U.S. patent number 3,904,420 [Application Number 05/395,792] was granted by the patent office on 1975-09-09 for information receiving element containing a yellow dye and an optical brightener.
This patent grant is currently assigned to Eastman Kodak Company. Invention is credited to C. Shelburn Hunter.
| United States Patent |
3,904,420 |
| Hunter |
September 9, 1975 |
| **Please see images for:
( Certificate of Correction ) ** |
Information receiving element containing a yellow dye and an
optical brightener
Abstract
An element comprising a support that transmits visible
radiation, a radiation sensitive layer, and containing both an
optical brightener and a yellow dye which, together, absorb
radiation in the range from about 300 to about 460 nm. The element
is useful for providing a microfilm from which an image cannot be
duplicated by the diazo process.
|
Inventors: |
Hunter; C. Shelburn (Rochester,
NY) |
|
Assignee: |
Eastman Kodak Company
(Rochester, NY)
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| Family
ID: |
26963176 |
| Appl.
No.: |
05/395,792 |
| Filed: |
September 10, 1973 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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285398 |
Aug 31, 1972 |
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| Current U.S.
Class: |
430/8; 283/60.1;
430/10; 430/933; 283/17; 283/91; 430/384 |
| Current CPC
Class: |
G03C
1/83 (20130101); G03C 1/7954 (20130101); G03C
1/8155 (20130101); Y10S 430/134 (20130101) |
| Current International
Class: |
G03C
1/815 (20060101); G03C 1/795 (20060101); G03C
1/83 (20060101); G03C 001/92 (); G03C 001/94 ();
G03C 001/52 () |
| Field of
Search: |
;96/84R,84UV,8N,87R,44,45,75 ;117/33.3,35.6 ;283/6,17,60 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Martin, Jr.; Roland E.
Assistant Examiner: Brammer; J. P.
Attorney, Agent or Firm: Milan; E. W.
Parent Case Text
This application is a continuation-in-part of U.S. Pat. application
Ser. No. 285,398, filed Aug. 31, 1972, now abandoned.
Claims
What is claimed is:
1. An information receiving film element for providing a processed,
substantially non-fluorescent, optically brightened, substantially
transparent information bearing, polymeric film element from which
the information processed thereon is substantially non-reproducible
when said information bearing film element is placed over a diazo
film or print paper and is subjected to exposure to radiation
having a wavelength in the range of between about 300 and 460
nanometers, said information receiving film element comprising:
i. a transparent polymeric film support that transmits visible
radiation, and which can absorb radiation having a wavelength in
the range between about 300 and 460 nanometers, said support having
incorporated therein
a. an optical brightening amount of at least one optical brightener
compound capable of absorbing radiation in said wavelength range,
and
b. a fluorescence and radiation absorbing amount of at least one
yellow dye capable of absorbing radiation in said wavelength range,
and
ii. at least one radiation sensitive layer, which, when exposed to
informaion-providing radiation and processed to develop the
information received forms an information bearing transparency,
said optical brightener and said yellow dye both being present in
said support in a total amount at least sufficient to absorb
radiation having said wavelength but insufficient to prevent
passage of visible light through the element while said yellow dye
also absorbs the fluorescence of said optical brightener both
before and after processing of the element to its information
bearing film element form, said optical brightener being a
fluorescent compound selected from
a. at least one fluorescent 4,4'-bis-(benzoxazol-2-yl) stilbene
compound;
b. 4,4'-bis(4,6-diphenyl-s-triaxin-2-yl)-stilbene;
c. 2,5,bis[5-(.alpha.,.alpha.-dimethylbenzyl)benzoxazol-2-yl]
-thiophene;
d. 7-(2H-naphtho[1,2-d] triazol-2-yl)-3-phenyl-2-chromanone;
e. 6-acetamido-2-butyl phenalene-1,3-(2H)-dione;
f. 6-(4-methyl-5-phenyl-v-triazol-2-yl)-3-phenyl-2-chromanone;
g. 2-(4,6-dimethoxy-2-s-triazinyl)pyrene;
h. phenyl-4-(2H-naphtho[1,2-d] triazol-2-yl)-2-stilbene
sulfonate;
i. 4'-(2-benzoxazolyl)-4-stilbene carboxylic acid;
j. 1,4-bis(2-benzoxazolyl)naphthalene;
k. 1,4-bis(5-methoxycarbonyl-2-benzoxazolyl) naphthalene;
l. methyl-4'-(2-benzoxazolyl)-4-stilbene carboxylate; and said
yellow dye being selected from
a. at least one dyestuff of the following formulas: ##SPC29##
wherein R.sup.2 is selected from the group consisting of 5 or 6
membered nitrogen-containing heterocyclic rings having a
heterocyclic nitrogen atom attached through a double bond to a
carbon atom of the ring through which R.sup.2 is attached;
b. 1,5-bis(1,2,4-triazol-5-ylthio)anthraquinone;
c. 2,2'-bis[4(2,2-dicyanovinyl)-N-ethyl-3-toluidino] diethyl
sulfone;
d. 2,2'-bis[4(2,2-dicyanovinyl)-N-ethyl anilino] diethyl
isophthalate;
e. N,N' -bis[2-{ 4-(2,2-dicyanovinyl)-N-ethyl-3-toluidino} ethyl]
terephthalamide;
f. 2,2'-bis[ 4(2,2-dicyanovinyl)-N-ethyl-3-toluidino] diethyl
succinate;
g. 2,2'-bis[ 4-(2,2-dicyanovinyl)-N-ethyl-3-toluidino] diethyl
adipate;
h. 2,6-bis(2-quinolyl)-s-hydrindacene-1,3,5,7-tetrone;
i. 2-(2-quinolyl)-1,3-indandione-5,6-dicarboxylic anhydride;
and
j. 2-(3-hydroxyquinol-2-yl)-1,3-indandione.
2. An element according to claim 1 characterized in that said
suport is a polyester, cellulose nitrate, cellulose acetate,
poly(vinyl acetal), polystyrene, or polycarbonate support.
3. An element according to claim 1 wherein said stilbene compound
is of the formula: ##SPC30##
wherein each R.sup.1 which can be the same or different is selected
from the group consisting of hydrogen atoms, halogen atoms, alkyl,
aryl, substituted aryl, hydroxy, alkoxy, aryloxy, acyl, acyloxy,
amino, and substituted amino radicals and each Y which can be the
same or different is selected from the group consisting of hydrogen
atoms, alkyl, aryl, and cyano radicals.
4. An element according to claim 3 wherein each R.sup.1 and each Y
are hydrogen atoms.
5. An element according to claim 3 wherein said yellow dye is
selected from the group consisting of: ##SPC31##
wherein R.sup.2 is selected from the group consisting of 5 or 6
membered nitrogen-containing heterocyclic rings having a
heterocyclic nitrogen atom attached through a double bond to a
carbon atom of the ring through which R.sup.2 is attached.
6. An element according to claim 4 wherein said yellow dye is
2-(2-quinolyl)-1,3-indandione.
7. An element according to claim 4 wherein said yellow dye is
2,2'bis[4(2,2 dicyanovinyl)-N-ethyl-3-toluidino] diethyl
adipate.
8. An information receiving film element according to claim 1
wherein said support is a linear polyester support wherein the
polyester is poly(ethylene terephthalate),
poly(1,4-cyclohexylenedimethylene terephthalate), poly(ethylene
isophthalate), poly(ethylene naphthalenedicarboxylate), or a
mixture of at least two of said polyesters.
9. A substantially non-fluorescent, optically brightened,
substantially transparent information bearing polymeric film
element from which the information carried thereon is substantially
non-reproducible when said element is placed over a diazo film or
print paper and is subjected to exposure to radiation having a
wavelength in the range between about 300 and 460 nanometers, said
element comprising:
i. a transparent polymeric film support that transmits visible
radiation, and which can absorb radiation having a wavelength in
the range between about 300 and 460 nanometers, said support having
incorporated therein
a. an optical brightening amount of at least one optical brightener
compound capable of absorbing radiation in said wavelength range,
and
b. a fluorescence and radiation absorbing amount of at least one
yellow dye capable of absorbing radiation in said wavelenth range,
and
ii. at least one information bearing layer, which when exposed to
information-reproducing radiation transmits visible radiation and
absorbs radiation in said wavelength range, said optical brightener
and said yellow dye both being present in said support in a total
amount at least sufficient to absorb radiation having said
wavelength but insufficient to prevent passage of visible light
through the element while said yellow dye also absorbs the
fluorescence of said optical brightener both before and after
processing of the element to its information bearing film element
form, said optical brightener being a fluorescent compound selected
from
a. at least one fluorescent 4,4'-bis- (benzoxazol-2-yl) stilbene
compound;
b. 4,4'-bis(4,6-diphenyl-s-triaxin-2-yl)-stilbene;
c. 2,5,bis[5-(.alpha.,
60-dimethylbenzyl)benzoxaol-2-yl]-thiophene;
d. 7-(2H-naphtho[ 1,2-d] triazol-2-yl)-3-phenyl-2-chromanone;
e. 6-acetamido-2-butyl phenalene-1,3-(2H)-dione;
f. 6-(4-methyl-5-phenyl-v-triazol-2-yl)-3-phenyl-2-chromanone;
g. 2-(4,6-dimethoxy-2-s-triazinyl)pyrene;
h. phenyl-4-(2H-naphtho[ 1,2-d] triazol-2-yl)-2-stilbene
sulfonate;
i. 4'-(2-benzoxazolyl)-4-stilbene carboxylic acid;
j. 1,4-bis(2-benzoxazolyl)naphthalene;
k. 1,4-bis(5-methoxycarbonyl-2-benzoxazolyl) naphthalene;
l. methyl-4'-(2-benzoxazolyl)-4-stilbene carboxylate; and said
yellow dye being selected from
a. at least one dyestuff of the following formuals: ##SPC32##
wherein R.sup.2 is selected from the group consisting of 5 or 6
membered nitrogen-containing heterocyclic rings having a
heterocyclic nitrogen atom attached through a double bond to a
carbon atom of the ring through which R.sup.2 is attached;
b. 1,5-bis(1,2,4-triazol-5-ylthio)anthraquinone;
c. 2,2'-bis[ 4(2,2-dicyanovinyl)-N-ethyl-3-toluidino] diethyl
sulfone;
d. 2,2'-bis[ 4(2,2-dicyanovinyl-N-ethyl anilino] diethyl
isophthalate;
e. N,N'-bis[ 2-{ 4-(2,2-dicyanovinyl)-N-ethyl-3-toluidino} ethyl]
terephthalamide;
f. 2,2'-bis[4(2,2-dicyanovinyl)-N-ethyl-3-toluidino] diethyl
succinate;
g. 2,2'-bis[ 4(2,2-dicyanovinyl)-N-ethyl-3-toluidino] diethyl
adipate;
h. 2,6-bis(2-quinolyl)-s-hydrindacene-1,3,5,7-tetrone;
i. 2-(2-quinolyl)-1,3-indandione-5,6-dicarboxylic anhydride;
and
j. 2-(3-hydroxyquinol-2-yl)-1,3-indandione.
10. An element according to claim 9 wherein said stilbene compound
is of the formula: ##SPC33##
wherein each R.sup.1 which can be the same or different is selected
from the group consisting of hydrogen atoms, halogen atoms, alkyl,
aryl, substituted aryl, hydroxy, alkoxy, aryloxy, acyl, acyloxy,
amino, and substituted amino radicals and each Y which can be the
same or different is selected from the group consisting of hydrogen
atoms, alkyl, aryl, and cyano radicals.
11. An element according to claim 10 wherein each R.sup.1 and Y are
hydrogen atoms.
12. An element according to claim 10 wherein said yellow dye is
selected from the group consisting of: ##SPC34##
wherein R.sub.2 is selected from the group consisting of 5 or 6
membered nitrogen-containing heterocyclic rings having a
heterocyclic nitrogen atom attached through a double bond to a
carbon atom of the ring through which R.sup.2 is attached.
13. An element according to claim 11 wherein said yellow dye is
2-(2-quinolyl)-1,3-indandione.
14. An element according to claim 11 wherein said yellow dye is
2,2'bis[ 4(2,2 dicyanovinyl)-N-ethyl-3-toluidino] diethyl
adipate.
15. A light projectable, substantially nonfluorescent, optically
brightened substantially transparent information bearing microfilm
element according to claim 9.
16. A microfilm element according to claim 15 wherein said stilbene
compound is of the formula: ##SPC35##
wherein each R.sup.1 which can be the same or different is selected
from the group consisting of hydrogen atoms, halogen atoms, alkyl,
aryl, substituted aryl, hydroxy, alkoxy, aryloxy, acyl, acyloxy,
amino, and substituted amino radicals and each Y which can be the
same or different is selected from the group consisting of hydrogen
atoms, alkyl, aryl, and cyano radicals.
17. A microfilm element according to claim 16 wherein each R.sup.1
and Y are hydrogen atoms.
18. A microfilm element according to claim 16 wherein said yellow
dye is selected from the group consisting of: ##SPC36##
wherein R.sup.2 is selected from the group consisting of 5 or 6
membered nitrogen-containing heterocyclic rings having a
heterocyclic nitrogen atom attached through a double bond to a
carbon atom of the ring through which R.sup.2 is attached.
19. A microfilm element according to claim 17 wherein said yellow
dye is selected from the group consisting of: ##SPC37##
wherein R.sup.2 is selected from the group consisting of 5 or 6
membered nitrogen-containing heterocyclic rings having a
heterocyclic nitrogen atom attached through a double bond to a
carbon atom of the ring through which R.sup.2 is attached.
20. A microfilm element according to claim 17 wherein said yellow
dye is 2-(2-quinolyl)-1,3-indandione.
21. A microfilm element according to claim 17 wherein said yellow
dye is 2,2'bis[4(2,2 dicyanovinyl)-N-ethyl-3-toluidino] diethyl
adipate.
22. A microfilm element according to claim 15 in which said support
is a polymeric support.
23. A microfilm element according to claim 22 in which said
polymeric support is a polyester, cellulose nitrate, cellulose
acetate, poly(vinyl acetal), polystyrene, or polycarbonate
support.
24. An information bearing film element according to claim 9
wherein said support is a linear polyester support wherein the
polyester is poly(ethylene terephthalate),
poly-(1,4-cyclohexylenedimethylene terephthalate), poly(ethylene
isophthalate), poly(ethylene naphthalenedicarboxylate), or a
mixture of at least two of said polyesters.
25. An information bearing film element according to claim 9
wherein said support is a polyester, cellulose nitrate, cellulose
acetate, poly(vinyl acetal), polystyrene or polycarbonate film
support.
26. A microfilm element according to claim 24.
Description
FIELD OF THE INVENTION
This invention relates generally to information receiving elements
and more particularly to a photographic film element suitable for
receiving microimages, such as microfilm.
BACKGROUND OF THE INVENTION
In recent years, microfilm has been used as a medium for publishing
books, reports, catalogs, and other useful information having a
market value to interested readers. Microfilm is ideally suited to
the publication field because it is a form of information receiving
element by means of which a large amount of information can be
condensed within a small storage area. One of the practical
difficulties that a producer or distributor of microfilms of
copyrighted material faces is the possibility of copying, or
duplication of the material, by persons without permission of the
copyright owner. Such unauthorized duplication often is carried out
by means of an inexpensive copying method, i.e., by the diazo
process. The possibility that such copying will occur often results
in reluctance on the part of copyright owners to make disclosures
to the public. As a result of the subject matter of this invention,
these copyright owners are now provided with means by which they
will be better able to control dissemination of their copyrighted
material and should be more inclined to copyright more information
for divulgation to the general public. Accordingly, it is an object
of the present invention to provide microfilm form of information
receiving element from which an image cannot be duplicated readily
by the diazo process.
Customarily, microimages are reproduced by the diazo process by the
use of radiation from a mercury lamp or a thorium doped mercury
lamp to project a microimage from a microfilm onto diazo film or
paper. The radiation reaching the film or paper consists primarily
of radiation of wavelengths 313.15, 366.3, 404.6, 420, and 435.8 nm
(nanometers). Diazo film and paper normally are sensitive to
radiation in a wavelength range from 300 to 460 nm.
It is an object of this invention to provide an information
receiving element which is useful for recording thereon a
microimage, and thereby make possible storage of information in
microsize form, and which also renders substantially impossible
duplication of the recorded microimage from the element onto diazo
paper or film. This object is accomplished by incorporation in the
element of materials which together absorb radiation to which the
diazo system is sensitive. Preferably, the information receiving
element is a photographic film. The invention will be exemplified
herein by means of such a film. As used generally, the term
"photographic film" includes an element having in combination a
radiation sensitive layer, a suppport material in the form of a
film, and various other layers which comprise a photographic
element.
The element of the present invention comprises a support and one or
more layers carried by the support. Generally, one of the layers
comprises a radiation sensitive composition suitable for recording
microimages therein. The element contains, in addition, an optical
brightener and yellow dye incorporated in the support and/or in at
least one of the layers coated on the support. Broadly, the element
of this invention is an element comprising a support that transmits
visible radiation and a radiation sensitive layer, said element
being characterized in that it contains both an optical brightener
and a yellow dye which, together, absorb radiation in the range of
about 300 to about 460 nm. Particularly, the element of the
invention is an element adapted to substantially impede duplication
of the image therefrom by the use of actinic radiation in the
region between 300 nm and 460 nm, said element comprising a support
having incorporated therein an optical brightener and a yellow dye
which together absorb actinic radiation in the range of about 300
to about 460 nm, and an image-bearing layer carried by said
support.
In practicing the invention, the dye and brightener are
incorporated preferably in a layer or layers other than a radiation
sensitive layer, since the dye and brightener can adversely affect
sensitometric properties of the radiation sensitive composition.
Within the context of the invention it is the intention that the
combination of the yellow dye and optical brightener does not
prevent the exposure of the radiation sensitive layer, i.e., the
radiation sensitivity of the layer is not restricted to that part
of the specturm in which said combination of dye and brightener
absorbs light radiation.
From U.S. Pat. Nos. 3,322,680 and 3,260,715, as well as from
Japanese Patent 11242/68, it is known to incorporate fluorescent
organic compounds as whiteners and brightening agents into a
variety of synthetic polymers. However, the incorporation is
carried out for the sole purpose of improving the whiteness and
brightness of industrial products and fabrics using such synthetic
resins. This prior art is not concerned with the problem solved by
the present invention, namely, effective suppression of
transmission of radiation in the region between 300 and 460 nm. The
present invention solves this problem by the combined use of an
otpical brightener and a yellow dye in the support and/or in at
least one of the layers coated on the support of an element, as
discussed above.
In this combined use, the optical brightener has the function of
suppressing transmission of radiation by absorbing between 300 and
400 nm in wavelength. The yellow dye has as one of its functions a
similar function, namely, to absorb radiation in the region between
400 and 460 nm and to suppress its transmission. In addition, the
yellow dye has the further function of absorbing the fluorescent
radiation accompanying light absorption by the optical brightener.
A preferred range of absorption of the combination of yellow dye
and optical brightener lies between 300 and about 435 nm. The
combined effect of optical brightener and yellow dye in the
element, or photographic film, prevents the copying of images
contained in an information receiving element made from
photographic film, such as a microfiche, by means of the diazo
copying method, or by any other copying method using as its
principal light source radiation between 300 and 460 nm. (e.g. a
mercury lamp).
The present invention is intended especially for use in film from
which microimages are projectable or readable by transmission of
light radiation. The expression "projectable or readable" is used
herein to refer to any film for producing images when light
radiation is directed therethrough and is intended to include
elements with image patterns consisting of silver, dyes, minute
bubbles, and other image forming materials in a light transmissive
medium. In a preferred embodiment the film comprises a silver
halide emulsion coated on a yellow, transparent linear polyester
support. The emulsion is developable by conventional methods.
Any of the support materials which will transmit at least some
visible radiation can be used in the practice of this invention.
Such support materials are typically polymeric and include, for
example, cellulose nitrate film, cellulose acetate film, poly
(vinyl acetal) film, polystyrene film, polycarbonate film and
related films or resinous materials. Linear polyester is a
preferred support material, since linear polyester materials have
excellent dimensional stability. These polyester materials are
generally linear polyesters of at least one glycol having 2 to 10
carbon atoms and at least one dibasic acid comprising at least 50
mole percent of an acid having two carboxyl radicals attached to a
carbocyclic nucleus having from 4 to 6 carbon atoms per ring. The
ester generally has a number average molecular weight of from about
10,000 to about 100,000, an inherent viscosity in a mixture of 60%
phenol and 40% chlorobenzene of at least about 0.3 to about 1.3
deciliters per gram and melts at from about 175.degree. to about
350.degree.C. Viscosity is determined at 25.degree.C. with
solutions of 0.25g of the polyester per 100 milliliters of phenol:
chlorobenzene.
In this regard, particularly preferred polyester materials are poly
(ethylene terephthalate), poly (1,4-cyclohexylenedimethylene
terephthalate), poly(ethyleneisophthalate), poly(ethylene
naphthalenedicarboxylate), and mixtures of at least two of these.
The term linear polyester also includes copolyesters based on these
polyesters, such copolyesters being obtained by replacing a portion
of the terephthalic acid by another acid or by a hydroxycarboxylic
acid, and/or by replacing a portion of the glycol with a different
glycol.
In conventional microfilm reproduction methods, the microimages are
reproduced on diazo film or paper by exposing the film or paper to
actinic light projected through the microimage carrying element.
According to the present invention, in order to prevent such
copying, an optical brightener and a yellow dye are incorporated
into the support or together in at least one of the layers other
than the radiation sensitive layer of the information receivng
element, or separately in at least two such layers. The location in
the element of a layer containing dye and/or brightener is not
important.
In a preferred embodiment, the brightener and dye both are
incorporated in a polyester support.
In such a preferred embodiment, any optical brightener that (a) is
compatible with the polyester, (b) does not adversely affect the
sensitometric properties of the radiation-sensitive layer, and (c)
is stable at the temperatures encountered in forming the polyester
support and in processing the photographic element can be used.
In a preferred embodiment, the optical brightener is a fluorescent
4,4'-bis(benzoxazol-2-yl) stilbene compound of the following
formula I: ##SPC1##
wherein R is a bivalent 4,4'-stilbene radical of the formula
##SPC2##
and A.sub.1 and A.sub.2 are each an o-phenylene radical of the
formula ##SPC3##
The substituents R.sup.1 of the bivalent 4,4'-stilbene radical and
each of the phenylene radicals can be the same or different
monovalent substituents. Typical substituents R.sup.1 which are
suitable include a hydrogen atom, a halogen atom, and alkyl, aryl,
substituted aryl, hydroxy, alkoxy, aryloxy, acyl, acyloxy, amino,
and substituted amino radicals. In the preferred embodiment the
substituents R.sup.1 are all hydrogen atoms. Other substituents are
defined in U.S. Pat. No. 3,322,680 which is incorporated herein by
reference.
The substituents Y which are suitable include a hydrogen atom, and
alkyl, aryl and cyano radicals. In the preferred embodiment the
substituents Y are hydrogen atoms. Reference may be had to the
above patent for further definition of Y substituents.
Among other optical brighteners that may be used in this invention
are those indicated below: ##SPC4##
4,4'-Bis(4,6-diphenyl-s-triaxin-2-yl)-stilbene ##SPC5##
2,5-Bis[5-(.alpha..alpha.-dimethylbenzyl) benzoxazol-2-yl ]-
thiophene ##SPC6##
7-(2H-Naphtho[1,2-d ]triazol-2-yl)-3-phenyl-2-chromanone
##SPC7##
6-Acetamido-2-butyl phenalene-1,3-(2H)-dione ##SPC8##
6-(4-Methyl-5-phenyl-v-triazol-2-yl)-3-phenyl-2-chromanone
##SPC9##
2-(4,6-dimethoxy-2-s-triazinyl)pyrene ##SPC10##
Phenyl 4-(2H-Naphtho[1,2-d ]triazol -2-yl)-2stilbene Sulfonate
##SPC11##
4'-(2-Benzoxazolyl)-4-stilbenecarboxylic acid ##SPC12##
1,4-Bis (2-benzoxazolyl) naphthalene ##SPC13##
1,4-Bis( 5-methoxycarbonyl-2-benzoxazolyl)naphthalene ##SPC14##
Methyl 4'-(2-Benzoxazolyl)-4-stilbenecarboxylate
In the preferred embodiment, the yellow dye is a dyestuff of the
following formulas: ##SPC15##
wherein X is selected from the group ##SPC16##
R.sup.2 represents a 5 or 6 membered nitrogen-containing
heterocyclic ring having a heterocyclic nitrogen atom attached
through a double bond to a carbon atom of the ring to which X is
attached. The heterocyclic ring may contain substituents or it may
form part of a fused ring system which may also contain
substituents such as the radical --COOR.sup.3 , wherein R.sup.3
represents hydrogen, alkyl, hydroxyalkyl, alkoxyalkyl, or
hydroxyalkoxyalkyl. One of R.sup.2 and X may be substituted by at
least one radical --COOR.sup.3 as hereinbefore defined.
A dye suitable for incorporation in the polyester supports
mentioned above is 2-(2-quinolyl)-1,3-indandione. In its pure form,
this dye is a skin sensitizer, but polyester film containing the
dye is not. This dye has the following structure: ##SPC17##
This yellow dye and other yellow dyes which may be used according
to this invention are disclosed in and prepared by the methods
disclosed in U.S. Pat. Nos. 3,417,048 and 3,622,582 incorporated
herein by reference. Among the other yellow dyes which may also be
used are the following: ##SPC18##
1,5 Bis( 1,2,4-triazol-5-ylthio)anthraquinone ##SPC19##
2,2'-Bis[ 4(2,2-dicyanovinyl)-N-ethyl-3-toluidino] diethyl Sulfone
##SPC20##
2,2'-Bis[4(2,2-dicyanovinyl)-N-ethyl anilino] diethyl Isophthalate
##SPC21##
N,n'-bis[2-{4-(2,2 dicyanovinyl)-N-ethyl-3-toluidino} ethyl]
terephthalamide ##SPC22##
2,2'-Bis[4(2,2 dicyanovinyl)-N-ethyl-3-toluidino] diethyl Succinate
##SPC23##
2,2'-Bis[4-(2,2-dicyanovinyl)-N-ethyl-3-toluidino] diethyl Adipate
##SPC24##
2,6-Bis( 2-quinolyl)-s-hydrindacene-1,3,5,7-tetrone ##SPC25##
2-(2-Quinolyl)-1,3-indandione-5,6-dicarboxylic anhydride
##SPC26##
2(3-Hydroxyquinol-2-yl)-1,3-indandione
In one embodiment, a polyester support is prepared in a
conventional manner by mixing an optical brightener and a yellow
dye with polyester powder or pellets and the mixture is then melted
at a temperature of about 250.degree. to 300.degree.C. The melt is
then extruded into sheet form which is then biaxially stretched in
conventional manner to form film useful as a support for a
photographic element. The dye may also be mixed with a small
portion of the polyester and then heated to about
160.degree.-190.degree.C for about 2 hours as taught in copending
U.S. Pat. application of Barkey et al., Ser. No. 285,397, filed
Aug. 31, 1972, incorporated herein by reference. The concentrate so
prepared can then be mixed with the remainder of the polyester and
the optical brightener as above.
The photographic element can be of conventional structure, and it
can be exposed in conventional manner to form a projectable or
readable microimage information bearing element. If an unauthorized
person attempts to duplicate the information onto diazo film or
paper, he or she is prevented from obtaining a diazo copy in the
normal way because the actinic light used to expose diazo emulsions
is absorbed by the film of this invention and its transmission is
suppressed.
When used with a polyester support, the optical brightener is added
to the polyester at a concentration of about 300 to 4000ppm, and
the yellow dye is added in amounts of from about 300 to about
8000ppm. These quantities would be suitable in polyester used for
casting a film support having a final thickness of about 0.004.
inches. Of course, the quantities could be adjusted for polyester
used for casting film support whose thickness is other than 0.004.
inches. The concentration of dye and optical brightener should be
inversely proportional to the thickness.
The following examples further illustrate the invention.
EXAMPLE I
To poly(ethylene terephthalate) resin having a number average
molecular weight of about 20,000 and an inherent viscosity of about
0.62 were added 2000ppm optical brightener of the formula:
##SPC27##
which compound is 4,4'-bis[benzoxazole-2-yl] stilbene. Also added
were 1750ppm yellow dye of the formula: ##SPC28##
which compound is 2-(2-quinolyl)-1,3-indandione sold by National
Aniline Division of Allied Chemical Corporation as Plasto Yellow Y.
The resin mixture was melted and extruded as 4 mil film base or
support. The filter factor for this film base was approximately
150.
Filter factor is defined as the increase in the amount of light
that is required to expose a diazo emulsion using a master coated
on the special (yellow) film base. The number 150 indicates that an
increase of 150 times in the amount of light is needed to get a
usable copy when the master is on the special (yellow) film base,
compared to the amount of light that is needed to get a usable copy
when the master is on regular (water white) film base.
EXAMPLE II
To poly(ethylene terephthalate) as in Example I were added 2000ppm
of the preferred optical brightener and 2000ppm of 2,2'bis[4-2,2
dicyanovinyl) N-ethyl-3toluidino] diethyl adipate. The mixture was
melted and extruded to form a support 4 mils thick. This support
had a filter factor of about 275.
Although in a preferred embodiment of the present invention, an
optical brightener and a yellow dye are incorporated into a
polyester support, it is also advantageous to prepare information
receiving elements of this invention in which the optical
brightener and the yellow dye are incorporated in one or several
other layers of the information receiving elements of the
invention; e.g., such layers can be interlayers between the support
and the radiation sensitive layer, or they may be outer layers or
overcoats on the side opposite the radiation sensitive layer, or on
the radiation sensitive layer itself. It should be emphasized that
the combination of the optical brightener and the yellow dye may be
incorporated in one and the same layer or the optical brightener
may be located in one layer and the dye in another while still
obtaining the advantages and benefits of the invention.
The invention has been described in detail with particular
reference to preferred embodiments thereof, but it will be
understood that variations and modifications can be effected within
the spirit and scope of the invention.
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