U.S. patent number 3,584,211 [Application Number 04/765,542] was granted by the patent office on 1971-06-08 for chemiluminescent liquid dispensing or display container.
This patent grant is currently assigned to American Cyanamid Company. Invention is credited to Michael McKay Rauhut.
United States Patent |
3,584,211 |
Rauhut |
June 8, 1971 |
CHEMILUMINESCENT LIQUID DISPENSING OR DISPLAY CONTAINER
Abstract
A device for providing chemiluminescent light from a chemical
reaction of suitable compounds in the presence of a fluorescent
compound, said device being both a self-contained light unit and a
chemiluminescent dispensing unit. Bending the flexible,
light-transmitting outer tube containing one chemiluminescent
component breaks a frangible inner container holding a second
component, allowing the substances to react. The luminescent
reaction product may be dispensed and used as a luminescent marker
or held in the closed device for use as an illumination wand.
Inventors: |
Rauhut; Michael McKay (Norwalk,
CT) |
Assignee: |
American Cyanamid Company
(Stamford, CT)
|
Family
ID: |
25073830 |
Appl.
No.: |
04/765,542 |
Filed: |
October 7, 1968 |
Current U.S.
Class: |
362/34; 222/94;
362/96; 252/700; 222/541.6 |
Current CPC
Class: |
F21K
2/06 (20130101) |
Current International
Class: |
F21K
2/00 (20060101); F21K 2/06 (20060101); F21k
002/00 () |
Field of
Search: |
;240/2.25 ;102/37.8
;161/196 ;250/71 ;222/94,136,541 ;195/103.5,54 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Matthews; Samuel S.
Assistant Examiner: Hutchison; Kenneth C.
Claims
I claim:
1. A chemiluminescent light device comprising an outer flexible,
light transmitting tube means and a sealed inner breakable tube
means enclosed within said outer tube means, a chemiluminescent
component in each of said tube means, said outer tube being sealed
at one end, and dispensing closure means the other end of said
outer tube; said components being capable of reaction upon
admixture to provide chemiluminescent light.
2. The device of claim 1, wherein said inner tube means comprises
more than one tube.
3. A device of claim 1, wherein the closure means for the outer
tube means comprises an opening and a removable cap therefor.
4. The device of claim 3, wherein said cap is threaded.
5. The device of claim 3, wherein said cap is a friction fit.
6. The device of claim 1, wherein said closure device is a heat
sealed tear spout.
7. The device of claim 1, wherein said closure device is a sealed
breakoff tip.
Description
This invention relates to systems and devices for providing
chemiluminescent light incorporating chemical components which
react chemically and provide excitation for a fluorescent compound.
The invention more particularly relates to systems and devices
whereby the reactive components are maintained in a nonreactive
condition until light is desired, the systems incorporating means
to bring said components into a reactive condition and means to
display the resultant light.
Under certain circumstances, it is desirable to have a source of
visible light which is not electrically activated. Light can be
provided by chemical systems, wherein the luminosity is solely the
result of chemical reaction without provision of any electrical
energy. Such light is known as chemiluminescent light.
Chemiluminescent light may be useful where there is no source of
electricity. For example in emergencies where sources of electrical
power have failed, a chemiluminescent system could provide light.
Since the system requires no externally generated source of energy,
devices can be made small and highly portable. Moreover,
chemiluminescent light is cold light and can be used where the heat
of conventional illumination is not desired. It is also useful
where electrical means could cause a fire hazard, such as in the
presence of inflammable agents. Chemiluminescent light is also
effective under water since there are no electrical connections to
short out. Thus it may be seen that chemiluminescent light can have
many useful applications.
A principal object of the present invention is to provide systems
and devices incorporating chemiluminescent components for the
provision of chemiluminescent light.
A further object of this invention is to provide means for
containing chemically reactive chemiluminescent components in a
nonreactive condition and means to combine said components when
desired to provide chemiluminescent light.
A further object is to provide a self-contained, highly portable
chemiluminescent lighting device having all chemical components
therein and in which the light is displayed and from which it may
be dispensed.
Another object is to provide a chemiluminescent lighting device
which is inexpensive to make, easy to activate and highly
effective.
Another object of the invention is to provide an illuminated wand
having a chemiluminescent lighting system.
These and other objects of the invention will become apparent as
the description thereof proceeds.
This invention comprises a device for the storage and subsequent
admixture and display or dispensing of a multicomponent
chemiluminescent system. The device consists essentially of an
elongated, transparent or translucent flexible outer tube and a
rigid or rupturable, breakable inner container or tube within the
outer tube. The inner tube may be free or fixed within the outer
tube. The inner tube is filled (wholly or in part) with one
component of a two-component chemical lighting system. The outer
tube is filled with the second component. The outer tube is
permanently sealed at one end and provided with a dispensing
closure at the other.
To operate the device, the outer, flexible tube is bent causing the
inner breakable tube to fracture and thus mix the two components
and initiate light production. The outer translucent tube thus
becomes a lighted wand for display purposes. If desired, all or
part of the chemiluminescent mixture may be dispensed by opening
the closure at one end of the outer tube.
It is clear that two or more inner tubes could be employed to store
separately the components of a three or multiple-component chemical
lighting system.
The chemiluminescent system of this invention thus comprises the
device as described accommodating the admixture of at least two
chemiluminescent components and providing for the admixture in the
device of at least two chemiluminescent components comprising
either (a) a component containing a chemiluminescent compound and a
second component containing a hydroperoxide compound, either or
both components containing a diluent, or (b) a dry solid component
containing both a solid chemiluminescent compound and a solid
hydroperoxide compound and a second component comprising a solvent
for said solid chemiluminescent compound and said solid
hydroperoxide compound. Any other necessary ingredients for the
production of chemiluminescent light, or for lifetime control, or
for intensity improvement, or for storage stabilization must of
course either be included in one of the two system components or
included as additional components. In particular with the preferred
oxalic-type chemiluminescent compounds of this invention, a
fluorescent compound must be included in the system.
The preferred chemiluminescent light is obtained in this invention
by the reaction of a hydroperoxide with a chemiluminescent
composition which, in combination, comprises a chemiluminescent
compound selected from the group consisting of (1) an oxalic-type
anhydride of the type disclosed and claimed in the copending
application, Ser. No. 485,920, now U.S. Pat. No. 3,399,137, which
is hereby incorporated by reference, (2) an oxalic-type amide of
the type disclosed and claimed in copending applications, Ser. Nos.
520,052, now U.S. Pat. No. 3,442,815, and 547,782, now abandoned,
which are hereby incorporated by reference, (3) an oxalic-type
O-acylhydroxylamine of the type disclosed and claimed in copending
application, Ser. No. 547,761, now abandoned, and (4) an
oxalic-type ester disclosed and claimed in application Ser. No.
491,896, now abandoned, in the presence of a fluorescer compound,
and a solvent. Other suitable chemiluminescent compounds are
3-aminophthalhydrazide, 3,4,5-triphenylimidazole,
10,10'-dialkyl-9,9'-biacridinium salts, and
9-chlorocarbonyl-10-methylacridinium chloride. The latter is
disclosed and claimed in copending application, Ser. No. 427,459,
now U.S. Pat. No. 3,352,791. All of the foregoing provide
chemiluminescence when reacted with a hydroperoxide compound in the
presence of a base. Other chemiluminescent materials are described
by K. D. Gunderman, Angew. Chemie, Int. Ed., 4, 566/1965.
The preferred chemiluminescent compound of this invention is an
oxalic-type ester selected from the group consisting of (a) an
ester of an oxalic-type acid and an alcohol characterized by acid
ionization constant in water greater than
1.3.times.10.sup..sup.-10, and (b) a vinyl ester of an oxalic-type
ester. Similarly, in a preferred embodiment thereof, the alcohol
would be an aromatic alcohol substituted by a substituent
characterized by a positive Hammett sigma value. The preferred
species of oxalic-type esters include
bis(substituted-phenyl)oxalate, such as bis(2-nitrophenyl)oxalate,
bis(2,4-dinitrophenyl)oxalate,
bis(2,6-dichloro-4-nitrophenyl)oxalate, bis(
3-trifluoromethyl-4-nitrophenyl)oxalate,
bis(2-methyl-4,6-dinitrophenyl)oxalate,
bis(1,2-dimethyl-4,6-dinitrophenyl)oxalate,
bis(2,4-dichlorophenyl)oxalate, bis(2,5-dinitrophenyl)oxalate,
bis(2-formyl-4-nitrophenyl)oxalate, bis(pentachlorophenyl)oxalate,
bis(1,2-dihydro-2-oxo-1-pyridyl)glyoxal, bis-N-phthalmidyl oxalate.
The preferred subspecies is bis(2,4,6-trichlorophenyl)oxalate.
The peroxides employed in the components of this invention may be
any hydroperoxide compound. Typical hydroperoxides include
t-butylhydroperoxide, peroxybenzoic acid, and hydrogen peroxide.
Hydrogen peroxide is the preferred hydroperoxide and may be
employed as a solution of hydrogen peroxide in a solvent or as an
anhydrous hydrogen peroxide compound such as perhydrate of urea
(urea peroxide), perhydrate of pyrophosphate (sodium pyrophosphate
peroxide), perhydrate of histidine (histidine peroxide), sodium
perborate, sodium peroxide, and the like. Whenever hydrogen
peroxide is contemplated to be employed, any suitable compound may
be substituted which will produce hydrogen peroxide.
The peroxide concentration may range from about 15 molar down to
about 10.sup..sup.-5, preferably about 3 molar down to about
10.sup..sup.-1 molar. The ester of this invention may be added as a
solid or in admixture with a suitable solid peroxide reactant or in
a suitable diluent, or alternatively dissolved directly in a
solution containing the peroxide reactant.
Typical diluents, which additionally may be used in conjunction
with the necessary diluent of this invention, are those which do
not readily react with a peroxide such as hydrogen peroxide, and
which do not react with an ester of oxalic acid.
Where a solvent is employed with the hydroperoxide-containing
component of this invention said solvent can be any fluid which is
unreactive toward the hydroperoxide and which accommodates a
solubility of at least 0.01 M hydroperoxide. Typical solvents for
the hydroperoxide component include water; alcohols, such as
ethanol or octanol; ethers, such as diethyl ether, diamyl ether,
tetrahydrofuran, dioxane, dibutyldiethyleneglycol, perfluoropropyl
ether, and 1,2-dimethoxyethane; and esters, such as ethyl acetate,
ethyl benzoate, dimethyl phthalate, dioctylphthalate, propyl
formate. Solvent combinations can, of course, be used such as
concentrations of the above with aromatic anisole, tetralin, and
polychlorobiphenyls, providing said solvent combination
accommodates hydroperoxide solubility. However, when oxalic-type
chemiluminescent materials are used, strong electron donor solvents
such as dimethyl formamide, dimethyl sulfonide, and
hexamethylphosphoramide should not, in general, be used as a major
solvent component.
Where a solvent is employed with a component containing the
chemiluminescent material any fluid can be used providing said
fluid solubilizes at least 0.01 M concentration of the
chemiluminescent material and is unreactive toward the
chemiluminescent material. Typical solvents include ethers, esters,
aromatic hydrocarbons, chlorinated aliphatic and aromatic
hydrocarbons, such as those cited in the preceding paragraph. For
oxalic-type chemiluminescent compounds, hydroxylic solvents such as
water or alcohols and basic solvents such as pyridine should not be
employed since such solvents used in general, react with and
destroy oxalic-type chemiluminescent compounds. Solvent
combinations may, of course, be used but such combinations when
used with oxalic-type chemiluminescent compounds should not include
strong electron donor solvents.
When a component comprising a solid chemiluminescent compound and a
solid hydroperoxide is used, the solvent or solvent composition
comprising the second component may vary broadly. Said solvent,
however, should preferably dissolve at least 0.02 M concentrations
of both, the hydroperoxide and the chemiluminescent compound, and
for oxalic-type chemiluminescent compounds, strong electron donor
solvents should be avoided as major solvent components.
The fluorescent compounds contemplated herein are numerous; and
they may be defined broadly as those which do not readily react on
contact with the peroxide employed in this invention, such as
hydrogen peroxide, likewise, they do not readily react on contact
with the chemiluminescent compound.
A fluorescent compound is required for light emission when the
prepared oxalic-type chemiluminescent compound of the invention is
employed. For other types of chemiluminescent compounds a
fluorescer is not required but may be used to shift the wavelength
of emitted light toward the red region of the spectrum so as to
change the color of emitted light. Fluorescent compounds for use
with oxalic-type chemiluminescent compounds should be soluble in
the reactive solvent at least to the extent of 0.0001 moles per
liter.
Typical suitable fluorescent compounds for use in the present
invention are those which have a spectral emission falling between
330 millimicrons and 1,000 millimicrons and which are at least
partially soluble in any of the above diluents, if such diluent is
employed. Among these are the conjugated polycyclic aromatic
compounds having at least three fused rings, such as anthracene,
substituted anthracene, benzanthracene, phenanthrene, substituted
phenanthrene, naphthacene, substituted naphtharene, pentacene,
substituted pentacene, and the like. Typical substituents for all
of these are phenyl, lower alkyl, chlorine, bromine, cyano, alkoxy
(C.sub.1 -C.sub.16), and other like substituents which do not
interfere with the light-generating reaction contemplated
herein.
Numerous other fluorescent compounds having the properties given
hereinabove are well known in the art. Many of these are fully
described in "Fluorescence and Phosphorescence," by Peter
Pringsheim, Interscience Publishers, Inc., New York, New York 1949.
Other fluorescers are described in "The Color Index," Second
Edition, Volume 2, The American Association of Textile Chemists and
Colorists, 1956, pp. 2907--2923. While only typical fluorescent
compounds are listed hereinabove, the person skilled in the art is
fully aware of the face that this invention is not so restricted
and that numerous other fluorescent compounds having similar
properties are contemplated for use herein.
A fluorescent oxalic-type ester, such as the oxalic acid ester of
2-napthol-3,6,8-trisulfonic acid, does not require a separate
fluorescent compound to obtain light. Other typical fluorescent
oxalic acid esters include esters of oxalic acid (1)
2-carboxyphenol, (2) 2-carboxy-6-hydroxyphenol, (3)
1,4-dihydroxy-9,10-diphenylanthracene, and (4) 2-naphthol. Thus, a
reactant including a fluorescent oxalic-type ester would thereby
include at least one fluorescent compound.
It has been found that the molar (moles per liter of diluent)
concentrations of the major components of the novel composition
herein described may vary considerably. It is only necessary that
components be in sufficient concentration to obtain
chemiluminescence. The ester of oxalic acid molar concentration
normally is in the range of at least about 10.sup..sup.-4 to 5
molar, preferably in the range of at least about 10.sup..sup.-3 to
about 1 molar; the fluorescent compound is present in the range
from about 10.sup..sup.-5 to 5, preferably 10.sup..sup.-4 to
10.sup..sup.-1 molar and the diluent must be present in a
sufficient amount to form at least a partial solution of the
reactants involved in the chemiluminescent reaction. If the ester
is liquid, it may serve as either the sole diluent or a partial
diluent.
The ingredients of the composition of this invention may be admixed
in a single stage of admixing or in a sequence of steps of admixing
the separate ingredients.
The wavelength of the light emitted by chemiluminescence of the
compositions of this invention, i.e., the color of the light
emitted, may be varied by the addition of any one or more energy
transfer agents (fluorescers) such as the known fluorescent
compounds discussed at length above.
The wavelength of the light emitted by the composition of this
invention will vary, depending upon the particular fluorescent
component employed in the reaction.
Additionally, it has been found that the superior intensity of
chemiluminescence is obtained when the final mixture producing the
luminescence is maintained at a temperature of between about
-40.degree. C. and 75.degree. C., preferably between about
20.degree. C. and 50.degree. C. However, temperature is not
critical and the luminescence of Applicant's process is not limited
to these ranges.
The lifetime and the intensity of the chemiluminescent light
obtained with the preferred oxalic-type chemiluminescent compounds
of this invention can be regulated by the use of certain regulators
such as:
1. By the addition of base to the chemiluminescent composition.
Both the strength and the concentration of the base are critical
for purposes of regulation.
2. By the variation of hydroperoxide. Both the type and the
concentration of hydroperoxide are critical for the purposes of
regulation.
3. By the addition of water.
4. By the addition of a catalyst which changes the rate of reaction
of hydroperoxide with the oxalic-type ester. Catalysts which
accomplish that objective include those described in M. L. Bender,
"Chem. Revs.," Vol. 60, p. 53 (1960). Also, catalysts which alter
the rate of reaction or the rate of chemiluminescence include those
accelerators of copending application, Ser. No. 577,595, now
abandoned, and decelerators of copending application, Ser. No.
577,615, now abandoned.
While acids are not in general accelerators for oxalic-type
chemiluminescent reactions it should be noted specifically that
acids are accelerators for the oxalic amide chemiluminescent
compounds of copending application, Ser. No. 547,782, now
abandoned.
More specifically, the advantages obtained by the corporation of a
catalyst of Ser. No. 577,595 may be obtained in conjunction with
the objects of this present invention, by employing, according to
the copending application, an ionized salt having a cation selected
from (a) an organic quaternary cation selected from the group
consisting of ammonium, arsenic and phosphorous, and (b) alkali
metal having an atomic weight above 22, the salt of said cation
preferably being soluble in an organic solvent and preferably being
characterized by a property of forming cation-aggregates when
reacted with the oxalic-type ester and a hydroperoxide. One of the
advantages is the fact that an excessive amount of the
chemiluminescent agent may be employed whereby a higher quantum
yield may be obtained when the ionized salt is employed, in
contrast to systems not employing the accelerator whereby such
systems would be limited to a much lower maximum concentration of
chemiluminescent agent which would continue to increase rather than
decrease the total quantum yield of chemiluminescent light.
Similarly, within the scope of the present invention is the
concurrent employment of one or more decelerators either alone in
the composition of this invention, or in conjunction with one or
more of the accelerators discussed in the preceding paragraphs. By
employing one of the accelerators of the preceding paragraph, it
would be possible to employ a greater total concentration of the
chemiluminescent agent while concurrently it would be possible to
employ a decelerator which would prolong the period during which
the light of high intensity is obtained from the chemiluminescent
reaction. Such decelerators set forth in the copending application,
Ser. No. 577,615, now abandoned, include for example a compound
such as oxalic acid.
When oxalate-type chemiluminescent compounds are used in a solution
component it may be desirable to include a stabilizing agent such
as those described in copending application, Ser. No. 614,397.
The chemical compounds, components and their reactions for
providing chemiluminescent light are described in copending,
commonly assigned applications, Ser. Nos. 442,802, now U.S. Pat.
No. 3,329,621; 442,818, now Pat. No. 3,425,949; and those
previously mentioned, and as such they do not form a part of the
present invention.
In this invention, the reactive components are stored in a multiple
compartment container device having a minimum of two compartments,
wherein the separate components may be brought into contact to
produce the reaction which provides chemiluminescent light to be
displayed in said container. When either the chemiluminescent
compounds, hydroperoxide, or both are fluid, they must be in
separate compartments. The diluent and fluorescent compounds can be
in either of these two compartments. If the chemiluminescent
compounds, hydroperoxide and fluorescent compounds are dry powdered
solids, they may be kept together in one compartment with the
diluent in the other compartment. The components in each
compartment are brought together by pressure on the outer tube to
break the inner container, and the combined components may be
dispensed as a chemiluminescent light mixture or used as a source
of light in the transparent container. The light mixture may be
dispensed directly from the container onto any surface by means of
the closure in one end of the outer tube, thus providing visible
light on the surface.
The invention may be better understood by reference to the drawings
in which FIG. 1 shows one outer flexible tube for one embodiment of
the chemiluminescent light device, with a screw cap closure and a
rigid inner tube. FIG. 3 shows one embodiment of the device with a
sealed, tear tip closure. FIG. 4 shows a friction fit cap for the
break tip of FIG. 2.
Referring to FIGS. 1 and 2, the device comprises a flexible tube 1
party threaded at 2 to receive a threaded cap 3 to close opening 4
of tube 1. The opposite end of tube 1 is sealed at 5 by a heat seal
or other suitable means. A sealed inner, rigid tube 6 contains one
chemiluminescent component, such as a hydrogen peroxide solution
and a fluorescer. Tube 1 is filled with the other component of the
chemiluminescent system, previously described, for example the
chemiluminescent compound in a diluent.
Tube 1 is a flexible transparent or translucent material, having
sufficient rigidity to maintain a shape, but sufficiently thin to
be readily flexible, such as low density polyethylene; high density
polyethylene; Teflon FEP Nylon 6; Nylon 6,6; Nylon 6,10; polyester;
polyacrylonitrile; polyvinylidine fluoride; polypropylene; and the
like.
It will be clear to those skilled in the art that blends and
laminates of the above can be used.
The thickness of the tubing will be from about 10 to 30 mils
depending on the material. Polyethylene (low density) is preferred
with a thickness of from about 15--20 mil.
Tube 6 may be a rigid, breakable or frangible material such as
glass, or a relatively brittle thermoset resin, e.g., thin wall
bakelite or other suitable material and need not be transparent or
translucent.
Alternatively tube 6 may be a rupturable pod formed from any of the
plastics used for tube 1. If tube 6 is of the same material as tube
1, it is preferably of less thickness so as to rupture readily
under pressure. The pod 6 may be heat sealed, or sealed by any
other suitable means. In addition, pod 6 could be aluminum foil, or
a laminate of polyethylene and aluminum foil, the aluminum foil
being on the outer side. It will therefore be obvious that pod 6
can be of any material, so long as it is inert to the solution put
in it, and to the solution in tube 1. While the wall areas of tube
1 are fairly thin, so as to be flexible as pointed out previously,
the closure area is somewhat thicker for the threaded and breakoff
tip types. Tube 1 could be molded so as to produce an integral
thicker tip. On the other hand, tube 1 could be made from sections
of extruded tube and separate molded tips which are heat sealed to
the tubular section.
To activate the device and provide light, tube 1 is flexed
sufficiently to break tube 6, allowing its contents to admix with
that of tube 1 to bring about the chemiluminescent reaction and to
obtain a chemiluminescent light mixture within tube 1 and provide
chemiluminescent light emission visible through tube 1. The device
may thus be used in this form as a source of light. If desired, cap
3 may be removed and some or all of the light mixture may be
dispensed through opening 4 to provide a glowing mark on any
surface. In the device shown in FIG. 2, opening 4 is within a
breakoff tip breakable at a scored point 7 for example. The inner
container can be a heat sealed pod 6, sealed into the seal 5 of
tube 1. A friction fit cap 8 may be used for the breakoff tip, as
shown in FIG. 4.
As shown in FIG. 3, the dispensing end of tube 1 may also be heat
sealed as shown at 9. This is done in such a manner that a
dispensing nozzle area 4 remains. A notch 10 is sealed area 9 makes
it possible to tear tube 1 along the line represented by chain line
A-A, thus providing the dispensing nozzle at 4.
Caps 3 and 8 may be formed of any plastic or other material inert
to the chemiluminescent solutions.
The device may have more than one breakable tube 6, so that more
than two chemiluminescent components may be kept separated. Such a
system is useful where rate regulators such as acidic or basic
materials may be used in the reaction.
The color of the light emission will depend on the type of
fluorescent compound and its spectral response. However, the
visible color could be varied by using a colored plastic for tube
1.
The invention provides a device for providing visible light
whenever and wherever desired, independent of conventional
electrical lighting methods and without the hazards and limitations
of electrical lighting. The chemiluminescent lighting systems can
be especially useful in emergency situations where all other forms
of lighting have failed. The systems do not have the fire of
ignitable lighting devices such as candles, gas, or oil lights.
It will be readily apparent that the chemiluminescent device is not
confined to emergency lighting, however. It can be used at any time
where a cold, safe illuminating means is desired. It is also useful
to provide illumination where electrical illumination is
unavailable. The device is highly portable and can be hand held for
signalling.
While certain specific embodiments and preferred modes of practice
of the invention have been describe, it will be understood that
this is solely for illustration, and that various changes and
modifications of the invention may be made without departing from
the spirit of the disclosure or the scope of the appended
claims.
* * * * *