U.S. patent application number 09/733786 was filed with the patent office on 2001-11-08 for aggregated dyes for radiation-sensitive elements.
Invention is credited to Barber, Gary Norman, Brick, Mary Christine, Gallo, Elizabeth Ann, Harrison, William James, Helber, Margaret Jones, Kortum, Steven Wade.
Application Number | 20010038978 09/733786 |
Document ID | / |
Family ID | 24258795 |
Filed Date | 2001-11-08 |
United States Patent
Application |
20010038978 |
Kind Code |
A1 |
Helber, Margaret Jones ; et
al. |
November 8, 2001 |
Aggregated dyes for radiation-sensitive elements
Abstract
A dispersion comprising an aqueous medium having dispersed
therein an aggregated dye of the Formula (I): 1 wherein X is oxygen
or sulfur; R.sup.1-R.sup.4 each independently represent an
unsubstituted or substituted alkyl group, an unsubstituted or
substituted aryl group or an unsubstituted or substituted
heteroaryl group; L.sup.1, L.sup.2 and L.sup.3 each independently
represent substituted or unsubstituted methine groups; M.sup.+
represents a proton or an inorganic or organic cation; and n is 0,
1, 2 or 3 and wherein the aggregated dye in the dispersion has an
absorption halfbandwidth of less than 55 nm.
Inventors: |
Helber, Margaret Jones;
(Rochester, NY) ; Harrison, William James; (Herts,
GB) ; Gallo, Elizabeth Ann; (Rochester, NY) ;
Brick, Mary Christine; (Webster, NY) ; Kortum, Steven
Wade; (Rochester, NY) ; Barber, Gary Norman;
(Penfield, NY) |
Correspondence
Address: |
Sarah Meeks Roberts
Patent Legal Staff
Eastman Kodak Company
343 State Street
Rochester
NY
14650-2201
US
|
Family ID: |
24258795 |
Appl. No.: |
09/733786 |
Filed: |
December 7, 2000 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09733786 |
Dec 7, 2000 |
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08565480 |
Nov 30, 1995 |
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6183944 |
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Current U.S.
Class: |
430/512 ;
430/517; 430/522 |
Current CPC
Class: |
C09B 67/008 20130101;
G03C 1/832 20130101 |
Class at
Publication: |
430/512 ;
430/522; 430/517 |
International
Class: |
G03C 001/83; G03C
001/815; G03C 001/825 |
Claims
What is claimed is:
1. A dispersion comprising an aqueous medium having dispersed
therein an aggregated dye of the Formula (I): 20wherein X is oxygen
or sulfur; R.sup.1-R.sup.4 each independently represent an
unsubstituted or substituted alkyl group, an unsubstituted or
substituted aryl group or an unsubstituted or substituted
heteroaryl group; L.sup.1, L.sup.2 and L.sup.3 each independently
represent substituted or unsubstituted methine groups; M+
represents a proton or an inorganic or organic cation; and n is 0,
1, 2 or 3 and wherein the aggregated dye in the dispersion has an
absorption halfbandwidth of less than 55 nm.
2. A dispersion in accordance with claim 1, wherein the dye is of
the Formula (II): 21wherein R.sup.5 represents a hydrogen atom or
substituted or unsubstituted alkyl, aryl or acyl group.
3. A dispersion in accordance with claim 2, wherein each of R.sup.1
and R.sup.2 is independently an unsubstituted or substituted alkyl,
aryl or heteroaryl group.
4. A dispersion in accordance with claim 3, wherein each of R.sup.3
and R.sup.4 is a hydrogen atom.
5. A dispersion in accordance with claim 4 wherein R.sup.5 is a
hydrogen atom or a methyl or ethyl group.
6. A dispersion in accordance with claim 5, wherein each of R.sup.1
and R.sup.2 is independently an unsubstituted or substituted phenyl
group.
7. A dispersion in accordance with claim 6, wherein the each of
R.sup.1 and R.sup.2 is independently a phenyl group substituted
with a substituent selected from hydroxyl, halogen, carboxyl,
alkyl, alkoxy, acyl, cyano, and --NHSO.sub.2Me.
8. A dispersion in accordance with claim 1, wherein the dye is of
Formula (III): 22wherein R.sup.5 represents a hydrogen atom or an
unsubstituted or substituted alkyl, aryl or acyl group.
9. A dispersion in accordance with claim 8, wherein each of R.sup.1
and R.sup.2 is independently an unsubstituted or substituted alkyl,
aryl or heteroaryl group.
10. A dispersion in accordance with claim 9, wherein each of
R.sup.3 and R.sup.4 is a hydrogen atom.
11. A dispersion in accordance with claim 10 wherein R.sup.5 is a
hydrogen atom or a methyl or ethyl group.
12. A dispersion in accordance with claim 11, wherein, each of
R.sup.1 and R.sup.2 is independently an unsubstituted or
substituted phenyl group.
13. A dispersion in accordance with claim 1, wherein the aqueous
medium comprises water and a hydrophilic colloid.
14. A dispersion in accordance with claim 13, wherein the
hydrophilic colloid is gelatin.
15. A method of preparing an aqueous dispersion in accordance with
claim 1, wherein the dye is added to the aqueous medium at a
temperature of from about 20 to about 100.degree. C. with agitation
and continuing agitation for from about 5 minutes to about 48
hours.
16. A method in accordance with claim 15, wherein the dye is added
to the aqueous medium in the form of microcrystalline solid
particles.
17. A method in accordance with claim 15, wherein the dye is added
to the aqueous medium as a powdered solid or an aqueous slurry
thereof.
18. A radiation-sensitive element containing an aggregated dye of
Formula (I), (II) or (III): 23wherein X is oxygen or sulfur;
R.sup.1-R.sup.4 each independently represent an unsubstituted or
substituted alkyl group, an unsubstituted or substituted aryl group
or an unsubstituted or substituted heteroaryl group; L.sup.1,
L.sup.2 and L.sup.3 each independently represent substituted or
unsubstituted methine groups; R.sup.5 represents a hydrogen atom or
substituted or unsubstituted alkyl, aryl or acyl group; M+
represents a proton or an inorganic or organic cation; and n is 0,
1, 2 or 3 and wherein the aggregated dye in the dispersion has an
absorption halfbandwidth of less than 55 nm.
19. A photographic element comprising a support bearing at least
one light sensitive layer, said element containing an aggregated
dye of Formula (I), (II) or (III): 24wherein X is oxygen or sulfur;
R.sup.1-R.sup.4 each independently represent an unsubstituted or
substituted alkyl group, an unsubstituted or substituted aryl group
or an unsubstituted or substituted heteroaryl group; L.sup.1,
L.sup.2 and L.sup.3 each independently represent substituted or
unsubstituted methine groups; R.sup.5 represents a hydrogen atom or
substituted or unsubstituted alkyl, aryl or acyl group; M+
represents a proton or an inorganic or organic cation; and n is 0,
1, 2 or 3 and wherein the aggregated dye in the dispersion has an
absorption halfbandwidth of less than 55 nm.
20. A photographic element according to claim 19 which further
comprises a non-light sensitive layer and said aggregated dye is in
said non-light sensitive layer.
21. A photographic element according to claim 20, wherein the
non-light sensitive layer is in an interlayer between two light
sensitive layers.
22. A photographic element according to claim 20, wherein the non
light-sensitive layer is an antihalation layer.
Description
FIELD OF THE INVENTION
[0001] This invention relates to a dispersion of an aggregated dye,
a method for preparing said dispersion and a radiation-sensitive
element containing said aggregated dye.
BACKGROUND OF THE INVENTION
[0002] Radiation-sensitive materials, including light-sensitive
materials, such as photographic materials, may utilize filter dyes
for a variety of purposes. Filter dyes may be used to adjust the
speed of a radiation-sensitive layer; they may be used as absorber
dyes to increase image sharpness of a radiation-sensitive layer;
they may be used as antihalation dyes to reduce halation; they may
be used to reduce the amount or intensity of radiation from
reaching one or more radiation-sensitive layers, and they may also
be used to prevent radiation of a specific wavelength or range of
wavelengths from reaching one or more of the radiation-sensitive
layers in a radiation-sensitive element. For each of these uses,
the filter dye(s) may be located in any number of layers of a
radiation-sensitive element, depending on the specific requirements
of the element and the dye, and on the manner in which the element
is to be exposed. The amount of filter dyes used varies widely, but
they are preferably present in amounts sufficient to alter in some
way the response of the element to radiation. Filter dyes may be
located in a layer above a radiation-sensitive layer, in a
radiation-sensitive layer, in a layer below a radiation-sensitive
layer, or in a layer on the opposite side of the support from a
radiation-sensitive layer.
[0003] Photographic materials often contain layers sensitized to
different regions of the spectrum, such as red, blue, green,
ultraviolet, infrared, X-ray, to name a few. A typical color
photographic element contains a layer sensitized to each of the
three primary regions of the visible spectrum, i.e., blue, green,
and red. Silver halide used in these materials has an intrinsic
sensitivity to blue light. Increased sensitivity to blue light,
along with sensitivity to green light or red light, is imparted
through the use of various sensitizing dyes adsorbed to the silver
halide grains. Sensitized silver halide retains its intrinsic
sensitivity to blue light.
[0004] There are numerous applications for which filtration or
absorbance of very specific regions of light are highly desirable.
Some of these applications, such as yellow filter dyes and magenta
trimmer dyes, require non-diffusing dyes which may be coated in a
layer specific manner to prevent specific wavelengths of light from
reaching specific layers of the film during exposure. These dyes
must have sharp-cutting bathochromic absorbance features on the
bathochromic side to prevent light punch through without adversely
affecting the speed of the underlying emulsions. Depending on the
location of these filter layers relative to the sensitized silver
halide emulsion layers, it would also be desirable to have
non-diffusing, layer specific filter dyes with absorption spectra
which are sharp-cutting on the hypsochromic edge as well as the
bathochromic edge. Such dyes are sometimes known as "finger
filters". Preferably these dyes should exhibit high extinction
coefficients, narrow halfbandwidths and sharp cutting hypsochromic
and bathochromic absorption envelopes when incorporated into
photographic elements. Typically, to achieve these properties,
solutions of dissolved, monomeric dyes (non-aggregated) have been
incorporated. Dyes introduced by this method cannot be coated in a
layer specific manner without the use of mordants, and therefore
they often wander into adjacent layers and can cause problems such
as speed loss or stain. Solubilized monomeric dyes may be mordanted
to prevent wandering through adjacent layers. While the use of
polymeric mordants can prevent dye wandering, such mordants
aggravate the stain problem encountered when the dye remains in the
element through processing.
[0005] Dyes with a high extinction coefficient allow maximum light
absorption using a minimum amount of dye. Lower requisite dye
laydown reduces the cost of light filtration and produces fewer
processing by-products. Lower dye laydowns may also result in
reduced dye stain in short duration processes.
[0006] Finger filters such as described above are highly desirable
for other uses such as protecting silver halide sensitized
emulsions from exposure by safelights. Such dyes must have
absorbance spectra with high extinction coefficients and narrow
halfbandwidths, and sharp cutting absorbance envelopes to
efficiently absorb light in the narrow safelight-emitting region
without adversely affecting the speed of the sensitized silver
halide emulsions. This affords protection for the sensitized
emulsion from exposure by light in the safelight's spectral region.
Useful absorbance maxima for safelight dyes include, but are not
restricted to 490 nm and 590 nm.
[0007] Similar properties are required for infrared absorbing
filter dyes. Laser-exposed radiation-sensitive elements require
high efficiency light absorbance at the wavelength of laser
emission. Unwanted absorbance from broadly absorbing dyes reduces
the efficiency of light capture at the laser emission wavelength,
and requires the use of larger amounts of dye to adequately cover
the desired spectral region. In photographic elements, unwanted
absorbance may also cause speed losses in adjacent silver halide
sensitized layers if the photographic element has multiple
sensitized layers present. Useful finger filter absorbance maxima
for absorbing laser and phosphor emissions include but are not
restricted to 790 nm, 633 nm, 670 nm, 545 nm and 488 nm. [Laser
ablation/non-photograph- ic]
[0008] In some photographic elements it is necessary to provide
light filtration or antihalation at deep cyan and infrared
wavelengths. Typically such protection has been achieved using
water soluble dyes or milled solid particle dyes. Typically, water
soluble monomeric dyes can provide relatively sharp, high
extinction absorbance, but are prone to interlayer wandering. Solid
particle dispersions of typical cyan filter dyes are broad
absorbing, see for example U.S. Pat. No. 4,770,984, and often
weakly absorbing at 700 nm.
[0009] One common use for filter dyes is in silver halide light
sensitive photographic elements. If, prior to processing, blue
light reaches a layer containing silver halide which has been
sensitized to a region of the spectrum other than blue, the silver
halide grains exposed to the blue light, by virtue of their
intrinsic sensitivity to blue light, would be rendered developable.
This would result in a false rendition of the image information
being recorded in the photographic element. It is therefore a
common practice to include in the photographic element a material
that filters blue light. This blue-absorbing material can be
located anywhere in the element where it is desirable to filter
blue light. In a color photographic element that has layers
sensitized to each of the primary colors, it is common to have the
blue-sensitized layer closest to the exposure source and to
interpose a blue-absorbing, or yellow filter layer between the
blue-sensitized layer and the green- and red-sensitized layers.
[0010] Another common use for filter dyes is to filter or trim
portions of the UV, visible or infrared spectral regions to prevent
unwanted wavelengths of light from reaching sensitized emulsions.
Just as yellow filter dyes prevent false color rendition from the
exposure of emulsions sensitized to a region of the spectrum other
than blue, UV, magenta, cyan and infrared filter dyes can prevent
false color rendition by shielding sensitized emulsion layers from
exposure to specific wavelength regions. One application of this
strategy is the use of green-absorbing magenta trimmer dyes. In one
type of typical color photographic element containing a layer
sensitized to each of the three primary regions of the visible
spectrum, i.e., blue, green, and red, the green-sensitized layer is
coated above the red-sensitized layer and below the blue-sensitized
layer. Depending on the chosen spectral sensitivity maxima for the
sensitized silver halide layers, there may be a region of overlap
between the spectral sensitivities of the green and red emulsions.
Under such circumstances, green light which is not absorbed by the
green-sensitive emulsion can punch through to the red sensitive
emulsion and be absorbed by the leading edge of the red spectral
sensitizing dye. This crosstalk between the green and red emulsions
results in false color rendition. It would, therefore, be highly
desirable to find a green-absorbing filter dye which upon
incorporation into a photographic element would absorb strongly
around the spectral maximum of the green-sensitized emulsion, and
possess a sharp cutting bathochromic absorbance such that there is
no appreciable absorbance just bathochromic to its absorbance
maximum. Though the position of optimal absorption maximum for a
magenta trimmer dye will vary depending on the photographic element
being constructed, it is particularly desirable in one type of
typical color photographic element containing a layer sensitized to
each of the three primary regions of the visible spectrum, i.e.,
blue, green, and red, that a magenta trimmer dye absorb strongly at
about 550 nm, and possess a sharp cutting bathochromic absorbance
such that there is no appreciable absorbance above about 550 nm.
Therefore it would be desirable to provide a filter dye for use in
photographic elements that possesses high requisite absorbance in
the green region of the spectrum below about 550 nm, but little or
no absorbance above about 550 nm, and furthermore does not suffer
from incubative or post process stain problems, and furthermore is
not prone to migration in the coated film, but is fully removed
upon processing.
[0011] One method used to incorporate soluble monomeric filter dyes
into photographic film element layers is to add them as aqueous or
alcoholic solutions. Dyes introduced by this method are generally
highly mobile and rapidly diffusing and often wander into other
layers of the element, usually with deleterious results. While the
use of polymeric mordants can prevent dye wandering, such mordants
aggravate the stain problem encountered when the dye remains in the
element through processing.
[0012] Filter dyes have also been prepared as conventional
dispersions in aqueous gelatin using standard colloid milling or
homogenization methods or as loaded latices. More recently,
ball-milling, sand-milling, media-milling and related methods of
producing fine particle size slurries and suspensions of filter
dyes have become standard tools for producing slurries and
dispersions that can readily be used in photographic melt
formulations. Solid particulate filter dyes introduced as
dispersions, when coated at sufficiently low pH, can eliminate
problems associated with dye wandering. However, milled, insoluble
solid particulate filter dyes provide relatively low absorption
coefficients, requiring that an excessive amount of dye be coated.
In addition, the time and expense involved in preparing serviceable
solid particulate filter dye dispersions by milling techniques are
a deterrent to their use, especially in large volume applications.
It is therefore desirable to provide dye dispersions that do not
necessarily require mechanical milling before use and that do not
wander but that wash out easily during processing leaving little or
no residual stain. It is also desirable that such filter dye
dispersions provide high light absorption efficiencies with
sharp-cutting absorbance peaks. One method of obtaining these
desirable dye features in solid particulate dispersions of oxonol
filter dyes was described by Texter (U.S. Pat. No. 5,274,109 and
U.S. Pat. No. 5,326,687). Texter describes a process by which
pyrazolone oxonol dyes are microprecipitated under strictly
controlled pH conditions to produce absorbance spectra which are
narrow, bathochromic and sharp cutting on the long wavelength side
relative to their corresponding milled solid particulate
dispersions. This technique, however, is impractical for large
volume applications.
PROBLEM TO BE SOLVED BY THE INVENTION
[0013] It is therefore desirable to have a filter dye which has a
high extinction coefficient, narrow halfbandwidth, sharp cutting on
both the hypsochromic and bathochromic edge, and capable of being
substantially completely removed or rendered colorless on process
of an exposed radiation-sensitive element comprising said dye. It
is also desirable to have a method for preparing a dispersion of a
filter dye that is suitable for high volume manufacture.
SUMMARY OF THE INVENTION
[0014] One object of this invention is to provide a filter dye
which when dispersed and aggregated in a hydrophilic colloid such
as gelatin, possesses a spectral absorbance maximum
bathochromically shifted and exhibits an unusually high extinction
coefficient and an exceptionally narrow halfbandwidth relative to
its non-aggregated solution absorbance spectrum.
[0015] Another object of this invention is to provide a filter dye
which when dispersed and aggregated in a hydrophilic colloid such
as gelatin, possesses narrow absorption bands exhibiting an
especially sharp-cutting absorbance envelope on the short and long
wavelength edges.
[0016] Another object of this invention is to provide a filter dye
which when dispersed and aggregated in a hydrophilic colloid such
as gelatin, exhibits low dye diffusibility and interlayer
wandering.
[0017] Another object of this invention is to provide a direct
gelatin dispersion method allowing easy and reproducible
incorporation of the inventive dyes in an aggregated state, with
all desirable properties intact, into photographic elements without
recourse to milling techniques.
[0018] Another object of this invention is to provide a filter dye
which when dispersed and aggregated in a hydrophilic colloid such
as gelatin exhibits excellent stability at high temperature and
humidity conditions.
[0019] Another object of the invention is to provide a silver
halide radiation-sensitive material containing at least one
aggregated dye, incorporated in a hydrophilic colloid layer, which
is decolorized irreversibly by photographic processing and which
causes no deleterious effects on the silver halide photographic
emulsions before or after processing.
[0020] A further object of the invention is to provide a silver
halide radiation-sensitive material in which a hydrophilic colloid
layer is dyed and exhibits excellent decolorizing properties upon
photographic processing.
[0021] Yet another object of the invention is to provide a silver
halide radiation-sensitive material in which a hydrophilic colloid
layer is dyed and exhibits high absorbance in a portion of the
spectral region at its absorbance maximum, but possesses
comparatively little absorbance around 20 nm above its absorbance
maximum.
[0022] Yet another object of the invention is to provide a silver
halide radiation-sensitive material in which a hydrophilic colloid
layer is dyed and exhibits high absorbance in a portion of the
spectral region at its absorbance maximum, but possesses
comparatively little absorbance around 20 nm below its absorbance
maximum.
[0023] We have now discovered that certain dyes of Formula I, II
and III, set forth below, aggregate when dispersed in an aqueous
medium (preferably containing a hydrophilic colloid) and provide
the advantages set for in the above objects of the invention. The
said dye dispersion can be prepared by dispersing powdered dye or
microcrystalline solid dye particles in an aqueous medium,
preferably containing gelatin or other hydrophilic colloid, using
the methods set forth herein.
[0024] One aspect of this invention comprises an aqueous dispersion
comprising an aqueous medium having dispersed therein an aggregated
dye of structural Formula I: 2
[0025] wherein X is oxygen or sulfur; R.sup.1-R.sup.4 each
independently represent an unsubstituted or substituted alkyl
group, an unsubstituted or substituted aryl group or an
unsubstituted or substituted heteroaryl group; L.sup.1, L.sup.2 and
L.sup.3 each independently represent substituted or unsubstituted
methine groups; M.sup.+ represents a proton or an inorganic or
organic cation; and n is 0, 1, 2 or 3 and wherein the aggregated
dye in the dispersion has an absorption halfbandwidth of less than
55 nm.
[0026] In another preferred embodiment of the invention the
aggregated dye of structural Formula I is of Formula II: 3
[0027] wherein R.sup.1 to R.sup.4 and M.sup.+ are as defined above
and R.sup.5 represents a hydrogen atom or an unsubstituted or
substituted alkyl, aryl or acyl group.
[0028] In yet another preferred embodiment of the invention the
aggregated dye of structural Formula I is of Formula III: 4
[0029] wherein R.sup.1 to R.sup.4, X, M.sup.+ and R.sup.5 are as
defined above.
[0030] Still another preferred embodiment of the invention
comprises a radiation-sensitive element, such as a photographic
element, containing an aggregated dye of structural Formula I, II
or III.
[0031] Yet another preferred embodiment of the invention comprises
a method of preparing a dispersion which comprises adding a dye of
structural Formula I, II or III to an aqueous medium at a
temperature of from about 20 to about 100.degree. C. and agitating
the mixture for about 5 minutes to about 48 hours.
ADVANTAGEOUS EFFECTS OF THE INVENTION
[0032] This invention provides a dye, useful as a filter dye in a
radiation-sensitive element, such as a photographic element, which
when dispersed in an aqueous medium, for example aqueous gelatin,
dissolves then spontaneously aggregates. In some instances, the
aggregated dye state constitutes an unusually well-ordered and
thermodynamically stable liquid crystalline phase. A dye in the
aggregated state possesses a coated .lambda..sub.max which is
substantially bathochromic to that of its monomeric non-aggregated
state and exhibits exceptionally high covering power at its coating
.lambda..sub.max Further the aggregated dye exhibits sharp-cutting
bathochromic and hypsochromic spectral features absorbing strongly
at its coating .lambda..sub.max while absorbing comparatively
little light at wavelengths just below or just above its absorbance
maximum. Further, the aggregated dye possesses an unusually narrow
halfbandwidth. The dyes can be formulated using methods for
producing microcrystalline solid particle dye dispersions (SPD's),
or as direct gelatin dispersions (DGD's) for incorporation in a
photographic element. In such an environment, the spontaneously
aggregated dyes exhibit little, if any tendency to wander within
the element and upon processing are substantially free of
post-process stain problems.
DETAILED DESCRIPTION OF THE INVENTION
[0033] As noted above, the dispersion of this invention comprises
an aggregated dye of Formula I: 5
[0034] wherein X is oxygen or sulfur; R.sup.1-R.sup.4 each
independently represent an unsubstituted or substituted alkyl
group, an unsubstituted or substituted aryl group or an
unsubstituted or substituted heteroaryl group; L.sup.1, L.sup.2 and
L.sup.3 each independently represent substituted or unsubstituted
methine groups; M.sup.+ represents a proton or an inorganic or
organic cation; and n is 0, 1, 2 or 3 and wherein the aggregated
dye in the dispersion has an absorption halfbandwidth of less than
55 nm.
[0035] In a preferred embodiment of the invention the aggregated
dye of structural Formula I is of Formula II: 6
[0036] wherein R.sup.1 to R.sup.4 and M.sup.+ are as defined above
and R.sup.5 represents a hydrogen atom or an unsubstituted or
substituted alkyl, aryl or acyl group.
[0037] In yet another preferred embodiment of the invention the
aggregated dye of structural Formula I is of Formula III: 7
[0038] wherein R.sup.1 to R.sup.4 , X and M.sup.+ are as defined
above.
[0039] In Formula (I), (II) and (III), illustrative alkyl groups
preferably contain 1 to 6 carbon atoms and include methyl, ethyl,
n-propyl, isopropyl, n-butyl, t-butyl, n-hexyl, and isohexyl.
Examples of aryl groups include phenyl, naphthyl, anthracenyl, and
styryl. Examples of substituted aryl groups include, for example,
tolyl, m-chlorophenyl and p-methanesulfonylphenyl, etc. Examples of
heteroaryl groups include pyridyl, thienyl, furyl, and pyrrolyl.
Examples of acyl groups include ethoxycarbonyl, amido, benzoyl,
carboxy and acetyl. M.sup.+ is preferably H, Na, K, triethyl
ammonium or pyridinium.
[0040] When reference in this application is made to a substituent
"group", this means that the substituent may itself be substituted
or unsubstituted (for example "alkyl group" refers to an
unsubstituted or substituted alkyl). Generally, unless otherwise
specifically stated, substituents on any "groups" referenced herein
or where something is stated to be possibly substituted, include
the possibility of any groups, whether substituted or
unsubstituted, which do not destroy properties necessary for the
photographic utility. For example, the filter dyes of this
invention should not contain a substituent or combination of
substituents, which render the dye too soluble at coating pH's,
favoring a mobile monomeric dye species instead of the preferred
aggregated dye species. It will also be understood throughout this
application that reference to a compound of a particular general
formula includes those compounds of other more specific formula
which specific formula falls within the general formula
definition.
[0041] Examples of substituents on any of the mentioned groups can
include known substituents, such as: halogen, for example, chloro,
fluoro, bromo, iodo; alkoxy, particularly those with 1 to 6 carbon
atoms (for example, methoxy, ethoxy); substituted or unsubstituted
alkyl, particularly lower alkyl (for example, methyl,
trifluoromethyl); alkenyl or thioalkyl (for example, methylthio or
ethylthio), particularly either of those with 1 to 6 carbon atoms;
substituted and unsubstituted aryl, particularly those having from
6 to 20 carbon atoms (for example, phenyl, naphthyl, anthracenyl or
styryl); and substituted or unsubstituted heteroaryl, particularly
those having a 5 or 6-membered ring containing 1 to 3 heteroatoms
selected from N, O, or S (for example, pyridyl, thienyl, furyl,
pyrrolyl); and others known in the art. Alkyl substituents may
specifically include "lower alkyl", that is having from 1 to 6
carbon atoms, for example, methyl, ethyl, and the like. Further,
with regard to any alkyl group, alkylene group or alkenyl group, it
will be understood that these can be branched or branched and
include ring structures.
[0042] Examples of preferred dyes of this invention are listed
below.
1TABLE I 8 Dye R.sup.6 R.sup.7 R.sup.8 R.sup.9 R.sup.10 R.sup.11
M.sup.+ 1 H H H OMe H Me H 2 H H Me OH H H H 4 H H H H OMe Me H 4A
H H H H OMe Me Na 5 H H H OH H Me H 7 H H H OMe H Et H 8 H H H H
OMe H H 8A H H H H OMe H TEAH 9 H H H H OH H H 9A H H H H OH H PyrH
10 H H H OH H H H 11 H OMe H H H H H 10A H H H OH H H PyrH 10B H H
H OH H H TEAH 12 H OMe H H OMe H H 14 H H H Me H Me H 15 H H H H Me
H H 16 H H H H OMe Me H 17 H H H Me H CONH.sub.2 H 18 H H H Cl H Me
H 19 H H H CN H Me H 20 H H H CONH.sub.2 H Et H 21 H H H Me H Et
TEAH 22 H H Me H H Me H 23 H H H OMe H COPh TEAH 24 H H H COOH H Et
H 25 H H H NHSO.sub.2Me H Me H 26 H H OMe H OMe Me H 27 H H CN H CN
Me H 28 H H Cl H H Et H 29 H H COOH H H Me H 30 H OMe OMe H H Me H
31 H OMe H Me H Et H 32 H OMe H Me H CONMe.sub.2 H 33 H H Cl OH Cl
Et H 34 H CN H H H H H 35 H H H H H Me H
[0043]
2TABLE II 9 Dye R.sup.6 R.sup.7 R.sup.8 R.sup.9 R.sup.10 R.sup.11
M.sup.+ 3 H H OH H H H H 3A H H OH H H H PyrH 6 H H H OH H H H 13 H
H H H H H H 13A H H H H H H TEAH 36 H OH H H H H TEAH 37 H H OH OH
H H H 38 H H H NHSO.sub.2Me H H TEAH 39 H H OH Me H H TEAH
[0044]
3TABLE III 10 Dye R.sup.6 R.sup.7 R.sup.8 R.sup.9 R.sup.10 R.sup.11
M.sup.+ 40 H H H H H H TEAH 41 H H H Cl H H TEAH 42 H H H Me H H
TEAH 43 H H H OH H H TEAH 44 H H H NHCOCH.sub.3 H H TEAH 45 H H OMe
H H H TEAH 46 H H OMe H H Me TEAH
[0045]
4TABLE IV DYE 47 11 DYE 48 12 DYE 49 13 DYE 50 14 DYE 51 15 DYE 52
16 DYE 53 17 DYE 54 18
[0046] The dyes of Formulas (I), (II) and (III) can be prepared by
synthetic techniques well-known in the art, as illustrated by the
synthetic examples below. Such techniques are further illustrated,
for example, in "The Cyanine Dyes and Related Compounds", Frances
Hamer, Interscience Publishers, 1964.
[0047] The dispersions of this invention can be prepared in any of
the ways known in the art (e.g., with the aid of a high-boiling
non-polar organic solvent or in suitable water-miscible solvents
such as methyl alcohol or dimethylformamide or the like), but are
preferably formulated using methods developed for producing solid
microcrystalline particles of dye (SPD's) or are more preferably
formulated as direct gelatin dispersions (DGD's) as described
herein.
[0048] A dispersion comprising solid microcrystalline particles of
dye (SPD) can be prepared by known methods. Such methods includes
forming a slurry of the dye in an aqueous medium comprising water
and a surfactant and the subjecting the slurry to a milling
procedure such as ball-milling, sand-milling, media-milling or
colloid-milling (preferably media-milling). The SPD can then be
added to an aqueous medium comprising water and a hydrophilic
colloid, such as gelatin, for use in a photographic element.
[0049] In another preferred embodiment, the dyes may be formulated
as a direct gelatin dispersion (DGD) wherein the finely powdered
dye or aqueous slurry thereof is simply mixed or agitated with
aqueous medium containing gelatin (or other hydrophilic colloid) at
a temperature of 40.degree. C. or higher. This method does not
require the use of organic solvents, surfactants, polymer
additives, milling processes, pH control or the like. It is
simpler, faster, more forgiving and more flexible than prior
processes.
[0050] In either of the preferred methods, the dyes may be
subjected to elevated temperatures before and/or after gelatin
dispersion, but to obtain desirable results, this heat treatment is
carried out preferably after dispersing in gelatin. The optimal
temperature range for preparing gelatin-based dispersions is
40.degree. C.-100.degree. C. but should remain below the
decomposition points of the dyes. The heating time is not
especially critical as long as the dyes are not decomposed, but in
general it is in the range of 5 minutes to 48 hours. A similar heat
treatment may be applied, if so desired, to dyes prepared as solid
particle dispersions before and/or after dispersion in aqueous
gelatin to obtain effective results. Furthermore, if so desired, pH
and/or ionic strength adjustments may be utilized to control the
solubility and aggregation properties of dyes prepared using SPD or
DGD formulation techniques. The direct gelatin dispersion method is
advantageous in that it does not necessarily require the use of
organic solvents, surfactants, polymer additives, milling
processes, pH control or the like. A related method described by
Boettcher for preparing concentrated sensitizing dye dispersions in
aqueous gelatin (PCT WO 93/23792) is equally effective when applied
to the inventive dyes. The entire disclosure of WO 93/23792 is
incorporated herein by reference.
[0051] Solid particle dispersion and direct gelatin dispersion
formulations of the compound of Formula (I-III) are useful as
general purpose filter dyes, alone or in combination with other
filter dyes in photographic elements. The dyes formulated as
described above possess finite but low solubilities and a
pronounced tendency to aggregate spontaneously at coating pH's of 6
or less (generally 4-6) so that they do not interact with other
components of the photographic element. However, they are highly
soluble at processing pH's of 8 or more (generally 8-12), such that
they are still fully removed during photographic processing.
[0052] A particular advantage of the inventive dyes is that in the
aggregated state, they provide higher covering power at their
coating .lambda..sub.max than comparable known dyes which are
insoluble and exist as microcrystalline solid particles in the
photographic medium. This advantage is particularly important in
modern film formats and processing conditions, as filter dyes with
high covering power need not be coated at as high a coverage as
dyes with lower covering power in order to achieve the same degree
of light filtration. In addition to reducing manufacturing costs,
lower levels of coated dyes will reduce the level of dye residue
built up in the processing solutions, and the resulting lower
levels of dissolved dye residue removed from photographic elements
will have reduced environmental impact.
[0053] A further advantage of dyes of the invention is that they
generally possess absorbance envelopes that are sharper cutting on
the bathochromic side than comparable known solid particle dyes
such as the structural analogs disclosed in Agfa U.S. Pat. No.
4,770,984. This feature is especially advantageous when strong
light absorbance is required in a spectral region up to a specific
.lambda..sub.max, and maximum light transmission is required past
the specified .lambda..sub.max. Such filter or trimmer dyes are
especially useful when coated in specific layers of color
photographic films to effectively prevent light of a specific
wavelength region from exposing radiation-sensitive layers below
the light filtration layer containing the dye, without causing
unwanted absorption of longer wavelength radiation. A green filter
dye coated directly above a red-sensitive silver halide layer is a
particularly advantageous example of such absorbance features, and
excellent green/red speed separation can be realized. In a typical
color photographic element, it is desirable to have a
green-absorbing filter dye which when coated absorbs strongly at
wavelengths close to 550 nm, but which absorbs comparatively little
at wavelengths greater than 550 nm. It should be emphasized that
the exact envelope of desirable light absorbance for a filter dye,
even specifically a green filter dye, varies tremendously from one
photographic element to another depending on the intended purpose
of the material. Some photographic elements might require a filter
dye, such as a green filter dye, which absorbs strongly up to a
wavelength somewhat shorter or longer than 550 nm, but is sharp
cutting on the bathochromic side, mostly transmitting wavelengths
of light past the desired absorbance .lambda..sub.max. The feature
of coated dye absorbance exhibiting a sharp cutting bathochromic
and/or hypsochromic characteristic is fundamentally useful for
wavelength-specific light filtration, though the exact wavelength
of desired spectral shift from absorbance to transmission may be
different for different photographic materials.
[0054] The dyes may be located in any layer of the element where it
is desirable to absorb light, but in photographic elements it is
particularly advantageous to locate them in a layer where they will
be solubilized and washed out during processing. Useful amounts of
dye range from 1 to 1000 mg/m.sup.2. The dye should be present in
an amount sufficient to yield an optical density at the absorbance
D.sub.max in the spectral region of interest before processing of
at least 0.10 density units and preferably at least 0.50 density
units. This optical density will generally be less than 5.0 density
units for most photographic applications.
[0055] The dyes of the invention can be used as interlayer dyes,
trimmer dyes, or antihalation dyes. They can be used to prevent
crossover in X-ray materials as disclosed in U.S. Pat. Nos.
4,900,652 and 4,803,150 and European Patent Application Publication
No. 0 391 405, to prevent unwanted light from reaching a sensitive
emulsion layer of a multicolor photographic element as disclosed in
U.S. Pat. No. 4,988,611, and for other uses as indicated by the
absorbance spectrum of the particular dye. The dyes can be used in
a separate filter layer or as an intergrain absorber.
[0056] The aggregated dyes of Formula (I-III) are useful for the
preparation of radiation sensitive materials. Such materials are
sensitive to radiation such as visible light, ultraviolet,
infrared, X-ray. The material can be an optical recording medium,
such as a CD or other medium sensitive to a laser, light emitting
diode, or a more conventional light-sensitive photographic
material.
[0057] Another aspect of this invention comprises a radiation
sensitive element containing an aggregated dye of Formula (I-III).
Preferably, the radiation sensitive element is a photographic
element comprising a support bearing at least one light sensitive
hydrophilic colloid layer and at least one other hydrophilic
colloid layer. A dye of Formula I, II or III may be incorporated in
a hydrophilic layer of the photographic element in any known
way.
[0058] The support of the element of the invention can be any of a
number of well-known supports for photographic elements as
discussed more fully below.
[0059] The photographic elements made by the method of the present
invention can be single color elements or multicolor elements.
Multicolor elements contain dye image-forming units sensitive to
each of the three primary regions of the spectrum. Each unit can be
comprised of a single emulsion layer or of multiple emulsion layers
sensitive to a given region of the spectrum. The layers of the
element, including the layers of the image-forming units, can be
arranged in various orders as known in the art. In an alternative
format, the emulsions sensitive to each of the three primary
regions of the spectrum can be disposed as a single segmented
layer.
[0060] A typical multicolor photographic element comprises a
support bearing a cyan dye image-forming unit comprised of at least
one red-sensitive silver halide emulsion layer having associated
therewith at least one cyan dye-forming coupler, a magenta dye
image-forming unit comprising at least one green-sensitive silver
halide emulsion layer having associated therewith at least one
magenta dye-forming coupler, and a yellow dye image-forming unit
comprising at least one blue-sensitive silver halide emulsion layer
having associated therewith at least one yellow dye-forming
coupler. The element can contain additional layers, such as filter
layers, interlayers, overcoat layers, subbing layers, and the like.
All of these can be coated on a support which can be transparent or
reflective (for example, a paper support).
[0061] Photographic elements of the present invention may also
usefully include a magnetic recording material as described in
Research Disclosure, Item 34390, November 1992, or a transparent
magnetic recording layer such as a layer containing magnetic
particles on the underside of a transparent support as in U.S. Pat.
No. 4,279,945 and U.S. Pat. No. 4,302,523. The element typically
will have a total thickness (excluding the support) of from 5 to 30
microns. While the order of the color sensitive layers can be
varied, they will normally be red-sensitive, green-sensitive and
blue-sensitive, in that order on a transparent support, (that is,
blue sensitive furthest from the support) and the reverse order on
a reflective support being typical.
[0062] The present invention also contemplates the use of
photographic elements of the present invention in what are often
referred to as single use cameras (or "film with lens" units).
These cameras are sold with film preloaded in them and the entire
camera is returned to a processor with the exposed film remaining
inside the camera. Such cameras may have glass or plastic lenses
through which the photographic element is exposed.
[0063] In the following discussion of suitable materials for use in
elements of this invention, reference will be made to Research
Disclosure, September 1994, Number 365, Item 36544, which will be
identified hereafter by the term "Research Disclosure I." The
Sections hereafter referred to are Sections of the Research
Disclosure I unless otherwise indicated. All Research Disclosures
referenced are published by Kenneth Mason Publications, Ltd.,
Dudley Annex, 12a North Street, Emsworth, Hampshire P010 7DQ,
ENGLAND. The foregoing references and all other references cited in
this application, are incorporated herein by reference.
[0064] The silver halide emulsions employed in the photographic
elements of the present invention may be negative-working, such as
surface-sensitive emulsions or unfogged internal latent image
forming emulsions, or positive working emulsions of internal latent
image forming emulsions (that are either fogged in the element or
fogged during processing). Suitable emulsions and their preparation
as well as methods of chemical and spectral sensitization are
described in Sections I through V. Color materials and development
modifiers are described in Sections V through XX. Vehicles which
can be used in the photographic elements are described in Section
II, and various additives such as brighteners, antifoggants,
stabilizers, light absorbing and scattering materials, hardeners,
coating aids, plasticizers, lubricants and matting agents are
described, for example, in Sections VI through XIII. Manufacturing
methods are described in all of the sections, layer arrangements
particularly in Section XI, exposure alternatives in Section XVI,
and processing methods and agents in Sections XIX and XX.
[0065] With negative working silver halide a negative image can be
formed. Optionally a positive (or reversal) image can be formed
although a negative image is typically first formed.
[0066] The photographic elements of the present invention may also
use colored couplers (e.g., to adjust levels of interlayer
correction) and masking couplers such as those described in EP 213
490; Japanese Published Application 58-172,647; U.S. Pat. No.
2,983,608; German Application DE 2,706,117C; U.K. Patent 1,530,272;
Japanese Application A-113935; U.S. Pat. No. 4,070,191 and German
Application DE 2,643,965. The masking couplers may be shifted or
blocked.
[0067] The photographic elements may also contain materials that
accelerate or otherwise modify the processing steps of bleaching or
fixing to improve the quality of the image. Bleach accelerators
described in EP 193 389; EP 301 477; U.S. Pat. No. 4,163,669; U.S.
Pat. No. 4,865,956; and U.S. Pat. No. 4,923,784 are particularly
useful. Also contemplated is the use of nucleating agents,
development accelerators or their precursors (UK Patent 2,097,140;
U.K. Patent 2,131,188); electron transfer agents (U.S. Pat. No.
4,859,578; U.S. Pat. No. 4,912,025); antifogging and anti
color-mixing agents such as derivatives of hydroquinones,
aminophenols, amines, gallic acid; catechol; ascorbic acid;
hydrazides; sulfonamidophenols; and non color-forming couplers.
[0068] The elements may also contain filter dye layers comprising
colloidal silver sol or yellow and/or magenta filter dyes and/or
antihalation dyes (particularly in an undercoat beneath all light
sensitive layers or in the side of the support opposite that on
which all light sensitive layers are located) formulated either as
oil-in-water dispersions, latex dispersions, solid particle
dispersions, or as direct gelatin dispersions. Additionally, they
may be used with "smearing" couplers (e.g., as described in U.S.
Pat. No. 4,366,237; EP 096 570; U.S. Pat. No. 4,420,556; and U.S.
Pat. No. 4,543,323.) Also, the couplers may be blocked or coated in
protected form as described, for example, in Japanese Application
61/258,249 or U.S. Pat. No. 5,019,492.
[0069] The photographic elements may further contain other
image-modifying compounds such as "Developer Inhibitor-Releasing"
compounds (DIR's). Useful additional DIR's for elements of the
present invention, are known in the art and examples are described
in U.S. Pat. Nos. 3,137,578; 3,148,022; 3,148,062; 3,227,554;
3,384,657; 3,379,529; 3,615,506; 3,617,291; 3,620,746; 3,701,783;
3,733,201; 4,049,455; 4,095,984; 4,126,459; 4,149,886; 4,150,228;
4,211,562; 4,248,962; 4,259,437; 4,362,878; 4,409,323; 4,477,563;
4,782,012; 4,962,018; 4,500,634; 4,579,816; 4,607,004; 4,618,571;
4,678,739; 4,746,600; 4,746,601; 4,791,049; 4,857,447; 4,865,959;
4,880,342; 4,886,736; 4,937,179; 4,946,767; 4,948,716; 4,952,485;
4,956,269; 4,959,299; 4,966,835; 4,985,336 as well as in patent
publications GB 1,560,240; GB 2,007,662; GB 2,032,914; GB
2,099,167; DE 2,842,063, DE 2,937,127; DE 3,636,824; DE 3,644,416
as well as the following European Patent Publications: 272,573;
335,319; 336,411; 346, 899; 362, 870; 365,252; 365,346; 373,382;
376,212; 377,463; 378,236; 384,670; 396,486; 401,612; 401,613.
[0070] DIR compounds are also disclosed in
"Developer-Inhibitor-Releasing (DIR) Couplers for Color
Photography," C. R. Barr, J. R. Thirtle and P. W. Vittum in
Photographic Science and Engineering, Vol. 13, p. 174 (1969),
incorporated herein by reference.
[0071] It is also contemplated that the concepts of the present
invention may be employed to obtain reflection color prints as
described in Research Disclosure, November 1979, Item 18716,
available from Kenneth Mason Publications, Ltd, Dudley Annex, 12a
North Street, Emsworth, Hampshire P0101 7DQ, England, incorporated
herein by reference. The emulsions and materials to form elements
of the present invention, may be coated on pH adjusted support as
described in U.S. Pat. No. 4,917,994; with epoxy solvents (EP 0 164
961); with additional stabilizers (as described, for example, in
U.S. Pat. No. 4,346,165; U.S. Pat. No. 4,540,653 and U.S. Pat. No.
4,906,559); with ballasted chelating agents such as those in U.S.
Pat. No. 4,994,359 to reduce sensitivity to polyvalent cations such
as calcium; and with stain reducing compounds such as described in
U.S. Pat. No. 5,068,171 and U.S. Pat. No. 5,096,805. Other
compounds useful in the elements of the invention are disclosed in
Japanese Published Applications 83-09,959; 83-62,586; 90-072,629,
90-072,630; 90-072,632; 90-072,633; 90-072,634; 90-077,822;
90-078,229; 90-078,230; 90-079,336; 90-079,338; 90-079,690;
90-079,691; 90-080,487; 90-080,489; 90-080,490; 90-080,491;
90-080,492; 90-080,494; 90-085,928; 90-086,669; 90-086,670;
90-087,361; 90-087,362; 90-087,363; 90-087,364; 90-088,096;
90-088,097; 90-093,662; 90-093,663; 90-093,664; 90-093,665;
90-093,666; 90-093,668; 90-094,055; 90-094,056; 90-101,937;
90-103,409; 90-151,577.
[0072] The silver halide used in the photographic elements may be
silver iodobromide, silver bromide, silver chloride, silver
chlorobromide, silver chloroiodobromide, and the like. For example,
the silver halide used in the photographic elements of the present
invention may contain at least 90% silver chloride or more (for
example, at least 95%, 98%, 99% or 100% silver chloride). In the
case of such high chloride silver halide emulsions, some silver
bromide may be present but typically substantially no silver
iodide. Substantially no silver iodide means the iodide
concentration would be no more than 1%, and preferably less than
0.5 or 0.1%. In particular, in such a case the possibility is also
contemplated that the silver chloride could be treated with a
bromide source to increase its sensitivity, although the bulk
concentration of bromide in the resulting emulsion will typically
be no more than about 2 to 2.5% and preferably between about 0.6 to
1.2% (the remainder being silver chloride). The foregoing % figures
are mole %.
[0073] The type of silver halide grains preferably include
polymorphic, cubic, and octahedral. The grain size of the silver
halide may have any distribution known to be useful in photographic
compositions, and may be either polydipersed or monodispersed.
[0074] Tabular grain silver halide emulsions may also be used.
Tabular grains are those with two parallel major faces each clearly
larger than any remaining grain face and tabular grain emulsions
are those in which the tabular grains account for at least 30
percent, more typically at least 50 percent, preferably >70
percent and optimally >90 percent of total grain projected area.
The tabular grains can account for substantially all (>97
percent) of total grain projected area. The tabular grain emulsions
can be high aspect ratio tabular grain emulsions--i.e., ECD/t>8,
where ECD is the diameter of a circle having an area equal to grain
projected area and t is tabular grain thickness; intermediate
aspect ratio tabular grain emulsions--i.e., ECD/t=5 to 8; or low
aspect ratio tabular grain emulsions--i.e., ECD/t=2 to 5. The
emulsions typically exhibit high tabularity (T), where T (i.e.,
ECD/t.sup.2)>25 and ECD and t are both measured in micrometers
(.mu.m). The tabular grains can be of any thickness compatible with
achieving an aim average aspect ratio and/or average tabularity of
the tabular grain emulsion. Preferably the tabular grains
satisfying projected area requirements are those having thicknesses
of <0.3 .mu.m, thin (<0.2 .mu.m) tabular grains being
specifically preferred and ultrathin (<0.07 .mu.m) tabular
grains being contemplated for maximum tabular grain performance
enhancements. When the native blue absorption of iodohalide tabular
grains is relied upon for blue speed, thicker tabular grains,
typically up to 0.5 .mu.m in thickness, are contemplated.
[0075] High iodide tabular grain emulsions are illustrated by House
U.S. Pat. No. 4,490,458, Maskasky U.S. Pat. No. 4,459,353 and Yagi
et al EPO 0 410 410.
[0076] Tabular grains formed of silver halide(s) that form a face
centered cubic (rock salt type) crystal lattice structure can have
either {100} or {111} major faces. Emulsions containing {111} major
face tabular grains, including those with controlled grain
dispersities, halide distributions, twin plane spacing, edge
structures and grain dislocations as well as adsorbed {111} grain
face stabilizers, are illustrated in those references cited in
Research Disclosure I, Section I.B.(3) (page 503).
[0077] The silver halide grains to be used in the invention may be
prepared according to methods known in the art, such as those
described in Research Disclosure I and James, The Theory of the
Photographic Process. These include methods such as ammoniacal
emulsion making, neutral or acidic emulsion making, and others
known in the art. These methods generally involve mixing a water
soluble silver salt with a water soluble halide salt in the
presence of a protective colloid, and controlling the temperature,
pAg, pH values, etc, at suitable values during formation of the
silver halide by precipitation.
[0078] The silver halide to be used in the invention may be
advantageously subjected to chemical sensitization with noble metal
(for example, gold) sensitizers, middle chalcogen (for example,
sulfur) sensitizers, reduction sensitizers and others known in the
art. Compounds and techniques useful for chemical sensitization of
silver halide are known in the art and described in Research
Disclosure I and the references cited therein.
[0079] The photographic elements of the present invention, as is
typical, provide the silver halide in the form of an emulsion.
Photographic emulsions generally include a vehicle for coating the
emulsion as a layer of a photographic element. Useful vehicles
include both naturally occurring substances such as proteins,
protein derivatives, cellulose derivatives (e.g., cellulose
esters), gelatin (e.g., alkali-treated gelatin such as cattle bone
or hide gelatin, or acid treated gelatin such as pigskin gelatin),
gelatin derivatives (e.g., acetylated gelatin, phthalated gelatin,
and the like), and others as described in Research Disclosure I.
Also useful as vehicles or vehicle extenders are hydrophilic
water-permeable colloids. These include synthetic polymeric
peptizers, carriers, and/or binders such as poly(vinyl alcohol),
poly(vinyl lactams), acrylamide polymers, polyvinyl acetals,
polymers of alkyl and sulfoalkyl acrylates and methacrylates,
hydrolyzed polyvinyl acetates, polyamides, polyvinyl pyridine,
methacrylamide copolymers, and the like, as described in Research
Disclosure I. The vehicle can be present in the emulsion in any
amount useful in photographic emulsions. The emulsion can also
include any of the addenda known to be useful in photographic
emulsions. These include chemical sensitizers, such as active
gelatin, sulfur, selenium, tellurium, gold, platinum, palladium,
iridium, osmium, rhenium, phosphorous, or combinations thereof.
Chemical sensitization is generally carried out at pAg levels of
from 5 to 10, pH levels of from 5 to 8, and temperatures of from 30
to 80.degree. C., as described in Research Disclosure I, Section IV
(pages 510-511) and the references cited therein.
[0080] The silver halide may be sensitized by sensitizing dyes by
any method known in the art, such as described in Research
Disclosure I. The dye may be added to an emulsion of the silver
halide grains and a hydrophilic colloid at any time prior to (e.g.,
during or after chemical sensitization) or simultaneous with the
coating of the emulsion on a photographic element. The dyes may,
for example, be added as a solution in water or an alcohol. The
dye/silver halide emulsion may be mixed with a dispersion of color
image-forming coupler immediately before coating or in advance of
coating (for example, 2 hours).
[0081] Photographic elements of the present invention are
preferably imagewise exposed using any of the known techniques,
including those described in Research Disclosure I, section XVI.
This typically involves exposure to light in the visible region of
the spectrum, and typically such exposure is of a live image
through a lens, although exposure can also be exposure to a stored
image (such as a computer stored image) by means of light emitting
devices (such as light emitting diodes, CRT and the like).
[0082] Photographic elements comprising the composition of the
invention can be processed in any of a number of well-known
photographic processes utilizing any of a number of well-known
processing compositions, described, for example, in Research
Disclosure I, or in T. H. James, editor, The Theory of the
Photographic Process, 4th Edition, Macmillan, New York, 1977. In
the case of processing a negative working element, the element is
treated with a color developer (that is one which will form the
colored image dyes with the color couplers), and then with a
oxidizer and a solvent to remove silver and silver halide. In the
case of processing a reversal color element, the element is first
treated with a black and white developer (that is, a developer
which does not form colored dyes with the coupler compounds)
followed by a treatment to fog silver halide (usually chemical
fogging or light fogging), followed by treatment with a color
developer. Preferred color developing agents are
p-phenylenediamines. Especially preferred are:
[0083] 4-amino N,N-diethylaniline hydrochloride,
[0084] 4-amino-3-methyl-N,N-diethylaniline hydrochloride,
[0085] 4-amino-3-methyl-N-ethyl-N-(.beta.-(methanesulfonamido)
ethylaniline sesquisulfate hydrate,
[0086] 4-amino-3-methyl-N-ethyl-N-(.beta.-hydroxyethyl)aniline
sulfate,
[0087] 4-amino-3-p-(methanesulfonamido)ethyl-N,N-diethylaniline
hydrochloride and
[0088] 4-amino-N-ethyl-N-(2-methoxyethyl)-m-toluidine di-p-toluene
sulfonic acid.
[0089] Development is followed by bleach-fixing, to remove silver
or silver halide, washing and drying.
SYNTHESIS OF DYE 1
[0090] 3-methyl glutacondialdehydedianil hydrobromide (6.6 g, 19
mmol) was added portionwise to a solution of
4-methoxyphenylbarbituric acid (9.6 g, 41 mmol) in 150 mL pyridine
at 80.degree. C. The blue mixture was heated at 80.degree. C. for
30 min, then allowed to cool to 25.degree. C. The precipitated dye
was collected by filtration and washed with acetonitrile. The
collected solid was suspended in 300 mL methanol and stirred while
100 mL concentrated HCl was added over 10 min, and the resulting
slurry was allowed to stir at 25.degree. C. for 30 min. The dye was
collected by filtration and dried. Isolated 6.2 g (46%) of Dye 1 as
a black solid. All analytical data were consistent with the
structure.
SYNTHESIS OF DYE 8
[0091] Glutacondialdehydedianil hydrochloride (7.3 g, 26 mmol) was
added portionwise to a solution of 3-methoxyphenylbarbituric acid
(12.0 g, 51 mmol) and triethylamine (7.8 g, 77 mmol) in 300 mL
ethanol at 25.degree. C. The mixture was heated to reflux and held
for 30 min. A blue solid precipitated from the hot reaction
mixture. The mixture was then allowed to cool to 25.degree. C., and
the precipitated dye was collected by filtration and washed with
ethanol. The collected solid was suspended in 250 mL ethanol and
heated to reflux while 3 mL concentrated HCl was added over 5 min.
The resulting slurry was heated at reflux for 10 min, then allowed
to cool to 25.degree. C. The dye was collected by filtration,
washed with methanol and dried. Isolated 11.3 g (84%) of Dye 8 as a
dark solid. All analytical data were consistent with the
structure.
EXPERIMENTAL EXAMPLES
Example A
Microcrystalline Dye Slurry (MDS) Formulation
[0092] Dyes were formulated as aqueous microcrystalline dispersions
of 0.2 microns mean particle size by ball-milling according to the
following procedure. Water (22.0 g) and a 10.0% solution of Triton
X-200.RTM., an alkyl aryl polyether sulfonate surfactant available
from Rohm and Haas, (1.0 g) were placed in a 120 mL screw-capped
bottle. A 1.0 g sample of dye was added to this solution. Zirconium
oxide beads (60 mL, 1.8 mm diameter) were added and the container
with the cap tightly secured was placed in a mill and the contents
milled for four days. The resulting mixture was then filtered to
remove the zirconium oxide beads. The resulting aqueous
microcrystalline dye slurries will be referred to in the following
examples as MDS's.
Example B
Solid Particle Dispersion (SPD) Formulation
[0093] Aqueous gelatin dispersions of the above MDS's were prepared
as follows. The vessel containing the dye MDS was removed and the
requisite weight of dye slurry was added to a 12.5% aqueous gelatin
solution (18.0 g) at 45.degree. C. This mixture was then diluted
with water to a weight of 88.87 g., yielding the final dye
dispersion. In the subsequent experimental sections
gelatin-containing dye dispersions prepared in this manner will be
referred to as solid particle dispersions (SPD's). The term "SPD"
is used throughout simply to denote dye dispersions which have been
formulated using well known milling techniques normally used for
preparing solid particle microcrystalline dye dispersions. This
does not imply that the physical state of the dye prepared in this
manner is exclusively microcrystalline in nature.
Example C
Direct Gelatin Dispersion (DGD) Formulation
[0094] Nominally 1.42500 g H.sub.2O then 0.07500 g deionized
gelatin were weighed into screw-topped glass vials and allowed to
soak at 25.degree. C. for at least 30 minutes. The swollen gelatin
was then melted at 50.degree. C. for 15 minutes with agitation. The
gelatin solution was cooled to 25.degree. C., then refrigerated at
5.degree. C. to set. Nominally 1.49700 g H.sub.2O was then added on
top of the set gelatin followed by 0.00300 g of powdered dye. The
dye powder was thoroughly wetted and dispersed in the water layer
by agitation and then allowed to stand at 25.degree. C. for 17
hours. The samples were then heated to 60.degree. C. in a water
bath for 2 hours and mixed with intermittent agitation. The samples
were subsequently cooled to 39.0.degree. C. over a period of
approximately 1 hour and maintained at this temperature until
measurement. In the subsequent experimental sections dispersions
prepared in this manner will be referred to as DGD's.
Example 1
Absorption Wavelength (.lambda..sub.max), Halfbandwidth (Hbw) and
Molar Extinction Coefficients (.epsilon..sub.max) of Wet Dye
DGD's
[0095] Direct gelatin dispersions (DGD's) of Dyes 1-16 and
Comparative Dyes A-D were prepared as described in Example C.
Aliquots of each dispersion, held at 39.degree. C., were
transferred to 0.0032 cm pathlength glass cells and their
absorption spectra measured at 25.degree. C. Solutions of Dyes 1-16
and Comparative Dyes A-D were prepared in a suitable organic
solvent (methanol or methanol with added triethylamine unless
otherwise noted) and their absorption spectra measured at
25.degree. C. The extinction coefficients were calculated according
to Beer's Law, and halfbandwidths (Hbw) measured. The data are
summarized in Table V.
5TABLE V .epsilon..sub.max soln. Hbw .lambda..sub.max
.epsilon..sub.max DGD Hbw .lambda..sub.max soln. (mol.sup.-1l
cm.sup.-1) soln. DGD (mol.sup.-1l cm.sup.-1) DGD Dye (nm) x10.sup.5
(nm) (nm) x10.sup.5 (nm) 1 611 1.81 34 793 8.19 18 2 587 1.92 38
738 6.97 19 3 488 1.12 29 558 5.18 12 3A 488 1.15 29 558 5.82 12 4
609 1.63 38 779 2.83 24 4A 609 1.60 38 778 3.89 16 5 609 1.42 38
790 5.29 19 6 488 1.32 30 555 3.59 17 7 615 1.69 35 785 2.82 17 8
586 1.71 39 721 3.58 40 8A 586 1.73 39 721 3.89 42 9 587 1.48 36
739 3.22 35 9A 587 1.48 36 740 4.96 37 10 587 1.86 36 717 4.01 46
10A 587 1.86 36 762 2.42 50 10B 587 1.86 36 717 3.54 46 11 586 1.79
39 755 2.45 30 12 586 2.25 35 758 2.83 29 13 586 1.95 36 554 1.88
15 13A 586 1.95 36 549 1.79 18 14 609 1.86 38 792 6.74 20 15 586
1.90 39 723 3.02 41 16 611 2.01 35 771 6.55 48 A 586 1.69 39 682
1.56 75 Aa 586 1.70 39 686 1.44 75 B 586 1.95 37 709 2.10 58 C 587
1.76 39 586 0.77 121 D 587 2.10 36 682 1.56 77
[0096] The above results demonstrate that the direct gelatin
dispersions containing the inventive dyes in an aggregated state
exhibit bathochromically shifted longer wavelength absorption
maxima relative to their solution (non-aggregated) absorption
maxima. Moreover, the inventive aggregated dyes as DGD's are
comparable or superior in both Hbw and extinction coefficient to
their solution (non-aggregated) counterparts. Moreover, as DGD's
the inventive dyes are far superior in both Hbw and extinction
coefficient to the comparative dyes A to D. 19
Example 2
Spectral Shape of Wet Dye DGD's
[0097] Direct gelatin dispersions (DGD's) of Dyes 1-16 and
Comparative Dyes A-D were prepared as described in Example C.
Aliquots of each dispersion, held at 39.degree. C., were
transferred to 0.0032 cm pathlength glass cells and their
absorption spectra measured at 25.degree. C. as wet gelatin films.
The ratio of each dye's optical density at .lambda..sub.max
(D.sub.max) to optical density (O.D.) at .lambda..sub.max+20 nm was
calculated. The ratio of each dye's optical density at
.lambda..sub.max (D.sub.max) to optical density (O.D.) at
.lambda..sub.max-20 nm was also calculated. These ratios are a
measure of spectral band sharpness. Dyes with higher ratios possess
sharper cutting spectral absorption envelopes which are desirable
for light filtration/absorption applications. The data are
summarized in Table VI.
6 TABLE VI .lambda..sub.max D.sub.max/O.D.at D.sub.max/O.D.at Dye
DGD.sub.wet(nm) .lambda..sub.max + 20 nm .lambda..sub.max - 20 nm 1
794 20.3 3.43 2 738 27.2 2.98 3 558 321 5.83 3A 558 158 6.70 4 788
4.81 2.48 4A 788 15.0 4.14 5 790 21.9 3.69 6 554 68.5 3.61 7 782
20.9 3.74 8 722 2.48 1.78 8A 722 2.50 2.00 9 738 3.20 2.09 9A 740
2.87 1.97 10 717 2.32 1.55 10A 762 2.18 1.48 10B 716 2.24 1.62 11
750 3.31 2.05 12 758 6.06 2.24 13 554 31.5 3.79 13A 549 30.9 3.22
14 792 7.29 3.68 15 722 2.47 1.77 16 774 10.2 1.67 A 682 1.39 1.17
Aa 684 1.53 1.24 B 710 1.96 1.25 C 586 1.48 1.43 D 682 1.50
1.19
[0098] The data clearly demonstrate that the inventive dyes 1-16
when aggregated in aqueous gelatin possess absorption spectra with
significantly sharper hypsochromic and bathochromic edges relative
to the comparative dyes A to D. Moreover, these useful spectral
features are largely retained in dried-down gelatin films and
layers.
Example 3
Spectral Properties of Wet Gelatin Layers Containing Dyes Added in
the Powdered or Microcrystalline State
[0099] Each of Dyes 1, 3, 8, 10, 11, 15 and Comparative Dyes A and
D in the powdered state were dispersed directly in aqueous gelatin
as described in Example C. The same dyes, formulated as aqueous
microcrystalline dye dispersions (MDS's) in accordance with Example
A, were also dispersed in aqueous gelatin at comparable
concentrations under identical conditions. Solution aliquots of
each dye dispersion were transferred to 0.0032 cm pathlength glass
cells and their absorption maxima measured at 25.degree. C. as wet
gelatin films. The corresponding extinction coefficients
(.epsilon..sub.max) were calculated using Beer's law, and
halfbandwidths (Hbw) measured. The data are compared in Table VII,
where the qualifers "powder" and "MDS" denote the original physical
state of the dye before mixing with gelatin.
7TABLE VII .lambda..sub.max .lambda..sub.max Hbw Hbw
.epsilon..sub.max powder .epsilon..sub.max MDS powder MDS powder
MDS (mol.sup.-1l cm.sup.-1) (mol.sup.-1l cm.sup.-1) Dye (nm) (nm)
(nm) (nm) x10.sup.5 x10.sup.5 1 793 793 18 18 8.19 4.63 3 558 558
12 13 5.18 3.80 8 721 721 40 41 3.58 4.14 10 717 715 46 48 4.01
1.99 11 755 755 30 30 2.45 2.37 15 723 724 41 41 3.02 2.36 A 682
680 75 80 1.56 1.39 D 682 681 77 80 1.56 1.24
[0100] The above data demonstrate that excellent results may be
obtained from wet aqueous gelatin dispersions containing the
inventive dyes added in either the powdered or ball-milled
microcrystalline state. It is clearly not essential, however, to
resort to the preparative complexities of dye milling in order to
achieve the desired spectral properties.
Example 4
Spectral Properties of Wet and Dried Dye DGD's
[0101] Direct gelatin dispersions (DGD's) of Dyes 1-16 and
Comparative Dyes A-D were prepared using powdered dye as described
in Example C. Aliquots of each dispersion, held at 39.degree. C.,
were transferred to 0.0032 cm pathlength glass cells and their
absorption spectra measured immediately at 25.degree. C. These
samples are referred to in Table VIII as "wet DGD's". Solution
aliquots of each dispersion were also smeared onto standard glass
microscope slides (0.8/1.0 mm thickness) to form uniformly thin wet
films which were allowed to dry at ambient temperature and humidity
for at least 17 hours such that their D.sub.max (dried) was less
than 4.0 absorbance units. The absorption spectra for these dried
gelatin films were then measured at 25.degree. C. These samples are
referred to in Table VIII as "dry DGD's". The data are summarized
in Table VIII.
8 TABLE VIII .lambda..sub.max l.sub.max DGD.sub.wet DGD.sub.dry Hbw
Wet Hbw Dry Dye (nm) (nm) (nm) (nm) 1 793 794 18 22 2 738 737 19 35
3 558 559 12 14 3A 559 560 12 14 4 779 781 24 35 4A 778 780 16 22 5
790 791 19 30 6 555 557 17 19 7 785 788 17 21 8 721 719 40 44 8A
721 722 42 50 9 739 739 35 40 9A 740 739 37 44 10 717 713 46 54 10A
762 772 50 52 10B 717 712 46 53 11 751 757 34 49 12 758 763 29 44
13 554 554 15 21 13A 549 553 18 20 14 792 794 20 23 15 723 724 41
45 16 771 771 48 59 A 682 684 75 82 Aa 686 686 75 85 B 709 709 58
64 C 586 602 121 178 D 682 684 77 81
[0102] The above results clearly demonstrate that the useful
spectral features of bathochromic absorbance maximum, narrow Hbw
and high extinction coefficient for each inventive dye aggregated
in wet aqueous gelatin, are largely retained in dried gelatin films
or layers.
Example 5: Spectral Properties of Dried Gelatin Layers Containing
Dyes Formulated Using DGD and SPD Procedures
[0103] Direct gelatin dispersions of the Inventive Dyes 2, 6, 8, 9,
11 and 15 were prepared as described in Example C at concentrations
equivalent to dye laydowns of 0.064 mg/m.sup.2. Solution aliquots
of each dispersion were smeared onto glass microscope slides
(0.8/1.0 mm thickness) to form uniformly thin wet films which were
then allowed to dry at ambient temperature and humidity for at
least 17 hours. The absorption spectra for these dried films were
then measured at 25.degree. C. These samples are referred to in
Table IX as "dry DGD's". The inventive Dyes 2, 6, 8, 9, 11 and 15
were also dispersed in aqueous gelatin according to the SPD
procedure described in Example B. These SPD's were coated on a
polyester support according to the following procedure. A spreading
agent (Olin 10G, an isononylphenoxy glycidol surfactand available
from Olin Corp.) and a hardener (bis(vinylsulfonylmethyl)ether)
were added to the dye-gelatin melt prepared as described above. A
melt from this mixture was then coated on a poly(ethylene
terephthalate) support to achieve a dye coverage of 0.064
g/m.sup.2, a gelatin coverage of 1.61 g/m.sup.2, and a hardener
level of 0.016 g/m.sup.2. The absorption spectrum of the dried SPD
coating was measured at 25.degree. C. The data are summarized in
Table IX.
9 TABLE IX .lambda..sub.max Hbw DGD.sub.dry DGD.sub.dry
.lambda..sub.maxSPD Hbw DPD.sub.dry Dye (nm) (nm) .sub.dry (nm)
(nm) 2 737 35 733 33 6 557 19 558 26 8 719 44 720 47 9 739 40 735
58 11 757 49 751 51 13 554 21 552 25 13A 553 20 552 25 15 724 45
719 48
[0104] The data show no significant differences in .lambda..sub.max
or Hbw for the dried gelatin films containing aggregated dyes
formulated according to the DGD or SPD procedures outlined in
Examples C and B, respectively.
Example 6
Process Removability of Dyes
[0105] The inventive Dyes 1-3, 5, 7-11, and 14-15 were formulated
according to the SPD procedure described in Example B. These dye
dispersions were coated on a polyester support according to the
following procedure. A spreading agent (surfactant 10G) and a
hardener (bis(vinylsulfonylmethyl)ether) were added to the
dye-gelatin melt prepared as described above. A melt from this
mixture was then coated on a poly(ethylene terephthalate) support
to achieve a dye coverage of 0.161 g/m.sup.2, a gelatin coverage of
1.61 g/m.sup.2, and a hardener level of 0.016 g/m.sup.2. The
absorption spectrum of the dried SPD coating was measured at
25.degree. C. Identical elements were subjected to Kodak E-6.RTM.
processing (which is described in British Journal of Photography
Annual, 1977, pp. 194-97) and the absorbance was measured for each.
The results are shown in Table X.
10 TABLE X .lambda..sub.maxSPD.sub.dry D.sub.max Dye (nm) D.sub.max
after E-6 Processing 1 790 >4.0 0.0 2 733 >4.0 0.0 3 558 2.8
0.0 5 758 >4.0 0.0 7 778 3.6 0.0 8 720 2.5 0.0 9 735 3.3 0.0 10
705 3.1 0.0 11 751 >4.0 0.0 13 552 1.6 0.0 13A 552 1.3 0.0 14
784 >4.0 0.0 15 721 >4.0 0.0
[0106] In spite of the inordinately high optical densities
(D.sub.max's) for the aggregated coated dyes, no residual
deleterious dye stain (optical density) could be detected after
processing.
Example 7
Dye Immobility and Thermal Stability
[0107] The inventive Dyes 1, 3, 9, 10 and 15 were formulated using
the SPD procedure described in Example B and coated on a polyester
support as outlined in Example 6. Each dye was coated at a laydown
such that the measured D.sub.max was less than 3.5. For each
example, the absorbance spectrum for the dyed gelatin coating was
measured both before and after incubation for seven days at
120.degree. C./50% relative humidity. The results are summarized in
Table XI.
11TABLE XI D.sub.max SPD Dye laydown .lambda..sub.maxSPD before
D.sub.max SPD after Dye (g/m.sup.2) (nm) incubation incubation 1
0.043 790 3.3 3.5 3 0.043 558 2.3 2.3 9 0.161 735 3.3 3.4 10 0.161
705 3.2 3.2 13 0.043 552 1.6 1.7 13A 0.043 552 1.3 1.4 15 0.043 721
1.7 1.7
[0108] It is clear from the data that the aggregated dyes in the
inventive examples show an excellent robustness toward high heat
and humidity as evidenced by the fact that little or no density
loss at the aggregate .lambda..sub.max is observed as a result of
incubation. Furthermore, the absence of any detectable optical
density at the monomeric .lambda..sub.max of the inventive dyes
following incubation demonstrates that little or no mobile
monomeric dye species is produced under these conditions.
Consequently, the aggregated inventive dyes exhibit excellent
robustness and fastness to diffusion at high temperature and
humidity.
[0109] The invention has been described in detail with particular
reference to preferred embodiments, but it will be understood that
variations and modifications can be effected within the spirit and
scope of the invention.
* * * * *