayama et al. ............. 252/301.4 R
76 Inventor: Irving Anders, 54 Crossway, Scarsdale, OTHER PUBLICATIONS
N.Y. 10583 Technical Bulletin for Lumi NovaG) dated Dec. 11, 1995
distributed by United Mineral & Chemical Corp.
(21) Appl. No.: 625,096
Primary Examiner-Peter A. Szekely
(22 Filed: Apr. 1, 1996 Attorney, Agent, or Firm-Lackenbach Siegel Marzullo
Aronson & Greenspan, P.C.
Related U.S. Application Data
57 ABSTRACT
60 Continuation-in-part of Ser. No. 525,850, Sep. 8, 1995,
abandoned, which is a division of Ser. No. 257,350, Jun. 9, The present invention relates to novel compositions useful,
1994, Pat. No. 5,472,737. for example, in water-based paints. The compositions con
(511 Int. Cl. .............. F21V 7/22; C08K 3/10 tain a moisture sensitive luminescent substance (for example
52 U.S. Cl. .................... 523/172; 252/301.36; 524/403; a phosphorescent substance having increased brightness and
524/434; 524/436; 524/437 longer lasting afterglow) and a polyurethane resin which is
(58) Field of Search .................................. 524/436, 437, water miscible or soluble, and which imparts moisture
524/403, 434; 523/172; 252/301.36 stability to the luminescent substance. As a result, this novel
composition when used in, for example, water-based high
56) References Cited way paints imparts an extended road surface life, and is
environmentally friendly because it does not contaminate
U.S. PATENT DOCUMENTS the surrounding environment with organic hydrocarbon
223,050 8/1879 Krause ................................. 252/462.1 products via vaporization or runoffs. In addition this paint
274,415 3/1883 Trotter, Jr. ... 252/301.36 composition may be used both indoors and outdoors for
1407,534 2/1922 Hering ........ ... 252/301.36 nighttime marking.
1,637,963 8/1927 Sauvage ..... ... 252/301.36
2,436,182 2/1948 Schmidling ........................ 252/301.36 14 Claims, No Drawings
 5,665,793
1. 2
PHOSPHORESCENT HOGHWAY PAINT Sunlight or artificial light (such as from headlights of
COMPOSITION automobiles) in the dark of night. After an initial exposure
to a light source, luminescence can be renewed by once
This application is a continuation-in-part application of again exposing the paints to either a natural or an artificial
and my U.S. patent application Ser. No. 08/525,850, filed light. Thus, highway paints have incorporated fluorescent or
Sep. 8, 1995, (now abandoned) entitled "Phosphorescent phosphorescent substances to demarcate the edges of high
Highway Paint Composition”, which in turn is a division of ways and the median line of the highway to differentiate the
U.S. Ser. No. 08/257,350, fied Jun. 9, 1994, now U.S. Pat. different directions of the highway vehicles. Previously
No. 5.472,737, issued Dec. 5, 1995. phosphorescent containing highway paints tended to lose
BACKGROUND OF THE INVENTION
10 their luminescence through chemical attack by the atmo
sphere (ultraviolet radiation and/or presence of moisture) on
1. Field of the Invention the phosphor. In such outdoor uses, the luminescent paint
The present invention relates to compositions useful, for compositions lost most of their phosphorescence capacity in
example, in water-based paints. The compositions contain a a matter of days.
15 U.S. Pat. No. 5.424,006 disclosures phosphorescent phos
moisture sensitive luminescent substance (for example a
phosphorescent substance having increased brightness and phors which can be utilized both indoors and outdoors as a
longer lasting afterglow) and a polyurethane resin which is nighttime display and show extremely long afterglow char
water miscible or soluble, and which imparts moisture acteristics. However, these phosphorescent phosphors must
stability to the luminescent substance. As a result, the be incorporated into chemical hydrocarbon solvent based
20 systems as they are adversely affected by moisture or
composition when used in water-based paints imparts an
extended road surface life, and is environmentally friendly aqueous systems. This reference is incorporated by refer
because it does not contaminate the surrounding environ ence in its entirety.
ment with organic hydrocarbon products via vaporization or Luminescent (phosphorescent) highway paint composi
runoffs. In addition this paint composition may be used both 25
tions should have the following characteristics: ease of
indoors and outdoors for nighttime marking. application, short track time, long wearability, moisture
2. Background Art stable (insensitive) luminescent pigment and suitably long
It is presently desirable to produce indoor and outdoor duration of afterglow luminescence. Of these, the most
luminescent paints whose compositions do not require difficult to achieve is long wearability under normal traffic
organic solvents whose vapors are undesirable when 30
conditions and long duration of afterglow luminescence.
released into the atmosphere and contaminate the surround Accordingly, it is a principal object of the present invention
ing soil or land near roadway surfaces via runoffs. U.S. Pat. to provide a composition suitable for use in highway or
No. 4,172,063 discloses an abrasion resistant reflective roadway paint that is environmentally protective, exhibits
marking composition containing cement, a fluorescent long duration afterglow luminescence and has increased
pigment, silica, glass fibers and a timing bonding acrylic 35
roadway life and durability, and is stable to the detrimental
polymer agent. This composition is, however, not environ effects of moisture as well as ultraviolet radiation.
mentally friendly nor does it exhibit any sustained lasting Other objects of the present invention, as well as particu
afterglow or extended durability or weatherability. lar features, elements, and advantages thereof, will be elu
The term "luminescence” as used in this specification and cidated in, or be apparent from, the following description of
in the appended claims is meant to be that property of a the invention.
material which causes visible light to be continued to be
emitted after an exciting light source has been removed as SUMMARY OF THE INVENTION
well as that property of a material to glow under a source of Now it has been discovered that environmentally friendly
light of low visibility and suitable wavelength. U.S. Pat. and energy saving water-based highway paints can be pro
Nos. 223,050; 274415; 1407,534 and 1,637,963 disclose 45 duced which have the desired characteristics of ease of
the use of luminous (phosphorescent) compositions in paint, application, short track time, suitable long duration and
enamels, and as a coloring in paper. These luminous or higher intensity of afterglow luminescence as well as the
phosphorescent materials exhibit reduced or degraded light most desired characteristic of extended service wear time
resistance over time. A paint mixture with an acrylic vehicle under traffic conditions even when subjected to the detri
but having an alkaline earth phosphor other than zinc sulfide, 50 mental factors of ultraviolet radiation and/or moisture.
which could be modified by replacing its alkaline earth The present invention achieves the above objects, among
phosphor with zinc sulfide to obtain a preferred phospho others, by providing a composition suitable for use in
rescent paint is described in U.S. Pat. No. 2,436,182. All of water-based highway or roadway paints comprising a mois
these cited references are incorporated in their entirety ture sensitive luminescent substance such as a phosphores
herein. 55 cent phosphor or a combination of a phosphorescent phos
As is well-known, fluorescent paints when excited by a phor and a fluorescent material and a polyurethane resin
source of light produce an emission of light but the light which is water compatible. Surprisingly, when this water
emission is limited to the period of excitation. Such paints compatible polyurethane resin is admixed with the water
can be selected to provide a day time coloration which will sensitive luminescent substance, the resulting mixture pro
demarcate and emphasize areas to be marked such as edges tects the luminescent substance from being attacked by the
of steps, corners of walls, highway edges and median traffic moisture in the air and the water in a water-based paint
divider stripes. composition. Thus, the luminescent substance is protected
Phosphorescent paints on the other hand, once they have immediately after being mixed with the polyurethane resin
been excited, remain luminous with a soft, slowly decaying in the paint composition.
emission or radiation. Such phosphorescent paints can gen 65 While the luminescent substance and the polyurethane
erate a useful level of luminous flux for periods of time resin may be added directly to a paint composition, in a
(even several hours) after being activated when exposed to preferred embodiment a premixture is formed by mechani
 5,665,793
3 4
cally mixing small incremental amounts of the luminescent The novel luminescent compositions of the present inven
substance with the water compatible/miscible polyurethane tion contain a water miscible or compatible polyurethane
resin to thoroughly coat the luminescent substance with the resin. The polyurethane resin (e.g. an acrylic urethane resin
polyurethane resin. The formation of the premixture permits in either a semi-gloss or gloss) used in the composition is a
even distribution of the luminescent particles within the thermoplastic polymer derived or produced by the reaction
polyurethane resin and assures that all or most of the of a polyisocyanate such as a diisocyanate (toluene
particles are coated. This premixture may be stored or diisocyanate) and a hydroxyl-containing material, for
immediately added to and mixed with water-based paint example, a polyol derived from propylene oxide or trichlo
compositions with adequate mechanical mixing to insure robutylene oxide, containing a water soluble group such as
high integration and distribution of the premixture through 10 hydroxy, carboxylic acid or amine group. The amount of
out the paint composition. The paint composition so pro water miscible polyurethane resin (semi-gloss or gloss) used
duced may be sealed and stored until ready to be used. At the ranges from about 1% to about 80%, with a preferred range
time it is to be used the highway paint composition should from about 3% to about 75%, more preferred from about 5%
be mixed mechanically again with conventional means. to about 70%, and a most preferred from about 10% to about
After applying a paint containing this novel composition 15 65% by volume of the novel luminescent composition.
to a surface, upon drying, the composition imparts wear The water-based dispersions employed in the present
ability to the surface such as resistance to surface wear by invention also can be used in commercially produced water
tires of motor vehicles using the roadway and thus provides based paints containing various colors used, for example, in
an extended surface life. Thus, highway or roadway marking painting highway roadway surfaces including white, yellow,
paints can be produced which provide pavement markings 20 orange, red, blue, and green. These types of paints may for
and patterns in accordance with state traffic regulations (e.g. example be used as a highway paint colored with the
New York State, Manual of Uniform Traffic Control devices appropriate highway or roadway colors of such as white
MUTCD). These paints are used for marking lines in the (titanium dioxide ASTM D476, Type II 100% purity),
path of traffic as well as those marking patterns located out yellow (medium chrome yellow ASTM D211, Type III
of the general path of traffic. 25 100% purity), orange and blue. The water based colored
The luminescent substance in the composition of the dispersion represents from about 30% to about 98%, a
invention may be either amoisture sensitive phosphorescent preferred range being from about 40% to about 95%, a more
substance (such as a phosphorescent phosphor oxide type or preferred range from about 50% to about 90%, and a most
a combination of a phosphorescent and a fluorescent sub preferred range being from about 55% to about 88% by
stance. The preferred luminescent substance contains phos 30 volume of the water based luminescent paint composition.
phorescent phosphors which exhibit extremely long duration The composition of the invention, when used in highway
of afterglow such as for example those phosphorescent paints, prevents or reduces or minimizes the flaking of the
phophors (disclosed in U.S. Pat. No. 5,424,006) which exposed surface by the tires of motor vehicles using the
comprise a compound expressed by the matrix MAl2O4 in roadway, this eliminates the need for an overcoat.
which M is at least one metal element selected from the 35
group consisting of calcium, strontium and barium or The selection of the amount of luminescent substance,
alternatively, is a matrix MAl-O in which M is a plurality colored paint dispersion, and polyurethane resin from within
of metal elements comprised of magnesium and at least one the ranges discussed above, is effected, for example, by the
element selected from the group consisting of calcium, color of the paint dispersion. Yellow paints require increased
strontium and barium. In a preferred form, 0.001 mol % to amounts of luminescent material in comparison to white
10 mol % of europium may be added to the matrix as an paints. The selected ranges permit a careful balance of the
activator, where the mol % is relative to the metal element water-based luminescent compositions of the invention with
expressed by M. In another preferred form, 0.001 mol % to other paint ingredients resulting, for example, in a highway
10 mol % of at least one element selected from a group paint composition with maximum desirable characteristics
consisting of lanthanium, cerium, praseodymium, for all traffic conditions.
45
neodymium, Samarium, gadolinium, terbium, dysprosium, Optionally, a particulate may be used to impart abrasive
holmium, erbium, thulium, ytterbium, lutetium, manganese, ness to the paint composition and is either a natural abrasive
tin and bismuth may be doped to the matrix expressed by material such as fine Sand, silica, ground marble (white
MAl-O as a co-activator in terms of mol % relative to the marble preferred), corundum (aluminum oxide, emery),
metal element expressed by M. These phosphorescent phos 50 pumice, iron oxide and feldspar. The more important syn
phors are commercially available under the trademarkLumi thetic types are silicon carbide, boron carbide, cerium oxide
Nova(E) distributed in the United States by United Mineral and fused alumina; or even some reflective substances (for
and Chemical Corporation. example crushed reflective glass) as long as they will impart
The novelluminescent compositions of the present inven an effective abrasiveness to the surface of the dried paint.
tion protects and shields the phosphorescent phosphor from 55 This abrasiveness reduces the likelihood of skidding by
the oxidizing action and humidity of the atmosphere, and motor vehicles both in clear weather as well as when the
from moisture. When the luminescent compositions include surface of the road is wet. The operable range is an additive
a combination of a phosphorescent and a fluorescent amount from about 1% to about 15% parts by volume, with
material, the fluorescent material present in the luminescent a preferred range of about from 1% to about 13%, with from
substance produces a daytime luminescence or reflectivity or 60 about 1% to about 9% the most preferred.
coloration in addition to the phosphorescence produced at The surface of the pavement or roadway is prepared to
night. The operable range for the concentration of phospho receive the new paint by being swept clean and then air
rescent substance is from about 1% to about 75%, with a blasted to remove dirt and other residues thereon.
preferred range from about 5% to about 70%, a more The applicating equipment for the paint is that which is
preferred range from about 10% to about 65%, and a most 65 commonly used to paint roadway surfaces, i.e. it shall be
preferred range of from about 15% to 60% by volume of the maneuverable to the extent that straight lines can be foll
novel luminescent composition. lowed and normal curves can be made in a true arc. Other
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accessories are utilized which allow for marking legends, 77 parts of white water based highway paint.
symbols, crosswalks, and other special patterns. This equip The ingredients are mixed at an ambient temperature of
ment is normally truck mounted to provide a self-contained 73°-5°F. The minimum temperature of the pavement is 50°
pavement marking machine to apply the paint and other F.The paint is then sprayed on the asphalt pavement surface
desired topical reflective materials such as glass spheres in of a roadway in four inch wide stripes. The surface of the
continuous and skip-line patterns. During application of the roadway has been swept clean and air blasted to remove dirt
water-based luminescent paint compositions of the present and dust and other residues such as oil, grease, and similar
invention, the surface temperature of the roadway should be foreign materials in the areas where the paint is to be
about 50° F or higher. applied. The paint is allowed to dry until it is no longer tacky
DETALED DESCRIPTION OF THE
10 to the touch (a no-tack condition) and this usually occurs in
PREFERRED EMBODIMENTS
about 30 minutes. It is completely dry in about an hour.
EXAMPLE 4
Some examples will be given to illustrate the essence of
the invention. All the ingredients are set forth as parts by A water-based highway paint is produced from the fol
volume unless otherwise indicated. 15 lowing ingredients:
15 parts of powered 80/20 LumiNova(8) phosphorescent/
EXAMPLE 1. fluorescent material mixture;
A water-based highway paint is produced from the fol 18 parts of water based acrylic polyurethane, gloss; and
lowing ingredients: 20
67 parts of yellow water-based highway paint.
5 parts of powdered LuminovacE* phosphorescent mate The ingredients are mixed at an ambient temperature of
rial; 73°-5F. The minimum temperature of the pavement is 50°
7 parts of water based acrylic urethane, semi-gloss; and F.The paint is then sprayed on the asphalt pavement surface
of a roadway in four inch wide stripes. The surface of the
88 parts of white water-based highway paint. 25 roadway has been swept clean and air blasted to remove dirt
*Luminova is a registered trademark. Technical literature-United Mineral and other residues in the areas where the paint is to be
& Chemical Corp, Dec. 11, 1995. This publication is incoporated by reference
in its entirety. applied. The paintis allowed to dry until it is no longer tacky
The phosphorescent phosphor and the acrylic urethane are to the touch (a no-tack condition) and this usually occurs in
first separately mixed together at an ambient temperature about 30 minutes. It is completely dry in about an hour.
73°-5° F and then mixed with the water-based highway 30
paint. The minimum temperature of the asphalt pavement ingredients Ex. 5* Ex. 6* Ex. 74
surface is 50°F. The paint is then sprayed on the pavement
surface of a roadway in four inch wide stripes. The surface phosphorescent powder 7 7 7
of the roadway has been swept clean and air blasted to acrylic polyurethane 9 9 9
remove dirt and other residues in the areas where the paint sand (fine) 15 5 13
35 highway paint white 69 79 71
is to be applied. The paint is allowed to dry until it is no
longer tacky to the touch (a no-tack condition) and this Ingredients Ex. 8* Ex. 9 Ex. 10*
usually occurs in about 30 minutes. It is completely dry in phosphorescent powder 7 7 7
about an hour.
acrylic polyurethane 9 9 9
EXAMPLE 2 sand (fine) 7 9 1.
highway paint white 77 75 73
A water-based highway paint is produced from the fol *All parts of these examples are parts by volume.
lowing ingredients:
10 parts of powdered LUMINOVAG) phosphorescent The ingredients are mixed at an ambient temperature of
material; 45 73°5°F. The minimum temperature of the pavement is 50°
13 parts of water based acrylic urethane (gloss finish); and F.The paint is then sprayed on the asphalt pavement surface
77 parts of yellow water-based highway paint. of a roadway in four inch wide or wider stripes. The surface
The phosphorescent phosphor and the acrylic urethane are of the roadway has been swept clean and air blasted to
first separately mixed together at an ambient temperature remove dirt and other residues in the areas where the paint
73°-5° F and then mixed with the water-based highway
50 is to be applied. The paint is allowed to dry until it is no
paint. The minimum temperature of the pavement is 50° F. longer tacky to the touch (a no-tack condition) and this
The paint is then sprayed on the asphalt pavement surface of usually occurs in about 30 minutes. It is completely dry in
a roadway in four inch wide stripes. The surface of the about an hour depending upon the moisture content of the
roadway has been swept clean and air blasted to remove dirt ambient air. The higher the moisture content of the air, the
and other residues in the areas where the paint is to be
55 longer the paint takes to dry completely.
applied. The paintis allowed to dry untilitis no longer tacky The dried highway paint exhibits greater durability,
to the touch (a no-tack condition) and this usually occurs in improved abrasiveness, and the luminescence materials
about 30 minutes. It is completely dry in about an hour. exhibit a longer life and greater intensity by the order of
magnitude of 10 than previously known because the poly
EXAMPLE 3 urethane resin in the paint composition tends to prevent
A water-based highway paint is produced from the fol oxidation of the luminescent materials in the paint. Previ
lowing ingredients: ously luminescent (phosphorescent) materials used outside
exhibited a useful life of a minimum of days before degra
10 parts of powdered 80/20 LUMINOVA (8) dation is obvious. The current effective useful life of lumi
phosphorescent/fluorescent material; 65 nescent materials in the paint composition of the present
13 parts of water based acrylic polyurethane, semi-gloss; invention has no minimum and is now a function of the
and longivity and/or wearability of the paint composition itself.
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The durability of the paint on the roadway is also greatly one metal element selected from the group consisting
increased due to the polyurethane resin and the abrasive in of calcium, strontium and barium or alternatively, is a
the paint reduces the tendency of vehicles driving over the matrix. MAO in which M is a plurality of metal
paint to skid, a marked safety factor. elements comprised of magnesium and at least one
When it is desirable to have reflectorized highway mark element selected from the group consisting of calcium,
ings or to increase the reflectivity of the highway paint, strontium and barium; a water miscible polyurethane
reflective glass beads (fine glass spheres) are injected into or resin; and a water-based colored paint dispersion.
dropped onto the surface of the wet paint on the roadway 4. The composition of claim 3, containing a fluorescent
surface manually or by a suitable mechanical device (such as Substance.
a sprinkler) at the rate of 20 to 25 pounds per gallon of 10 5. A method of producing a water miscible luminescent
mating. Insufficient glass bead coverage or inadequate glass
bead retention are to be avoided. Excessive glass bead composition stance
which comprises, admixing aluminescent sub
expressed by the matrix MAl-O in which M is at
coverage is also to be avoided as it would reduce the least one metal element selected from the group consisting
effective afterglow quality by scattering the energizing light
prior to it activiting the phosphors. Approximately about ten 15 of calcium, strontium and barium or alternatively, is a matrix
percent of the reflective beads applied to the painted surface MAl-O in which M is a plurality of metal elements com
adhere to the wet surface of the paint. ... prised of magnesium and at least one element selected from
All necessary spray equipment, mixers, compressors and the group consisting of calcium, strontium and barium; with
other appurtenances for the placement of the luminescent a water miscible polyurethane resin.
highway paint or reflectorized highway pavement markings 20 . 6. A method of producing a water miscible luminescent
are well known in the prior art. paint composition which comprises admixing aluminescent
When reflective glass spheres are used with the highway substance expressed by the matrix MAl-O in which M is at
paint of the invention and due to wear are worn of the least one metal element selected from the group consisting
surface of the paint (since the glass spheres are considered of calcium, strontium and barium or alternatively, is a matrix
a topical coating), the reflectivity of the paint is still present 25 MAl-O in which M is a plurality of metal elements com
because of the luminescent material in the paint which has prised of magnesium and at least one element selected from
not been removed and continues to be present until the paint the group consisting of calcium, strontium and barium; with
is completely worn away or physically removed. a watermiscible polyurethane resin to form a watermiscible
It will thus be seen that the objects set forth above, among luminescent composition; and admixing the water miscible
those elucidated in, or made apparent from, the preceding luminescent composition with a water-based paint compo
30
description, are efficiently attained and, since certain sition.
changes may be made in the above composition without 7. The composition of claim 1 containing europium as an
departing from the scope of the invention, it is intended that activator.
all matter contained in the above description shall be inter 8. The composition of claim 7 in which the concentration
preted as illustrative only and not in a limiting sense. 35
of the activator is from about 0.001 mol % to about 10 mol
While the water based paint composition of the present %, the mol % being relative to the metal element expressed
invention is directed toward application to roadway by M.
Surfaces, including both roadway pavement writing and 9. The composition of claim 7 containing a co-activator
markings, it could also be used on overhead road and selected from the group consisting of lanthanium, cerium,
shoulder signs. In such applications as these an aggregate praseodymium, neodymium, samarium, gadolinium,
such as crushed reflective glass beads or fine whim marble terbium, dysprosium, holmium, erbium, thulium, ytterbium,
would be used in an additive amount in the paint composi lutetium, manganese, tin and bismuth.
tion to enhance the reflectivity of the paint. 10. The water-based luminescent paint composition of
It is also to be understood that the following claims are claim 2 containing europium as an activator.
intended to cover all of the generic and specific features of 45
11. The water-based luminescent paint composition of
the invention herein described and all statements of the claim 10 in which the concentration of the activator is from
scope of the invention which, as a matter of language, might about 0.001 mol % to about 10 mol %, the mol % being
be said to fall therebetween.
I claim: relative to the metal element expressed by M.
1. A luminescent composition comprising: 50
12. The water-based luminescent paint composition of
claim 11 containing a co-activator selected from the group
a luminescent substance comprising a compound consisting of lanthanium, cerium, praseodymium,
expressed by the matrix MAl-O in which M is at least neodymium, Samarium, gadolinium, terbium, dysprosium,
one metal element selected from the group consisting holmium, erbium, thulium, ytterbium, lutetium, manganese,
of calcium, strontium and barium or alternatively, is a 55
tin and bismuth.
matrix MAl-O in which M is a plurality of metal 13. The water-based luminescent paint composition of
elements comprised of magnesium and at least one claim 2 wherein the color of the paint dispersion is selected
element selected from the group consisting of calcium, from the group consisting of white, yellow, orange, blue,red
strontium and barium; and a water miscible polyure and green.
thane resin. 14. The water-based luminescent paint composition of
2. The composition of claim 1, containing a fluorescent claim 2 containing in an additive amount an abrasive par
Substance. ticulate selected from the group consisting of a natural
3. A luminescent paint composition comprising: abrasive material and a synthetic abrasive material.
a luminescent substance comprising a compound
expressed by the matrix MAl-O in which Mis at least ce : k : :