U.S. patent number 3,683,336 [Application Number 04/848,686] was granted by the patent office on 1972-08-08 for formation of visible and/or fluorescent images.
This patent grant is currently assigned to American Cyanamid Company, Stamford, CT. Invention is credited to Ken Matsuda, Thomas Harland Brownlee.
United States Patent |
3,683,336 |
|
August 8, 1972 |
FORMATION OF VISIBLE AND/OR FLUORESCENT IMAGES
Abstract
Method of processing information by the use of derivatives of
aromatic compounds which do not fluoresce, but which may be
converted to fluorescent compounds by the action of heat or short
wave ultraviolet radiation, and reconverted to the original
non-fluorescent form by longer wavelength ultraviolet radiation. 8
Claims, No Drawings
Inventors: |
Thomas Harland Brownlee
(Westport, CT), Ken Matsuda (Stamford, CT) |
Assignee: |
American Cyanamid Company,
Stamford, CT (N/A)
|
Family
ID: |
25304002 |
Appl.
No.: |
04/848,686 |
Filed: |
August 8, 1969 |
Current U.S.
Class: |
430/332; 250/302;
252/301.35; 427/157; 430/346; 252/301.16; 365/106; 365/119;
430/340; 250/484.4 |
Current CPC
Class: |
B41M
5/28 (20130101); G03C 1/73 (20130101) |
Current International
Class: |
B41M
5/28 (20060101); G03C 1/73 (20060101); G11c
013/04 (); G11c 011/42 () |
Field of
Search: |
;250/71R,71T
;117/1,93.3,33.5R ;346/135 ;96/45.1 ;252/301.2,301.3
;340/173LS,173CC |
Other References
badger, Structures and Reactions of the Aromatic Compounds,
Cambridge .
Univ. Press, London, 1954, 364-377. .
Mouneu et al., Compt. issued 186 (1928). p. 1166-1168. .
Southern et al., J. Chem. Soc., 1960, 4340-4346..
|
Primary Examiner: Alfred L. Leavitt
Assistant Examiner: Wm. E. Ball
Attorney, Agent or Firm: Charles J. Fickey
Claims
1. A process which comprises applying a differential energy pattern
to a member containing a polycyclic aromatic compound having an
oxidized and reduced state, said compound being fluorescent in one
of said states, said energy being from between about 3 .times.
10.sup.- .sup.2 A. to 3.0 .times. 10.sup. 3 A. and between about 7
.times. 10.sup. 3 A. and 3 .times. 10.sup. 5 A. wavelength in the
electromagnetic spectrum, said application being sufficient to form
a differential pattern on said
2. The process of claim 1 wherein said polycyclic aromatic compound
is an
Description
This invention relates to a new method of forming detectable
information. It more definitely relates to the formation of images
which are fluorescent under ultraviolet radiation, by the
application of suitable energy to aromatic polycyclic compounds
which are not fluorescent.
Numerous imaging systems are known based on the thermal or photo
conversion of chemical compounds from one color to a different
color or from a colorless state to a colored form. Most of these
methods are mainly permanent conversions, i.e., the compounds once
exposed to radiation and converted in form, cannot be returned to
their original form. Moreover, most such systems depend on a
visible change in form so that they are only useful where the final
image can be left in its permanent form and position.
We have now found that images may be formed by the application of
suitable energy to polycyclic aromatic type compounds, such as
endoperoxides, according to the following equation, using
9,10-diphenyl anthracene as an example: ##SPC1##
Some endoperoxides are fluorescent and the fluorescence and color
and intensity will change with irradiation. The images which are
formed are fluorescent and detectable under suitable long wave
ultraviolet radiation and may or may not be visible. The process is
also reversible, so that the fluorescent image may be erased, and a
new image formed. This cycle may be performed any number of
times.
The endoperoxide compounds may be incorporated with numerous
substrates and matrixes such as paper or various plastics, by
coating, impregnation or compounding. Excellent results can be
obtained with only from about 0.05 to 0.1 mg. of the active
compound per square centimeter of paper surface.
A large variety of fluorescent colors can be achieved depending on
the specific aromatic endoperoxide or other aromatic employed. Such
colors range from blue (9,10-diphenyl-anthracene) to orange
(rubrene).
The requisite energy for the conversion of the endoperoxides and
formation of images may be applied in different ways. It may be
done by the physical contact of a hot die to the substrate
incorporating the endoperoxide. In this instance, the die will have
the shape of the desired image. A temperature of from about
20.degree. to 200.degree. C., preferably 150.degree. to 200.degree.
C., is suitable. Images can be produced in from 1 to 3 seconds at
higher temperatures. The time and temperature will be variable
depending on the substrate material and effect desired.
The substrate could also be irradiated by an imagewise pattern of
infrared radiation, or short wave ultraviolet radiation of about
2,000 to 3,000 A. wavelength. Energies of about chemical
joules/cm.sup.2 have been found adequate. The radiant source may be
of various types providing ultra-violet or infra-radiation,
including lamps, electric arcs, or ultra-violet and infra-red
lasers. The image can be formed in any well-known manner as by
focusing a radiant beam, projecting a beam through a stencil, by
use of moving mirror systems with lasers and the like. Other forms
of radiation may also be used such as X-rays, electron bombardment,
cathode rays, ionizing radiation, and the like. When infrared
radiation is used, it is advantageous to incorporate
infrared-absorbing agents such as charcoal, or chemical absorbers,
with the aromatic polycyclic imaging compounds.
For reversing the process and erasing the image, the aromatic
compound is irradiated with long wave ultraviolet light, most
advantageously of 3,500 A. wavelength, in the presence of air or
oxygen to cause conversion of the aromatic compound to the original
aromatic endoperoxide. The same types of irradiating sources may be
used.
Although it has been indicated that a fluorescent image could be
produced by application of energy in the form of heat, or infrared
or ultraviolet radiation to the reducible aromatic compound, it
will be readily apparent that an image could be created in the
reverse manner. In this way, the aromatic compounds may be present
on a substrate in the reduced state, i.e., the fluorescent state.
Irradiation with a differential pattern of long wave ultraviolet
(about 3,500 A.) light in the presence of air or oxygen will bleach
parts of the substrate to give a non-fluorescent image on a
fluorescent back ground.
In all the imaging methods, the image can be any type of mark,
signal, or intelligence, and be of either of the types
conventionally known as positive or negative image. Moreover, it
may simply consist of areas of varying fluorescent intensity. Since
the present material has a further characteristic that the amount
of detectable fluorescence is proportional to the amount of latent
fluorescer which has been converted to the fluorescent state, the
amount converted on any radiated area depends on the duration of
time of exposure to the irradiating energy. The longer the time
period is, the more latent fluorescer there will be converted per
unit of exposed area and thus the more intense the fluorescence
upon subsequent radiation and detection. This characteristic makes
it possible to produce detectable, variable tone fluorescent
radiation over a given area. This is much like the tone variation
in a photographic negative or a magnetic sound tape. Thus the
present invention could be used to prepare a sound tape by audio
modulation of the radiant source. The sound is detectable by
conventional fluorescent detection means coupled with audio output
means by a suitable transducer. A sound track could be put on a
movie film in the same manner, either beside the picture, or
pointed directly on the film. A phonograph disc could be prepared
and played by the same principal.
It will be obvious that the process may be used in various ways for
imaging. For example a substrate may incorporate the aromatic
compound and an image formed thereon. The image may be erased and a
new image put on. If the initial endoperoxide and the image are
colorless, a system is provided whereby information is not apparent
to the ordinary observer, but is detectable under ultraviolet
radiation when in the fluorescent form. Such a system would be
useful for putting additional information on top of other
information, which was ordinarily visible, for example, recognition
codes or signals on microfilm or labels, and the like.
It is also possible to put the endoperoxide compounds onto a
surface in a printed form, i.e., only in image areas and to
activate them to the fluorescent form and reverse when
desirable.
In some instances, the aromatic compounds of the invention will be
colored in either one or the other form, and the process is
sometimes irreversible depending on the substrate associated with
the endoperoxide.
It will be obvious that many variations will be suggested within
the purview of the process of this invention. For example, a
printing ink could be made incorporating the endoperoxides of the
invention. Thus, the present invention can be useful in coding all
types of articles, for control, etc., data storage, acquisition and
display, printing, coded inks, novelties, toys, and many other
uses.
In general, any compound capable of forming an endoperoxide will
work in this system as long as this endoperoxide is decomposable
under the types of energy previously discussed, to a colored and/or
fluorescent product.
Some of the names used in the literature to describe these cyclic
peroxides include: transannular peroxides.sup.(2) , 1,4-
peroxides.sup.(2), photo-oxides.sup.(3), photo-peroxides.sup.(3),
transannular epidioxides.sup.(4), 1,4-epiperoxides.sup.(8),
aromatic peroxides (with or without numbers to indicate the
positions involved, i.e.,
9,10-dimethylanthracene-9,10-peroxide.sup.(5) or
9,10-dimethylanthracene peroxide, also rubrene peroxide),
endoperoxides.sup.(5)(7) (or endoperoxides.sup.(1B)), (also with or
without numbers, i.e., 9,10-diphenylanthracene-9,10-endoperoxide or
9,10-diphenylanthracene endoperoxide) and dioxabicyclo
systems.sup.(6) (i.e., 5,6-dioxabicyclo-[2.2.2.]octene-2: (see
literature references below.)
For the reversible system, the heat generated image can be
converted back to the endoperoxide. This is usually accomplished by
U.V. light and air. Using 9,10 -diphenylanthracene endoperoxide as
an example, the reactions are: ##SPC2##
For the irreversible system, the heat generated image can not be
converted back to the starting endoperoxide. Thus, the image
produced by heating the endoperoxide may be an oxidation product
(quinone, etc.) for other fluorescent decomposition product not
capable of being converted to colorless and non-fluorescent
material. Also, a normally reversible system can be made
irreversible by preventing oxygen from reacting with the aromatic
(see Table I).
Numerous aromatic endoperoxide compounds are disclosed in the
following literature references: 1A. Phenomenon observed in 1867 by
Fritzsche using naphthacene. Fritzsche, Compt. rend., 64,
1035(1867). 1B. E. McKeown and W. A. Waters, J. Chem. Soc.,
1040B(1966). 1. c. moureu, C. Dufraisse and P. M. Dean, Compt.
rend., 182, 1440, 1584(1926). C. Moureu, C. Dufraisse and L.
Girard, Compt. rend., 186, 1027(1928). 2. W. Bergmann and M. J.
McLean, Chem. Revs., 28, 367(1941). 3. G. M. Badger, "Structure and
Reactions of Aromatic Compounds", Cambridge Univ. Press, London
(1954), Chap. 9, pp. 364-382. 4. Yu. A. Arbuzou, Russ. Chem. Revs.,
34, 558(1965). 5. E. J. Corey and W. C. Taylor, J. Am. Chem. Soc.,
86, 3881(1964). 6. C. S. Foote and S. Wexler, J. Am. Chem. Soc.,
86, 3879(1964). 7. E. G. E. Hawkins, "Organic Peroxides, Their
Formation and Reactions", E. and F. F. Spon Ltd., London, 1961. 8.
A. G. Davies, "Organic Peroxides", Butterworths, London, 1961. 9.
Technical Report No. 3, "Chemiluminescent Material", Dec.
1,1963-Feb. 29, 1964, ARPA No. 299 Amed. 3, Contract Nonr.
4200(00), Task NR 365-452, pp. 18, 19.
The initial endoperoxide may be prepared using U.V. light in the
presence of air or oxygen.sup.(1,2,3,4) (with or without a
sensitizer), chemical synthesis.sup.(1B,6), or with active oxygen
prepared by electrodeless discharge.sup.(5).
A variety of compounds containing a 1,3-diene structure are known
to give peroxides: ##SPC3## The most useful class of compounds for
this invention is the aromatic acenes and their derivatives i.e.,
anthracene, naphthacene, pentacene, hexacene, etc.).
Additional aromatic endoperoxides within the scope of this
invention are disclosed in "Organic Chemistry, A Series of
Monographs", Vol. 8, J. Hamer, ed., 1967, p. 299: Anthracene
Endoperoxides p. 374; ref. (3) p. 385; ref. (2) pp. 18, 19; ref.
(9) p. 369; ref. (3) Tetracene Endoperoxides p. 238; ref. (7) p.
384; ref. (2) Pentacene Endoperoxides p. 382; ref. (2) and p. 238;
ref. (7) Hexacene Endoperoxides -- p. 367; ref. (3)
Larger polynuclear aromatic endoperoxides are known as follows:
##SPC4## C. dufraisse and M. T. Mellier, Compt. rend., 215,
576(1942). ##SPC5## ##SPC6##
Other polycyclic hydrocarbons that can be converted to
endoperoxides are: 1,2-benzoanthracenes, rubrene, napthacene,
9,10-diphenylnaphthacene,
1,2,3,4-tetradhydro-9,10-diphenylnaphthacene,
9,11-diphenyl-10,12-bis- (biphenyl)naphthacene,
2,6,10,12-tetraphenyl-9,11- bis(biphenyl)naphthacene (A),
1,2,8,9-dibenzpentacene, heterocoerdianthrone (B), and the three
isomeric p-toly- tetraphenylcyclopentadienols. ##SPC7## p. 239;
ref. (7) and p. 370; ref. (3): ##SPC8## Bis-endoperoxide of
9,9',10,10' -tetraphenyl-1,1'dianthryl. Endoperoxides obtained from
1,3-diene derivatives: (While the following cyclic peroxides are
known, it is not known whether they will produce color or
fluorescence upon heating.) ##SPC9##
Other endoperoxides derived from 1,3-diene derivatives, p. 93; ref.
(8): ##SPC10##
Also endoperoxides were prepared from: 24-methyl-cholesta-5,7-dien-
3.beta.-ol, 3.beta.-acetoxy-24-methylcholesta-6,8(14),
9(11),22-tetraene, 3-acetoxy-2-methylcholesta-3,5,7,22-tetraene,
3-acetoxy-24-methylcholesta- 3,5,7,9(11),22-pentaene,
3-acetoxy-5.alpha.-pregna-6,8(14),9(11)-trien-20-
one,3.beta.,21-diacetoxy-5.alpha.-pregna-6,8(14),9(11)-triene-20-one,
lumisteryl acetate, cholesta-5,7-diene-3.beta.-ol, 3.beta.-
acetoxycholesta-5,7-diene, cholesta-5,7,24-trien-3.beta.-ol,
cholesta-2,4-diene, cholesta-1,3,5-triene-7-one,
androsta-5,7-diene-3,17- diol.
Other derivatives of polycyclic aromatic compounds may be useful
provided they have an oxidized and a reduced state and are
fluorescent in one such state, and are capable of being changed
from one state to the other by the application of suitable energy.
By oxidized and reduced state is meant a polycyclic aromatic
compound having at least one ring with a diene structure which is
capable of being converted to a monoene structure by 1,4 addition
to the ring. The endoperoxides of anthracene are illustrative, as
previously pointed out. In addition, halogen derivatives of
anthracene would also be applicable, for example.
The following specific examples are given to illustrate the
invention and are not intended to be limitative.
EXAMPLE I
The 9,10-diphenylanthracene endoperoxide (DPA.sup.. 0.sub.2 ) was
prepared from commercially available 9,10-diphenylanthracene as
follows: 9,10-Diphenylanthracene Endoperoxide
Potassium hydroxide (12 g. ) was added slowly one-half hour) to 37
ml. of 30 percent hydrogen peroxide with stirring at .degree. C.
(ice-water bath). A solution of 1.01 g. (3 mM)
9,10-diphenyl-anthracene in 50 ml. of chlorobenzene was added to
the reaction vessel. The mixture was stirred gently, so that the
boundary between the two liquid phases was not broken and bromine
(5ml.) in chloroform (5 ml.) was added to the lower
(aqueous-KOH--H.sub.2 0.sub.2 ) phase through a capillary tube
during a period of 4 hours. The organic phase was separated from
the aqueous phase and washed with water. The organic solution was
concentrated under reduced pressure to a yellow mud. This material
was chromatographed on F-20 Alumina (eluted with 50:50
n-hexane:benzene). After recrystallization from n-hexane/benzene,
0.612 g. (55percent yield) of 9,10-diphenylanthracene endoperoxide
and 0277 g. (27percent recovered) 9,10-diphenylanthracene was
obtained.
A solution of DPA.sup.. 0.sub.2 in an organic solvent (such as
benzene) was allowed to dry on non-fluorescent paper to leave 0.05
mg. to 0.1 mg. of DPA.sup.. 0.sub.2 per square centimeter. An image
was rapidly produced by applying a heated object of about
200.degree. C. The images were bright blue fluorescent and had no
visible color. If too hot an object or too long a contact time was
used, then the image was transferred to the underlying substrate
(paper). Higher concentrations of DPA.sup.. 0.sub.2 gave images
which were yellow colored and blue fluorescent.
The images produced on paper coated with DPA.sup.. 0.sub.2 were
bleached after 15 minutes to 1/2 hour exposure to 3,500 A.
ultraviolet light in air (Rayonet Photochemical Reactor). Also some
fading of the blue fluorescent images was observed after 4 days in
the direct afternoon sunlight. New images were produced on the
above papers by reapplying the heated objects. One treated paper
was carried through six cycles.
EXAMPLE II 1-methoxy-9,10-diphenylanthracene endoperoxide as
described in C. Dufraisse, L. Velluz, R. Demuynck, Compt. rend.
215, 111(1942).
A benzene solution of this endoperoxide was allowed to dry on a
piece of white, non-fluorescent paper to leave a colorless,
non-fluorescent circle. Heated (150.degree.-200.degree. C.) objects
(i.e., keys, metal with raised letters, etc.) developed blue-green
fluorescent images (no visible color) when placed on the treated
paper for less than a second. Higher temperatures or longer contact
time caused the fluorescent (no visible color) images to be
transferred to the material (paper) under the treated paper. These
images were bleached in the Rayonet Photochemical Reactor at 3,500
A. in 15 minutes. No new images could be developed by heated
objects in the areas where the first images were. Good images were
formed in areas where no first images were.
EXAMPLE III
9,10-bis(phenylethynyl)anthracene
A benzene solution of this compound was allowed to dry on a piece
of white (non-fluorescent) paper to leave a slightly orange-colored
and yellow-fluorescent circle. The endoperoxide was formed by
irradiating the paper for 15 minutes in the Rayonet Photochemical
Reactor at 3,500 A. The yellow-green fluorescence was bleached but
the paper was still slightly orange. Heated (about 200.degree. C.)
objects (keys, etc.) placed on this paper developed yellow-colored
and yellow-green fluorescent images in about 1 second. The
yellow-colored and yellow-green fluorescent images were also
transferred to ordinary paper by using longer contact time (2-4
seconds) or higher temperatures. These images could be bleached by
3,500 A. ultraviolet light but new images were difficult to produce
on top of bleached images.
9,10-Bis(phenylethynyl)anthracene may be prepared as described by
W. Ried, W. Donner and W. Schlegelmilch, Ber., 94, 1051(1961).
EXAMPLE IV rubrene
A benzene solution of rubrene was allowed to dry on white,
non-fluorescent paper to leave a pink-colored and orange
fluorescent circle. The pink color and orange fluorescence was
bleached in two minutes by ultraviolet irradiation (3,500 A.) in
air (Rayonet Photochemical Reactor), thus forming the endoperoxide.
When heated (about 200.degree. C.) objects (keys, etc.) were placed
on this bleached paper, a pink-colored and orange fluorescent image
was formed in less than one second. These images were similarly
bleached in a few minutes by ultraviolet irradiation (3,500 A.) in
air. Ordinary fluorescent laboratory light, also bleached the
images slowly. The process was repeated three times on the same
coated paper. Lower temperatures and/or shorter contact times of
the heated objects produced only the orange fluorescent image (no
visible color). These transformations can again be explained by the
reversible formation of the endoperoxide.
Images were also transferred to an underlying substrate when hotter
objects and/or longer contact times were used.
EXAMPLE V ##SPC11## 5,12-bis(phenylethynyl)tetracene
5,12-Bis(phenylethynyl)tetracene was prepared as follows: As
disclosed in copending commonly assigned application Ser. No.
712,922, filed Mar. 14, 1968. A benzene solution of this compound
was allowed to dry on a piece of white (non-fluorescent) paper to
leave a dull gray and slightly orange fluorescent circle. Dilute
concentrations of this compound on paper were almost colorless and
slightly orange fluorescent. The endoperoxide was formed more
easily on this paper since the orange fluorescence was bleached
slowly in air by laboratory fluorescent light and more rapidly (5
to 10 minutes) in the Rayonet Photochemical Reactor at 3,500 A.
Heated (about 200.degree. C.) objects (keys, etc.) rapidly (1-3
seconds) generated red visible colored and orange fluorescent
colored images on this paper. If lower temperature objects were
used, then only the orange fluorescent images were formed. These
images were also transferred to untreated paper (as in the above
cases) by using slightly hotter objects or longer contact time. The
images were bleached in Rayonet Photochemical Reactor at 3,500 A.
in 15 minutes. This was a reversible system since one treated paper
was carried through six cycles.
EXAMPLE VI 1,2,8,9-dibenzpentacene, obtained commercially from L.
Light & Co., Ltd., Colnbrook, England.
A benzene (or xylene) solution of this compound was allowed to dry
on a piece of white, non-fluorescent paper to leave a colorless and
non-fluorescent circle. Higher concentrations of the compound on
paper were slightly purple colored and non-fluorescent. Ordinary
fluorescent laboratory light caused formation of the
non-fluorescent endoperoxide. The endoperoxides were also formed by
ultraviolet radiation (3,500 A., Rayonet) in 5 minutes. Heated
(about 200.degree. C.) objects (keys, etc.) rapidly (1-3 seconds)
produced yellow fluorescent and colorless images. These images were
bleached slowly by the fluorescent laboratory lights and in 5
minutes in the Rayonet Photochemical Reactor at 3,500 A. to form
the endoperoxide again. Heated objects again formed the fluorescent
images on this paper. As in the other cases, hotter objects or
longer (2-4 seconds) contact time transferred the yellow
fluorescent (no visible color) images to untreated paper or any
substrate used under the treated paper.
The results of Examples I to VI are summarized in Table I.
EXAMPLE VII
Other aromatic derivatives (in addition to the endoperoxide) may be
useful for imaging by heat or ultraviolet light. Thus, an attempt
to prepare the endoperoxide of BPEA
(9,10-bis(phenylethynyl)anthracene) using the procedure described
for DPA.sup.. 0.sub.2 [E. McKeown and W. A. Waters, J. Chem. Soc.,
1040B(1966)] gave a small amount of non-fluorescent material which
had an infrared and mass spectrum indicating: ##SPC12##
A small amount of this material was dissolved in benzene and the
solution allowed to dry on filter paper to leave a colorless and
non-fluorescent circle. When a heated (about 200.degree. C.) object
was placed on the treated paper (about 1 second), a yellow-green
fluorescent image was produced. Longer contact time caused the
image to be transferred to the underlying substrate.
The images were bleached by 3,500 A. ultraviolet (10 minutes,
Rayonet Photochemical Reactor) and yellowish fluorescent images
regenerated by the heated objects.
A high molecular weight polyethylmethacrylate (PEMA) film
containing a small amount of the above dibromo compound was weakly
yellow colored and not fluorescent. Irradiation with 2,537 A.
ultraviolet light (H100 A4/T Mercury lamp with pyrex envelope
removed) for 1-2 minutes produced yellow colored and greenish
fluorescent images in the film. Applying the heated (about
200.degree. C.) objects also produced similar images in this
film.
The following reactions are also useful in the same manner:
##SPC13## H. cerfontain, J. Chem. Soc., 6602(1965).
THERMAL IMAGING OF PLASTIC FILMS CONTAINING AN AROMATIC
ENDOPEROXIDE
EXAMPLES VIII TO XVI
Plastic films were prepared containing DPA.sup.. 0.sub.2 .
All the films were solvent cast on glass microscope slides (except
PVA). Each film of Examples VIII to XIII contained less than 40 mg.
DPA.sup.. 0.sub.2 per gram of polymer. The films of Examples XIV to
XVI contained compounds as indicated. The images were developed by
applying a heated (150.degree.-200.degree. C.) key to the sample
for approximately 1-2 seconds. All the samples became soft and
sticky, and some (see Table II) became brown when too hot
(>200.degree. C.) an object was used. The bleaching studies were
performed in the Rayonet Photochemical Reactor with 3,500 A.
ultraviolet lamps.
EXAMPLE VIII
PEMA: High molecular weight polyethyl methacrylate, Elvacite 2042,
DuPont Chemical Co. The films were cast from a mixture of toluene,
methyl-ethyl-ketone and ethanol. The imaging (by the heated key)
and bleaching (by 3,500 A. U.V.) was repeated three times on one
area of the film.
EXAMPLE IX
CAB: Cellulose acetate butyrate, EAB-380-20, Eastman Chemical Co.
The films were cast from acetone.
EXAMPLE X
VAGH: Bakelite, vinyl chloride-acetate copolymer with about 91
percent vinyl chloride. The films were cast from a mixture of
acetone and methyl ethyl ketone.
EXAMPLE XI
PVC: Polyvinyl chloride. The films were cast from methylene
chloride.
EXAMPLE XII
PVA: Polyvinyl alcohol, Elvanol 71-30, DuPont Chemical Co. The
films were cast from a mixture of ethanol and water. An attempt to
dry the film under reduced pressure gave large tough bubbles, which
were cut into samples for testing.
EXAMPLE XIII
H-15 Acrylite: The films were cast from benzene.
EXAMPLE XIV
A clear, colorless and weakly fluorescent H-15 Acrylite film
(American Cyanamid Co. polymethyl methylacrylate) containing 6
percent by weight of 1-methoxy-9,10-diphenylanthracene endoperoxide
gave a colorless but good blue fluorescent image (and bubbles) when
the heated key was applied.
EXAMPLE XV
A clear, weakly yellow colored and weakly blue fluorescent PEMA
film containing 1 percent by weight BPET endoperoxide gave an
orange-pink colored and orange fluorescent image (and bubbles),
when the heated key was applied. This image was bleached after one
day in the laboratory fluorescent lights. The initial endoperoxide
was also prepared by exposing the PEMA-BPET film to the laboratory
lights for four days.
EXAMPLE XVI
A clear, weakly yellow-colored and weakly blue fluorescent PEMA
film containing 1 percent by weight rubrene endoperoxide gave a
pink-colored and yellow-orange fluorescent image (and bubbles),
when the heated key was applied. The image was bleached, and the
endoperoxide prepared as described above for the perma-B BPET
film.
The results of thermal imaging are illustrated in Table II for
Examples VIII to XIII. As may be seen, the system can be reversible
or irreversible depending on the plastic matrix.
IMAGING BY INFRARED IRRADIATION OF PEMA FILMS CONTAINING DPA.sup..
O.sub.2
EXAMPLES XVII to XXII
All the films were prepared with high molecular weight polyethyl
methacrylate (PEMA) of Example VIII and were cast on glass slides
from a mixture of acetone, methyl-ethyl-ketone, toluene and
ethanol. The infrared absorbers (Cyasorb IR-117 and Cyasorb IR-165)
are products of American Cyanamid Company. All the tests were
performed by holding the sample about 5 inches from a 250W, G.E.
infrared bulb. The additives increased the sensitivity of the
system to infrared light in the following order: None <IR-117
<IR-165 <charcoal. Lower ##SPC14## concentrations of the
additives were still effective as sensitizers for this system.
The reversibility study was performed with Example XVIII. Thus,
colorless but good blue fluorescent images were produced by
irradiation for 1-2 minutes with the 250W. G.E. infrared light bulb
(sample about 3 inches from the bulb). The images were bleached
after 15-45 minutes irradiation with 3,500 A. U.V. light (Rayonet
Photochemical Reactor). This process of imaging and bleaching was
repeated 12 times. After this series, the film was still colorless
(except for the black charcoal particles).
The results are shown in Table III.
An additional PEMA film containing 3 percent DPA.sup.. 0.sub.2 was
cast from toluene, methyl-ethyl-ketone and ethanol and was clear,
colorless and weakly fluorescent. When irradiated by infrared as
above at 7 cm. for 2 to 5 minutes, a colorless but blue fluorescent
image was produced.
IMAGING BY ULTRAVIOLET IRRADIATION OF FILMS CONTAINING DPA.sup..
0.sub.2
EXAMPLES XXIII to XXIX
The films were the same ones as used in the thermal imaging in
Example XIX, containing 20-50 mg. DPA.sup.. 0.sub.2 per gram of
polymer. The 2,600 A. and 3,000 A. light was obtained from a 450W
Xenon lamp in conjunction with a B & L Monochromator (No.
33-86-07) and water filter. The intensity of the light at 2,600 A.
was 0.2 mW/cm.sup.2 and at 3,000 A. it was 1.14 mW/cm.sup.2. The
2,537 A. light was obtained from a 100 W mercury lamp (H100 A4/T
with the Pyrex envelope removed. The 3,500 A. light was obtained
with the Rayonet Photochemical Reactor using 3,500 A. bulbs. None
of the images had any visible color (just the blue
fluorescence.
The images produced in Examples XXIII to XXIX were bleached by
3,500 A. ultraviolet radiation. ##SPC15##
The results are shown in Table IV.
EXAMPLE XXX
A film containing 2.7 percent by weight of DPA.sup.. 0.sub.2 in
H-15 Acrylite Molding Compound was prepared by allowing a methylene
chloride solution to dry on a glass slide. The dried film was
clear, colorless and only very weakly blue fluorescent. After
irradiating the film for about 1 sec. with 2,537 A. ultraviolet
light (same lamp as in Example XXVIII), a colorless but good blue
fluorescent image was produced.
EXAMPLE XXXI
A film containing 2.3 percent by weight of DPA.sup.. 0.sub.2 in
H-15 Acrylite Molding Compound was prepared by allowing an acetone
solution to dry on a glass slide. The dried film was clear,
colorless and only faintly blue fluorescent. After irradiating the
film for about 1 second with 2,537 A. ultraviolet light (same lamp
as above) a colorless but good blue fluorescent image was produced.
A stronger blue fluorescent (and colorless) image was produced
after 5 seconds ultraviolet irradiation at 2,537 A. The intensity
of the blue fluorescent image was reduced after 1/2 hour
irradiation at 3,500 A. (Rayonet Photochemical Reactor).
A second exposure to 2,537 A. ultraviolet light for 5 seconds
increased the intensity of the blue fluorescence slightly. A blue
fluorescent image still remained (only slightly reduced intensity)
after 3 hours in 3,500 A. ultraviolet light (Rayonet Photochemical
Reactor). A third exposure to 2,537 A. ultraviolet light for 5
seconds only slightly increased the intensity of the image. Again,
the blue fluorescent image remained after 2-hour exposure to 3,500
A. ultraviolet light. A fourth exposure to 2,537 A. ultraviolet
light for 5 seconds increased the intensity of the image only very
slightly. Another 11/2 hours of ultraviolet irradiation at 3,500 A.
only caused a slight reduction in the intensity of ##SPC16## the
blue fluorescence of the image. The image was slightly yellow
colored after all the above irradiations. Since the image could not
be bleached, this is an example of a one-way system.
EXAMPLE XXXII
A film containing 3.4 percent by weight of DPA.sup.. 0.sub.2 in
H-15 Acrylite Molding Compound was prepared by allowing a benzene
solution to dry on a glass slide. The dried film was clear,
colorless and only weakly blue fluorescent. After irradiating the
film for about 1 second with 2,537 A. ultraviolet light, a
colorless but good blue fluorescent image was produced. The
Examples XXX, XXXI, and XXXII show that the system is not dependent
upon the solvent used to cast the film.
EXAMPLE XXXIII
A film containing 3 percent by weight of DPA.sup.. 0.sub.2 in high
molecular weight polyethyl methacrylate (Elvacite 2042) was
prepared by allowing a benzene-toluene-methyl ethyl ketone solution
to dry on a glass slide. The dried film was clear, colorless, and
only faintly blue fluorescent. After irradiating the film for about
1 second with 2,537 A. light, a colorless but very good blue
fluorescent image was produced. Another colorless but good
fluorescent image was produced by irradiating the film for 5 sec.
with 2,537 A. ultraviolet light. This image was completely bleached
after 15 minutes irradiation with 3,500 A. ultraviolet light
(Rayonet Photochemical Reactor). This process of imaging and
bleaching was repeated 21 times on the same area of the film. The
resulting film was still colorless. This is an example of the
reversible formation of colorless but blue fluorescent images by
ultraviolet light.
EXAMPLE XXXIV
A film containing 6 percent by weight of 1-methoxy-9,10-
diphenylanthracene endoperoxide in H-15 Acrylite Molding Compound
was prepared by allowing a benzene solution to dry on a glass
slide. The dried film was clear, colorless and faintly blue
fluorescent. After irradiating the film for about 1 second with
2,537 A. ultraviolet light, a colorless but good blue fluorescent
image was produced.
EXAMPLE XXXV
A film containing 10 percent by weight of DPA.sup.. 0.sub.2 in high
molecular weight polyethyl methacrylate was prepared as described
in Example XIII with the exception that this film was cast on 3 mil
bond-coated Mylar. The dried film was clear, colorless, weakly blue
fluorescent, and 1.5 mils thick. Five different colorless but blue
fluorescent images were produced on this film by irradiation with
2,537 A. ultraviolet light for different lengths of time.
Image No. 1: 1-2 Seconds of exposure gave colorless and weakly blue
fluorescent image.
Image No. 2: 5 Seconds of exposure gave colorless and stronger blue
fluorescent image.
Image No. 3: 20 Seconds of exposure gave colorless and still
stronger blue fluorescent image.
Image No. 4: 40 Seconds of exposure gave colorless and only
slightly stronger blue fluorescent image.
Image No. 5: 1 Minute of exposure gave colorless and blue
fluorescent image of same intensity as in No. 4.
Image No. 5 was completely bleached after 10 minutes of irradiation
with 3,500 A. ultraviolet light. This image No. 5 (as well as all
the other [Nos. 1 - 4]) remained colorless after the above
irradiations.
EXAMPLE XXXVI
A benzene solution of DPA.sup.. 0.sub.2 was allowed to dry on paper
to leave a colorless, non-fluorescent circle containing
approximately 0.1 mg. DPA.sup.. 0.sub.2 per cm.sup.2. Irradiating
the paper for 1-2 seconds with the 2,537 A. U.V. light at a
distance of 5 inches (of Example XXVIII) gave a blue fluorescent
and slightly yellow-colored image. The image was completely
bleached after 15 minutes exposure to 3,500 A. U.V. light
(Rayonet), and the cycle repeated four times.
While we have set forth certain specific embodiments and modes of
practice of the invention, it will be understood that this is
solely for the purpose of illustration and that various changes and
modifications may be made without departing from the scope of the
disclosure or spirit of the appended claims.
* * * * *