U.S. patent number 3,765,896 [Application Number 05/200,830] was granted by the patent office on 1973-10-16 for photographic element containing a light sensitive photobleachant and a colored stable 2-amino-aryl-7-oxyl-3-oxide-2-imidazoline free radical.
This patent grant is currently assigned to Eastman Kodak Company. Invention is credited to Charles J. Fox.
United States Patent |
3,765,896 |
Fox |
October 16, 1973 |
PHOTOGRAPHIC ELEMENT CONTAINING A LIGHT SENSITIVE PHOTOBLEACHANT
AND A COLORED STABLE 2-AMINO-ARYL-7-OXYL-3-OXIDE-2-IMIDAZOLINE FREE
RADICAL
Abstract
Direct-positive photographic compositions are disclosed, the
compositions including a radiation-sensitive photobleachant and a
colored, stable 2-amino-aryl-1-oxyl-3-oxide-2-imidazoline free
radical. When the compositions are exposed to activating radiation
for the photobleachant, the colored stable-free radical is bleached
or decolorized such that the exposed areas of the composition
exhibit lower density and/or different coloring than the unexposed
areas. Direct positive images are produced thereby. These
compositions can be carried on a support to prepare photographic
elements.
Inventors: |
Fox; Charles J. (Rochester,
NY) |
Assignee: |
Eastman Kodak Company
(Rochester, NY)
|
Family
ID: |
22743386 |
Appl.
No.: |
05/200,830 |
Filed: |
November 22, 1971 |
Current U.S.
Class: |
430/171; 430/334;
430/339; 430/374 |
Current CPC
Class: |
G03C
7/02 (20130101); G03C 1/73 (20130101) |
Current International
Class: |
G03C
1/73 (20060101); G03C 7/02 (20060101); G03c
001/72 (); G03c 001/68 () |
Field of
Search: |
;96/89,90,91R,115R,48R |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Torchin; Norman G.
Assistant Examiner: Louie, Jr.; Won H.
Claims
There is claimed:
1. A direct-positive photographic composition comprising a
radiation-sensitive photobleachant selected from the group
consisting of 4-dialkylaminobenzene diazonium salts,
4-alkoxybenzenediazonium salts, 4-aryloxybenzenediazonium salts,
bis-2,4,5-triphenylimidazoles, azobispropionitriles, poly-(ethylene
glycols), benzophenones, tetraphenyl pyrroles, benzo-peroxides,
cumene hydroperoxides, 1,8-pyrenediones and mixtures thereof and a
colored, stable free radical having the formula: ##SPC5##
wherein:
a. each of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 independently
represents one of an alkyl group having from one to eight carbon
atoms, an alkoxy group or an aryl group having from six to 14
carbon atoms, and
b. R.sup.5 represents an aminoaryl group having from six to 14
atoms in a mono or polycyclic aromatic nucleus, said amino moiety
having the formula ##SPC6##
R.sup.6 and R.sup.7 each representing independently one of an alkyl
group or an aryl group as described above.
2. A direct-positive photographic composition as described in claim
1 wherein, in the free radical, each of R.sup.1, R.sup.2, R.sup.3
and R.sup.4 is a lower alkyl group and each of R.sup.6 and R.sup.7
are alike and are either a methyl group, and ethyl group or a
phenyl group.
3. A direct-positive photographic composition as described in claim
1 wherein said free radical and said photobleachant are included in
a molar ratio of from 1:1 to about 1:10.
4. A direct-positive photographic composition as described in claim
1 and further comprising a film-forming polymeric binder.
5. A direct-positive photographic composition as described in claim
4 wherein said binder is cellulose acetate, cellulose acetate
butyrate, cellulose acetate propionate or gelatin.
6. A photographic element comprising a support having thereon a
direct-positive photographic composition as described in claim
1.
7. A photographic element comprising a support having thereon a
direct-positive photographic composition as described in claim
1.
8. A photographic element as described in claim 6 wherein said
support comprises a porous material and said direct-positive
photographic composition is imbibed into the pores of said support.
Description
FIELD OF THE INVENTION
The present invention relates to photography and particularly to
direct-positive photographic compositions and elements including a
colored, stable-free radical and a photobleachant.
PRIOR ART
General reference to the use of stable-free radicals in single
component imaging systems has been made in papers presented by W.
R. Bard at SPSE 2nd Symposium on Unconventional Photographic
Systems, Washington, D. C. Oct. 21-28, 1967 and at the Society of
Plastics Engineers, Mid-hudson Section November, 1967.
The use of stable-free radicals as sensitizers to increase the
photoresponsive characteristics of photoconductive insulating
compositions and photohardenable polymer compositions is described
in U. S. Pat. No. 3,434,833 to Fox issued Mar. 25, 1969.
Negative working direct imaging systems, i.e. those which are based
on the formation of increased color or density in exposed areas,
which systems relate to combinations of a color generator with a
photooxidant are described in, for example, British Pat. No.
1,047,796; U. S. Pat. Nos. 3,359,109; 3,360,370; 3,395,018;
3,445,233; 3,445,234; and Canadian Pat. No. 798,260.
Furthermore, Canadian Pat. No. 822,049 discloses the use of
light-sensitive free radicals which upon exposure to actinic
radiation react with a color forming compound to produce areas of
density in a negative system, and in a positive system a colored
compound which is bleached to provide less density in the exposed
areas.
Although many of these systems, as already described, make use of
photo-imaging systems comprising a photo-active compound and a
color producing compound which reacts with the photoactivator upon
exposure to light, no systems have been disclosed which utilize
2-aminoaryl-1-oxyl-3-oxide-2-imidazoline colored stable-free
radicals to produde a direct positive and photo-bleachant image.
Other patents, describing the use of colored free radicals in
combination with photobleachants are U. S. Pat. No. 3,600,168 and
its corresponding patent, Canadian Pat. No. 874,372 and British
Pat. No. 1,213,823.
A system such as the one described herein overcomes many of the
disadvantages exhibited by conventional materials of this type
which include relatively high cost, instability of images,
generation of offensive odors or poisonous vapors making them
difficult to handle, low speed, poor contrast and insufficient
resolution. Furthermore, in many known systems, the use of
halogenated organic photoactivators which are generally extremely
volatile and poisonous is required.
Accordingly, it is an object of this invention to provide novel
direct-positive photographic compositions and elements.
Another object of this invention is to provide new direct positive
photographic processes.
Still other objects and advantages of the present invention will
become apparent from a reading of the following specification and
appended claims.
STATEMENT OF THE INVENTION
The objects of this invention are accomplished with direct-positive
photographic compositions including a radiation-sensitive
photobleachant, (i.e., a compound that when exposed to activating
rays forms a species that can react with a colored, stable free
radical to lower the density or change the color of the free
radical) and a colored, stable free radical are provided. They are
non-toxic, efficient and produce positive images on exposure. These
compositions can be used in conjunction with a support material to
prepare photographic elements. The photographic compositions can be
coated on a support as a layer or imbibed into a porous support
material.
DESCRIPTION OF PREFERRED EMBODIMENT(S)
Direct-positive (i.e. producing a positive image directly on
exposure) photographic compositions of the present type include a
radiation-sensitive photobleachant and a colored, stable free
radical having the formula: ##SPC1##
wherein:
a. each of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 independently
represents one of alkyl group, an alkoxy group or an aryl group,
and
b. R.sup.5 represents an aminoaryl group having from six to 14
atoms in a mono- or polycyclic aromatic nucleus, with the amino
moiety having the formula ##SPC2## wherein each of R.sup.6 and
R.sup.7 independently represents one of an alkyl group or an aryl
group (preferably phenyl). In one preferred embodiment, R.sup.6 and
R.sup.7 are alike.
As used herein, the term alkyl group includes straight or branched
chain aliphatic groups having from one to eight carbon atoms in the
carbon chain used to define the group nomenclature, such as methyl,
ethyl, 2-chloroethyl, isopropyl, butyl, pentyl, heptyl, n-octyl,
7-methyloctyl and the like alkyl groups. Lower alkyl groups having
one to four carbon atoms are preferred. The term alkoxy group
refers to etherified alkyl groups, also designated alkyloxide
groups, and include an alkyl moiety such as those described herein
chemically bonded to an oxygen atom, for example, methoxy, ethoxy,
propoxy, isobutoxy, pentyloxy, n-octyloxy, etc. Lower alkoxy groups
having from one to four carbon atoms are preferred. The term aryl
group, as used herein, refers to and includes aromatic groups
derived from mono- and polycyclic carbocyclic nuclei and having
from six to 14 atoms in a mono- or polycyclic nucleus, such as
phenyl, p-tolyl, naphthyl, anthryl, etc.
Free radical precursors from which free radicals of the present
type can be prepared are themselves able to be prepared by the
reaction of an ortho bis(hydroxylamino) alkane with an appropriate
arylamino benzaldehyde in an organic solvent. Depending on the
particular substituents represented by R.sup.1, R.sup.2, R.sup.3
and R.sup.4, the ortho bis(hydroxylamino) alkane can be substituted
with alkyl, alkoxy or aryl groups. As an example, when each of
R.sup.1, R.sup.2, R.sup.3 and R.sup.4 is a methyl radical, the
alkane is 2,3-bis(hydroxylamino)-2,3-dimethylbutane. Other
precursors useful in preparing stable free radical precursors and
stable free radicals described herein include such compounds as
2,3-bis(hydroxylamino)-2,3-dimethoxybutane, etc.
The stable free radicals of the present type are prepared by
treatment of the appropriate stable free radical precursor with a
suitable oxidation catalyst, for example active lead dioxide in
benzene solution, or any other similar oxidation catalyst well
known to those skilled in the art.
As mentioned herein, the colored, stable free radical is used in
conjunction with a light-activatable photobleachant. When exposed
to activating rays, e.g. ultraviolet light, other actinic rays
visible light or the like, the photobleachants useful herein are
capable of reacting with the free radical. It is theorized that
this capability may be the result of the photogeneration of a
reactive species such as a radical, radical ion, ion or hydrogen
atom. Amplification factors may be introduced in some instances
since two or more reactive species may be formed upon absorption of
a single photon.
Exemplary photobleachants that may be utilized herein include the
following: ##SPC3##
Generally, any one or more of the above-described photobleachants
may be used in combination with the aforementioned stable-free
radicals so that upon exposure to light, a reaction occurs which
bleaches the colored free radical and produces a decrease in color
density in exposed regions, thereby producing desired direct
positive image. Generally, the mole ratio of free radical to
photobleachant ranges from about 1:1 to about 1:10 and preferably
between from about 1:1 to about 1:5.
To prepare a composite photographic composition, the colored free
radical and the photobleachant can be included in a coating
solution, optionally containing a polymer suitable support or cast
or extruded into a self-supporting film and dried. Coating can be
accomplished by dipping, flow coating, hopper coating, doctor blade
coating, etc. It is desirable that the polymer binder for the free
radical and the photobleachant as well as the solvent therefor and
the support upon which the coating solution may be applied do not
react with either the stable-free radical or the photobleachant.
Among the polymeric binders which have been found useful herein are
cellulose esters such as for example, cellulose acetate, cellulose
acetate butyrate and cellulose acetate propionate; polyester
materials, especially poly(ethylene therephthalate), polyvinyl and
poly-.alpha.-olefin resins, all of which may be codissolved with
the photoreactants using conventional solvents such as the
alcohols, acetone, methylene chloride, naphtha and a wide variety
of other materials. When a binder is used, the concentration of the
combined free radical and photo-bleachant generally range from
about 1 weight percent to about 90 weight percent, based on the
total weight of the composition, with a preferred range occurring
from about 2 weight percent to about 60 weight percent. However,
the concentration of photo-reactants would be 100 percent in the
case where a binder is not used and the active components are, for
example, imbibed into a porous support.
If a support is utilized to prepare a photographic element. Useful
materials include conventional photo-graphic support like glass,
metal, paper or the resinous supports, e.g., cellulose acetate,
poly(ethylene terephthalate), poly-.alpha.-olefins, polystyrenes,
etc., which are well known in the photographic arts, may be
used.
Once prepared, the photographic compositions or elements of the
present type can be exposed to actuating rays for the
photobleachant and image formation occurs directly on exposures. It
is theorized that the reaction which occurs upon exposure of the
photosensitive compositions of the present invention to activating
rays may be described generically and most simply as follows:
##SPC4##
The following examples are included for a further understanding of
the invention.
EXAMPLE I
A photographic composition of the present type is prepared by
dissolving 0.03 g. of 1-oxyl-2-[4-dimethyl-amino
phenyl]-4,4,5,5-tetramethyldehydroimidazole-3-oxide and .131 g. of
4-diethylaminobenzenediazonium tetra-fluoroborate along with 10 g.
of cellulose acetate butyrate, in 25 mls. of 2-methoxyethanol plus
75 mls. of methylene chloride. The coating solution is coated on a
paper support at a wet thickness of 0.005 inches. When dry, a
portion of the photographic element is imagewise exposed to
ultraviolet rays in the exposure in a Filmsort 086 unit of a diazo
printer which contains a mercury arc source. The coating bleached
to nearly colorless in the exposed area, while it remains unchanged
in unexposed areas. Color change is from blue to colorless in
exposed areas. A control coating is prepared in the same manner,
except that the diazonium salt photobleachant is omitted. This
coating is then exposed in the same manner, in a Filmsort 086 Diazo
printer. After a period of 10 minutes, the element is removed, and
shows no visible signs of bleaching in the exposed areas. No
differential density between the exposed and unexposed areas can be
detected thereby indicating that the free-radical exhibits high
stability.
EXAMPLE II
The procedure described in Example I is used except that the
diazonium salt component is replaced by 0.5 g. of polyethylene
glycol, average MW 600. This coating is also bleached in the
exposed areas from blue to colorless, but remains unchanged in
unexposed areas.
EXAMPLE III
The procedure described in Example I is used to prepare another
photographic element, except the diazonium salt is replaced by 0.04
g. of benzophenone, and 0.04 g. of benzhydrol were used; and also 2
g. of cellulose acetate butyrate in 5 mls. of 2-methoxyethanol plus
15 mls. of methylene chloride is used. The resultant element
bleaches in exposed areas but remains unchanged in unexposed area.
Color change is from blue to colorless.
It will be appreciated that the convenient procedures described
herein, such as in the Examples, can be used with any stable free
radicals and photo-bleachants of the present type. Such variations
will be apparent to those skilled in the art.
Other ingredients such as sensitizers, matting agents,
plasticizers, etc. may also be added to the imaging systems of the
present invention to improve various aspects and characteristics
thereof. Fixing and/or stabilization treatments may be used to
improve the quality and/or stability of the images formed using the
imaging products of the present invention.
For example, in some instances, e.g., when a
bis-2,4,5-triarylimidazole is used as the photobleachant, it may be
desirable to obtain a degree of fixation such as might be required
for use of the image in the presence of ultraviolet light. This can
be accomplished by preferentially eliminating the photo-bleachant,
e.g., bis-2,4,5-triarylimidazole, from the unexposed areas through
the use of solvent washout of the photobleachant or a redox system
such as the quinone-polyethylene oxide system which is activated at
wavelengths different than the photo-bleachant and on activation
deactivates the photobleachant. When a diazonium salt is used as
the photobleachant, it may be removed from the non-image areas by
incorporating a conventional diazo coupler, for example
2-hydroxynaphthol in the system and coupling the diazonium salt by
exposure of the system to a basic medium without generating
extensive density in the non-image area.
There has thus been described herein a series of imaging elements
which find advantageous use in applications wherein photosensitive
elements which react only to, for example, light of short
wavelength, e.g., specific wavelengths of ultraviolet light, but
have low sensitivity to light of longer wavelengths, e.g., visible
light, so that the resulting image is substantially stable under
normal conditions of use and does not require additional fixation
or stabilization treatments.
The invention has been described in detail with specific reference
to preferred embodiments thereof, however, it will be readily
recognized that variations and modifications can be made within the
spirit and scope of the invention and the same should not be
limited except as defined in the appended claims.
* * * * *