U.S. patent application number 11/470944 was filed with the patent office on 2007-09-06 for phosphorescent marine products.
This patent application is currently assigned to MarineGlo Corporation. Invention is credited to John R. Goedel.
Application Number | 20070205397 11/470944 |
Document ID | / |
Family ID | 22542669 |
Filed Date | 2007-09-06 |
United States Patent
Application |
20070205397 |
Kind Code |
A1 |
Goedel; John R. |
September 6, 2007 |
PHOSPHORESCENT MARINE PRODUCTS
Abstract
In one embodiment of the invention, a marine article of the
invention includes a phosphorescent phosphor. A particularly
advantageous phosphorescent phosphor comprises MAl.sub.2O.sub.4. As
used herein, "M" is at least one cation selected from a group
consisting of calcium, strontium, and barium. The phosphor
comprises 0.001% to 10% of a europium activator, and 0.001% to 10%
of at least one dopant selected from the group consisting of
lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium,
dysprosium, holmium, erbium, thulium, ytterbium, lutetium, tin and
bismuth as a co-activator, in terms of mol % relative to the metal
element expressed by M. The phosphorescent marine article has an
afterglow corresponding to a luminance of at least 0.3 mCd/m.sup.2
for at least 420 minutes.
Inventors: |
Goedel; John R.; (Eden
Prairie, MN) |
Correspondence
Address: |
MERCHANT & GOULD PC
P.O. BOX 2903
MINNEAPOLIS
MN
55402-0903
US
|
Assignee: |
MarineGlo Corporation
Eden Prairie
MN
|
Family ID: |
22542669 |
Appl. No.: |
11/470944 |
Filed: |
September 7, 2006 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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11316797 |
Dec 22, 2005 |
|
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11470944 |
Sep 7, 2006 |
|
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10791363 |
Mar 1, 2004 |
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11316797 |
Dec 22, 2005 |
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|
09778973 |
Feb 6, 2001 |
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10791363 |
Mar 1, 2004 |
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09152377 |
Sep 14, 1998 |
6253698 |
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09778973 |
Feb 6, 2001 |
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Current U.S.
Class: |
252/301.36 ;
252/301.4P |
Current CPC
Class: |
C09K 11/7734 20130101;
C09K 11/02 20130101; B63C 9/21 20130101; Y10T 428/28 20150115; C09K
11/7792 20130101; Y10T 428/31504 20150401; B63B 51/00 20130101;
B63B 45/04 20130101 |
Class at
Publication: |
252/301.36 ;
252/301.40P |
International
Class: |
C09K 11/08 20060101
C09K011/08 |
Claims
1. A phosphorescent marine product comprising; a marine article;
and a phosphorescent phosphor; wherein, the phosphorescent phosphor
comprises MAl.sub.2O.sub.4 wherein M is at least one cation
selected from a group consisting of calcium, strontium, and barium,
wherein the phosphor comprises 0.001% to 10% of a europium
activator, and wherein the phosphor comprises 0.001% to 10% of at
least one dopant selected from the group consisting of lanthanum,
cerium, praseodymium, neodymium, samarium, gadolinium, dysprosium,
holmium, erbium, thulium, ytterbium, lutetium, tin and bismuth as a
co-activator, in terms of mol % relative to the metal element
expressed by M.
2. The phosphorescent marine product of claim 1, wherein the
phosphorescent phosphor is incorporated into a tape and the tape is
affixed to the marine article.
3. The phosphorescent marine product of claim 1, wherein the marine
article comprises a polymer and the phosphorescent phosphor is
incorporated into the polymer.
4. The phosphorescent marine product of claim 3, wherein the
polymer is selected from the group consisting of polycarbonate,
polyethylene, polypropylene, polystyrene, polyurethane, copolymer
of ethylene, copolymer of vinyl acetate, terpolymer of
acrylonitrile, terpolymer of butadiene and terpolymer of
styrene.
5. The phosphorescent marine product of claim 1, wherein the
phosphorescent phosphor is incorporated into a paint and the paint
covers at least a portion of the marine article.
6. The phosphorescent marine product of claim 5, wherein the paint
comprises polyurethane.
7. The phosphorescent marine product of claim 1, wherein the marine
article is a dock accessory selected from the group consisting of
dock fenders, post fenders, bumpers, dock trim, step trim, cleats,
ladders, post caps and dock lights.
8. The phosphorescent marine product of claim 1, wherein the marine
article is a boat accessory selected from the group consisting of
bumpers, sails, masts, lettering, numbering, marine rope, trailer
guides, trailer rollers, ladders, covers, shift knobs, throttle
knobs, steering wheels and instrument gauges.
9. The phosphorescent marine product of claim 1, wherein the marine
article is a personal accessory selected from the group consisting
of jackets, knives, coolers, drinking glasses, tools, and
patches.
10. The phosphorescent marine product of claim 1, wherein the
marine article is a floatation device selected from the group
consisting of buoys, buoy wraps, buoy caps, life jackets, floating
key rings, ring buoy/life savers and floating cushions.
11. A phosphorescent marine product comprising; a buoy cap or a
dock post cap; and a phosphorescent phosphor; wherein, the
phosphorescent phosphor comprises MAl.sub.2O.sub.4 wherein M is at
least one cation selected from a group consisting of calcium,
strontium, and barium, wherein the phosphor comprises 0.001% to 10%
of a europium activator, and wherein the phosphor comprises 0.001%
to 10% of at least one dopant selected from the group consisting of
lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium,
dysprosium, holmium, erbium, thulium, ytterbium, lutetium, tin and
bismuth as a co-activator, in terms of mol % relative to the metal
element expressed by M.
12. A phosphorescent marine product comprising; a marine article;
and a phosphorescent phosphor; wherein, the phosphorescent phosphor
has an afterglow corresponding to a luminance of at least 0.3
mCd/m.sup.2 for at least about 420 minutes.
13. The phosphorescent marine product of claim 12, wherein the
phosphorescent phosphor is incorporated into a tape and the tape is
affixed to the marine article.
14. The phosphorescent marine product of claim 12, wherein the
marine article comprises a polymer and the phosphorescent phosphor
is incorporated into the polymer.
15. The phosphorescent marine product of claim 14, wherein the
polymer is selected from the group consisting of polycarbonate,
polyethylene, polypropylene, polystyrene, polyurethane, copolymer
of ethylene, copolymer of vinyl acetate, terpolymer of
acrylonitrile, terpolymer of butadiene and terpolymer of
styrene.
16. The phosphorescent marine product of claim 12, wherein the
phosphorescent phosphor is incorporated into a paint and the paint
covers at least a portion of the marine article.
17. The phosphorescent marine product of claim 16, wherein the
paint comprises polyurethane.
18. The phosphorescent marine product of claim 12, wherein the
marine article is a dock accessory selected from the group
consisting of dock fenders, post fenders, bumpers, dock trim, step
trim, cleats, ladders, post caps and dock lights.
19. The phosphorescent marine product of claim 12, wherein the
marine article is a boat accessory selected from the group
consisting of bumpers, sails, masts, lettering, numbering, marine
rope, trailer guides, trailer rollers, ladders, covers, shift
knobs, throttle knobs, steering wheels and instrument gauges.
20. The phosphorescent marine product of claim 12, wherein the
marine article is a personal accessory selected from the group
consisting of jackets, knives, coolers, drinking glasses, tools,
and patches.
Description
[0001] This application is a continuation of application Ser. No.
11/316,797, filed Dec. 22, 2005, which is a continuation of
application Ser. No. 10/791,363, filed Mar. 1, 2004, now abandoned,
which is a continuation of application Ser. No. 09/778,973, filed
Feb. 6, 2001, now abandoned, which is a continuation of application
Ser. No. 09/152,377, filed Sep. 14, 1998, now U.S. Pat. No.
6,253,698, which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] During recent years, maritime activities both commercial and
recreational have increased dramatically. As a consequence,
visibility of marine articles is more important as U.S. bodies of
water become crowded. The current means of increasing visibility of
marine articles, such as, for example, buoy markers and boat
indicators, include phosphorescent or fluorescent materials and
brightly colored paints. However, these current means suffer from
serious visibility and durability challenges.
[0003] Generally, the afterglow time of a fluorescent substance is
short, i.e., the light emitted from the fluorescent substance
decays immediately after removal from the source of excitation.
Unlike such a fluorescent substance, some substances emit light
after having absorbed ultraviolet radiation, and afterglow thereof
that can be visually observed for a considerable time (ranging from
several tens of minutes to several hours) after the source of
stimulus is cut off. Such substances are called phosphorescent
phosphors.
[0004] Phosphorescent phosphors are known. Sulfide phosphorescent
phosphors are also known and include for example CaS:Bi (which
emits light of violet blue), CaStS:Bi (which emits light of blue),
ZnS:Cu (which emits light of green) and ZnCdS:Cu (which emits light
of green) and ZnCdS:Cu (which emits light of yellow or orange).
However, many of these sulfide phosphorescent phosphors are
chemically unstable and show degraded light resistance, i.e., they
suffer from problems that must be solved for practical use.
[0005] The most extensively used phosphorescent phosphor among such
sulfide phosphorescent phosphors is zinc sulfide phosphorescent
phosphor (ZnS:Cu). However, zinc sulfide phosphorescent phosphor is
decomposed as the result of irradiation by ultraviolet radiation in
the presence of moisture and thus, over time, blackens or reduces
the phosphor's luminance. Therefore, it is difficult to use this
phosphorescent phosphor in fields where it is placed outdoors and
exposed to a direct sunlight, that is, application is limited to
luminous clocks/watches or clocks/watches and instrument dials,
evacuation guiding signs or indoor night-time display.
[0006] Even when zinc sulfide phosphorescent phosphor is used for a
luminous clock, the afterglow allows the time to be visually
recognized lasts only from 30 minutes to 2 hours. Therefore, the
phosphorescent phosphor must be doped with a radioactive substance
and a self-luminous paint to keep emitting light by absorbing the
energy of radiation from the radioactive substance.
[0007] The use of brightly-colored paints, including fluorescent
paints, on marine floats do not solve the visibility problem in
darkness. Brightly-colored and fluorescent paints can only be seen
if light is present to be reflected thereby. Also, these paints
become eroded or worn from the relatively soft and pliable surface
of microporous resinous or foam marine floats, during use, so that
any advantage which justifies the expense of applying such a paint
is soon lost or severely diminished.
[0008] Thus, a need exists to develop phosphorescent marine
products that provide long lasting afterglow characteristics, are
chemically stable and physically durable in an outdoor marine
environment.
SUMMARY OF THE INVENTION
[0009] The invention solves the prior art's visibility and
durability problems of marine products by developing a highly
visible and durable marine compatible product. In one embodiment, a
marine article of the invention includes a phosphorescent phosphor.
A particularly advantageous phosphorescent phosphor comprises
MAl.sub.2O.sub.4. As used herein, "M" is at least one cation
selected from a group consisting of calcium, strontium, and barium.
The phosphor comprises 0.001% to 10% of a europium activator, and
0.001% to 10% of at least one dopant selected from the group
consisting of lanthanum, cerium, praseodymium, neodymium, samarium,
gadolinium, dysprosium, holmium, erbium, thulium, ytterbium,
lutetium, tin and bismuth as a co-activator, in terms of mol %
relative to the metal element expressed by M. The phosphorescent
marine article has an afterglow corresponding to a luminance of at
least 0.3 mCd/m.sup.2 for at least 1000 minutes. In a preferred
embodiment of the invention the phosphorescent phosphor is
incorporated into a polymer forming a phosphorescent buoy or dock
post cap.
BRIEF DESCRIPTION OF THE DRAWING
[0010] FIG. 1 is a perspective view of a marine cap.
[0011] FIG. 2 is a front elevation view of a marine cap.
[0012] FIG. 3 is a top plane view of a marine cap.
[0013] FIG. 4 is a bottom plane view of a marine cap.
DETAILED DESCRIPTION
[0014] A marine article includes a phosphorescent phosphor. A
disclosure of one example of a phosphorescent phosphor suitable for
a marine product of the invention is U.S. Pat. No. 5,424,006
incorporated by reference herein. The phosphorescent marine
articles described below show much longer afterglow characteristics
that last longer than presently available phosphorescent marine
articles and are chemically stable in the presence of moisture and
UV light (marine environment).
[0015] It is important the marine article be visible throughout an
entire night of darkness. This insures that marine articles are
able to be seen and to alert aquatic users to dangers the marine
articles are marking even in darkness. Typically the marine
articles should display a visible afterglow for at least about
seven-eight hours (420-480 minutes), preferably greater than about
ten hours (600 minutes), more preferably greater than about 1000
minutes. This length of time is adequate for a typical summer
period of darkness for most regions. However, longer afterglow
periods of time are desirable.
[0016] The Phosphorescent Phosphor
[0017] One phosphorescent phosphor suitable in the invention is
known commercially as "Luminova". "Luminova" is manufactured by
Nemoto & Co., Ltd., of Japan. The present invention provides a
phosphorescent phosphor which comprises a compound expressed by
MAl.sub.2O.sub.4 whose host material is a compound in which M is at
least one cation selected from a group consisting of calcium,
strontium and barium.
[0018] A phosphorescent phosphor which includes a compound
expressed by MAl.sub.2O.sub.4 whose host material is a compound
composed of a plurality of metal cations in which M is at least one
metal cation selected from a group consisting of calcium, strontium
and barium to which magnesium is added.
[0019] The phosphor contains 0.001 mol % to 10 mol % of a europium
activator in terms of mol % relative to the cation expressed by M.
The phosphor also typically contains 0.001 mol % to 10 mol % of at
least one dopant selected from a group consisting of lanthanum,
cerium, praseodymium, neodymium, samarium, gadolinium, terbium,
dysprosium, holmium, erbium, thulium, ytterbium, lutetium,
manganese, tin and bismuth as a co-activator in terms of mol %
relative to the metal element expressed by M.
[0020] The phosphorescent phosphor may show a glow peak of
thermo-luminescence in a high-temperature region of 50.degree. C.
or above when irradiated by ultraviolet or visible rays having a
wavelength of 200 to 450 nm at room temperatures. The
phosphorescent phosphor's afterglow remains visible for at least
1000 minutes. Visible is defined as a light intensity corresponding
to a luminance of about 0.3 mCd/m.sup.2.
[0021] The Marine Article
[0022] The Applicants have found the above described phosphorescent
phosphor useful in a variety of marine articles. Examples of marine
articles include dock accessories, boat accessories, personal
accessories, and floatation devices. Virtually any article that
relates to outdoor water activities is useful in the invention.
[0023] One particularly useful marine articles are phosphorescent
marine caps. Marine caps include buoy caps and dock post caps.
These marine caps can mount on top of the buoy or dock post body.
FIGS. 1-4 illustrate one embodiment of a preferred configuration of
a marine cap. The overall appearance of the embodiment illustrated
in FIGS. 1-4 is not exhaustive of appearances which are within the
scope of the invention but are merely representative of one
configuration which is ornamental but maintains some or all of the
functional aspects of a marine cap of the invention.
[0024] Dock Accessory
[0025] Dock accessories are articles that are used in conjunction
with the construction, operation, and maintenance of a dock or
pier. An listing of dock accessories includes, for example, dock
fenders, post fenders, bumpers, dock trim, step trim, cleats,
ladders, post caps and dock lights.
[0026] Boat Accessory
[0027] Boat accessories are articles that are used in conjunction
with the construction, operation, and maintenance of a boat, ship,
or personal water craft. An listing of boat accessories includes,
for example, bumpers, sails, masts, lettering, numbering, marine
rope, trailer guides, trailer rollers, ladders, covers, shift
knobs, throttle knobs, steering wheels and instrument gauges.
[0028] Personal Accessory
[0029] Personal accessories are articles that are used in
conjunction with the person while in a marine environment. An
listing of personal accessories includes, for example, jackets,
knives, coolers, drinking glasses, tools and patches.
[0030] Flotation Device
[0031] Flotation devices are articles that have the ability to stay
on the surface of water. A listing of flotation devices includes,
for example, buoys, buoy wraps, buoy caps, life jackets, floating
key rings, ring buoy/life savers and floating cushions.
[0032] Tape
[0033] The phosphorescent phosphor can be incorporated into a tape.
The tape can be affixed to a marine article using known methods.
The tape can be a multi-layer film typically consisting of a
phosphorescent backing, an adhesive and a liner.
[0034] Polymer
[0035] The phosphorescent phosphor can be incorporated into a
polymer. An listing of useful polymers includes, for example,
polycarbonates, polyethylenes, polypropylenes, polystyrenes,
polyurethanes, copolymers of ethylene, copolymers of vinyl acetate,
terpolymers of acrylonitrile, terpolymers of butadiene and
terpolymers of styrene.
[0036] The manufacturing process for polymeric marine articles is
typically a vacuum\thermoforming process although other methods are
known in the art. The phosphorescent phosphor can be mixed with the
liquid polymer to form the phosphorescent phosphor/polymer mixture.
The plastic can then typically be formed into sheets. The sheets
are heated and placed over a mold. A vacuum pulls the sheet around
the mold to form the marine article. Finally, the article is
hardened by cooling the polymer. The phosphorescent
phosphor/polymer mixture may also be formed into pellets that are
extruded and further processed into the marine article using known
methods. Injection molding is another common process for forming
the marine articles of the invention.
[0037] The phosphorescent phosphor can also be incorporated into a
paint such as a polyurethane paint. The phosphorescent phosphor
paint may then be applied to the marine article to provide the
luminance quality using known methods.
[0038] The above specification, and figures provide a complete
description of the composition of the invention. Many embodiments
of the invention can be made without departing from the spirit and
scope of the invention.
* * * * *