Note: Descriptions are shown in the official language in which they were submitted.
`
Field of Invention ~0~8S6~ ~
This invention relates to the art of photography and
more particularly, to color diffusion transfer photography
employing magenta dye-providing compounds.
Description of Prior Art
Color diffusion transfer processes generally involve
the use of a photographic element comprising a support, at least
one silver halide emulsion layer and an image dye-provicling
material which is contained in or contiguous said layer. The
image dye-providing material typically can be thought o~ as
having the structure Car-Col where:Ln Col is a colorant such as
a dye or a dye precursor and Car is an associated carrier or
monitoring group which as a function of alkaline processing
effects a substantial change in the diffusivity of at least
the Col portion of the compound.
After exposure, a photographic element as described
above is treated with an alkaline processing solution to effe~t
imagewise discrimination in the element. As mentioned previously,
the imagewise discrimination is generally brought about by the
monitoring or carrier group which, in the presence of the alkaline
processing solution, is responsible for a substantial change in
; the diffusivity of at least the dye portion of the dye-providing
material. As is known in the art, the dye-providing material
can be initially immobile or initially mobile in the processing
solution. Upon alkaline processing of an initially immobile
dye-providing material, a mobile dye can be released imagewise
or the material can be imagewise rendered soluble and thus mobile.
If the material is initially mobile, the processing solution
typically renders the material insoluble (and thus immobile) in
an imagewise fashion.
~ )38~316~ ~It is well known in the art to utilize image dye-providing
materials in a photographic element wherein an imagewise exposed element
can be contacted with an alkaline processing solution to effect an
imagewise difference in mobility of at least a portion of the dye- `
providing material, i.e., to effect release of a dye or dye precursor,
to render said compound insoluble or soluble. It is the particular
carrier or monitoring group which determines what form the change in
diffusivity (of at least the dye portion of the material~ will take. In
,
certain instances, an increase in solubility of a given compound can be
.:,
- 10 accomplished by substantially reducing the molecular weight of the
5,~ compound; see, for example, the disclosure in Gompf U. S. Patent No.
3,698,897, issued October 17, 1972. Exemplary of systems wherein the
dye-providing compound splits o~f a dye are those described in Whitmore
U. S. Patent No. 3,227,552, is~ued January 4, 1966 and Bloom U. S.
Patent No. 3,443,940, issued May 13, 1969 and Canadian Patent No.
~; 602,607, issued August 2, 1960. Similarly, Yutzy U. S. Patent ~o. 2,756,142,
issued July 24, 1956, U. S. Patent No. 2,774,668, issued December 18,
1956 and U. S. Patent ~o. 2,983,606, issued May 9, 1961 describe photographic
~,
elements wherein a dye-providing compound is rendered immobile in an
imagewise fashion.
-- 3 --
,
~3~C9~
All o~ these prior systems have utility; however, it
is desired to provide new compounds which provide dyes having
improved properties, such as improved hue, diffusibility,
mordantability and the like.
Summary of the Invention
We have found a class of magenta, azo dye-providing
compounds well suited for use in color diffusion transfer
color elements. The dye-providing compounds, as a function
of typical processing under alkaline conditions, provide a
magenta-colored substance having a mobility different than
that of the compound.
Description of Preferred Embodiments
The objects of the present invention are achieved
through the use in color diffusion transfer elements of a
new class of magenta, azo dye-providing compounds. Typically,
these compounds are utilized in a photosensitive element which
comprises a support having thereon at least one photosensitive
silver halide emulsion, and at least one of said layers having
associated therewith a magenta, azo dye-providing compound of
this invention.
The compounds of this invention can be represented
by the following formulas:
I ~038864
I. Car -[X~(NR~~q~
G ~ ~ - ~ 1
, .
Il ~Car _ X-J~
III Car -[X-~NR-J) j ~ N= N ~ G
... ,,,, , ~ ,m ~ zl E ~ Q
~herein: ,
',~ Car represents a carrier which is a moiety that,as
a function of oxidation under alkaline conditions, provides a
substance having a mobility dif~erent than that of said compound;
X represents a bivalent linking group of the formula:
, -R2- ~ -R2p- where each R2 can be the same or different and
- 10 each represents an alkylene radical having 1 to about 8 carbon
atoms a phenylene radical or a substituted phenylene radical
havlng 6 to 9 carbon atoms; L repxesents a bivalent radical
such as oxy (-O-), carbonyl (-CO-), carbamoyl ~-NHCO-), sul-
: fonamido ~-SO2NH-), carboxamido ~-CONH-), sulfamoyl t-NHSO-),
8ulfinyl (-SO-), sulfonyl (-SO2-) etc; n is an integer having
a value of 0 or 1; p is 1 when n equals 1 and p is 1 or 0 when
n equals 0 provided that when p is 1 the carbon content of the
sum of both R2 radicals does not exceed 14 carbon atoms.
R represents a hydrogen atom, an alkyl radical having
; cO 1 to 6 carbon atoms;
. _5_ .
._ _ __. _. . .. ..... .
,_ _ __,__ .. _._ ._,,_.~.. __,... _ ..... . r~
`` ~0388~
J represents a bivalent radical selected from sul-
fonyl (-S02-) or carbonyl t-CO-);
m and q each represent an integer having a value of
O or l;
. ~ Q represents a hydrogen atom, a hydroxy radical or
a radical having the formula -N~CoR3 or -NHSo2R3 wherein R3
is an alkyl radical having 1 to about 6 carbon atoms, a substi-
: tuted alkyl radical having 1 to 6 carbon atoms, benzyl, phenyl,
. : or a substituted phenyl radical having 6 to 9 carbon atoms;
.~: 10 G represents a hydroxy radical or salt thereof, or
a hydrolyzable acyloxy group, having the formula:
O O
CR4 or -oCoR4
wherein R4 is an alkyl radical having 1 to about 18 carbon
atoms, phenyl or substituted phenyl having 6 to 18 carbon
. atoms;
Z represents one or more electron-withdrawing groups
- . selected from a cyano radical (-CN), a trihalomethyl radical
(e.g., -CF3, -CC13, etc), a carboxy radical including salts
thereof, such as alkali metal salts or amine salts (e.g., -COOH,
-COO-Li+~-COO-K+, -COO~Na+, -COO-NH3+, etc), a carboxylic acid
ester such as alkyl or aryl esters having 1 to about 18 carbon
atoms in the alkyl or aryl moiety (e.g., -CooR4 wherein R4 is as
defined above)S an alkylsulfonyl radical having 1 to about 8 ca~bon
atoms in the alkyl moiety (e.g., -S02CH3, -S02C2H5, etc), a
sulfamoyl radical of the formula -So2NR5R6 wherein R5 is hydrogen,
-6-
:
38~64 ~;
alkyl of 1 to about 8 carbon atoms or aryl of 6 to about 13 carbon
- atoms (e.g., phenyl, tolyl, etc), R6 can represent the same sub-
stituents as R5 or alkyl- or arylcarbonyl as well as alkyl- or
arylsulfonyl having 1 to about 8 carbon atoms in the alkyl or
aryl moiety (e-g-, -COCH3, -COC3H7~ -C0C6H5~ -C0cH2c6H5~ -Coc6H4cH3
-S02C6H5, -S02C~2C6H5, etc), a carbamoyl radical of the formula
-CoN(R5)2 ~herein each R5`can be the same or diffe~ent and R5 is
as described previously), and R5 and R6 when taken together, can
represent l-(dialkylamino)alkylidene (having 1 to about 8 carbon
atoms in the alkyl moiety and 1 to about 4 carbon atoms in the
alkylidene moiety), a sulfo radical including salts thereof,
such as alkali metal or amine salts (e.g., -S03H, -S03 Li~,
-S03 K , -S03 Na , -S03 NH3 , etc), or a halogen atom (e.g.,
Cl, F, Br, etc), as well as a radical of the formula
Car -~X-(NR-J)~]m wherein each member is as described above.
Rl represents a hydrogen atom, an alkoxy radical having
from 1 to about 8 carbon atoms, a halogen atom (e.g., Cl, F,
Br, etc), an alkyl radical (including substituted alkyl) having
from 1 to about 8 carbon atoms (e.g., CH3, C2H5, C4Hg, C5HloCOOH,
CH2C6H5, etc), or the carbon atoms necessary to form a fused
ben~o ring attached at the 2- and 3-position or the 3- and 4-
positions;
E, which can be in the 3-, 5-, 6- or 7-positions rela-
tive to G, a carbamoyl radical, a sulfamoyl radical, a carboxy
radical, a carboxylic acid ester or a sulfo radical, all as
described above for Z or E can represent a hydrogen atom,
zl represents a hydrogen atom or any of the electron-
withdrawing substituents described for Z;
and all the compounds herein are with the proviso that
there can be only one sulfo or carboxy radical present.
.
1(~3i 3864
In Formula II above, the dotted line is used to represent the fact that
the carrier and associated linking group can be attached to either ring
of the naphthalene nucleus; particularly, it is attached at the 3-9 5-,
6- or 7-positions relative to the moiety G.
As mentioned above, the present compounds contain a carrier
moiety which, as a function (direct or inverse~ of oxidation under
alkaline conditions, provides substance having a mobility different than
that of the starting compound. Depending upon the carrier used, the
dye-providing compounds of this invention can be of two basic types:
(1) initially immobile compounds of which at least a portion is rendered
mobile or diffusible as a funct-Lon of development or (2) initlally
mobile or difusible compounds which are renclered immobLle as a ~mction
of development. Carriers useful in initially immobile dye-providing
compounds such as those wherein the carrier, under alkaline conditions,
effects a splitting off of a ballast group from the dye moiety are
described further in Whitmore Canadian Patent 602,607, dated August 2,
1960 and Whitmore U. S. Patent No. 3,227,552, issued January 4, 1966.
Among the preferred initially immobile compounds are those in which the
carrier, as a function of oxidation under alkaline conditions, releases
a dye having a mobility diferent than that of the starting immobile
compound. For example, useful carriers for compounds in which the carrier
moiety undergoes intramolecular ring closure upon oxidation to split off
a dye are described in U. S. Patents 3,443,939, 3,443,940 and 3,443,941,
all issued May 13, 1969.
. . .
:
~)3~
Still other useful carriers are described in U. S. Paten~ No. 3,628,952,
issued December 21, 1971. Additionally, carriers useful in the formation
of initially mobile compounds such as those wherein the carrier functions
as a developer are described in Friedman U. S. Patent 2,543,691, issued
February 27, 1951, U. S. Patent 2,983,606, issued May 8, 1961 and U. S.
Patent 3,255,001, issued June 7, 1966.
Preferred compounds are those having formulas I, II and III
above wherein:
Car represents a carrier moiety which, as a function of oxidation
under alkaline conditions, releases a dye having a mobility different
than that of said compound;
Q represents a hydrogen atom, a hydroxy radical, or a radical
having the formula -NHCoR3 or -NHSo2R3 whereln R3 preferably is alkyl of
1 to about 4 carbon atoms substituted with hydroxy, cyano, sulfamoyl,
. carboxy or sulfo; benzyl, phenyl or phenyl substituted with carboxy,
chloro, methyl, methoxy or sulfamoyl and when Q is hydroxy -NHCORJ or
:,
:. -NHSo2R3, it is located in the 5- or 8-position relative to G,
; G represents a hydroxy radical;
~- : Z represents a halogen atom, a cyano radical, a trihalomethyl
radical, an alkylsulfonyl radical having 1 to 4 carbon atoms, or a
sulfamoyl radical of the formula -S02NR R wherein
:
:
~ _ g_
:.
~3886~L '
R5 is hydrogen, alkyl of 1 to about 4 carbon atoms or aryl of
6 to about 8 carbon atoms and R can represent the same substi-
; tuents as R5 or alkyl- or arylcarbonyl as well as alk~l- or
arylsulfonyl wherein th~ alkyl and ar~l mo-ieties are as described
for R5, and R5 and R6, when taken together, represent a dialkyl-
aminomethylene radical ha~ing 1 to about 4 carbon atoms in the
alkyl moiety;
Rl represents a hydrogen atom, an alkoxy radical of
1 to about 4 carbon atoms or a halogen atom;
E represents a hydrogen atom or a sulfamoyl radical
as described for Z in the preceding paragraph, and
zl represents a hydrogen atom.
I Especially preferred compounds are those having
j formulas I, II and III above wherein Car- represents a radical
of the formula:
.
OH
IV. ,~~ ~
y ~ Ball
NHS02-
wherein Ball represents an organic ballasting group of such size
and configuration (e.g., simple organic groups or polymeric groups)
as to render the compound nondiffusible during development in the
alkaline processing composition and Y represents the carbon atoms
necessary to complete a benzene or naphthalene nucleus including
substituted benzene or naphthalene. When Y represents the atoms
necessary to complete a naphthalene nucleus, Ball can be attached
to either ring thereof.
--10--
~ . . . .
~ ~03~864
The nature of the ballast group (Ball) in the Formula
IV for the compounds described above is not critical as long
as it confers nondiffusibility to the compounds. Typical ballast
groups include long chain alkyl radicals linked directly or
indirectly to the compound as well as aromatic radicals of the
benzene and naphthalene series indirectly attached or fused
directly to the benzene nucleus, etc. Useful ballast groups
generally have at least 8 carbon atoms such as a substi-tuted
or unsubstituted alkyl group of 8 to 22 carbon atoms, an amide
radical having 8 to 30 carbon atoms, a keto radical having 8 to
30 carbon atoms, etc, and may even comprise a polymer backbone.
Especially preferred compounds are those wherein the ballast
is attached to the benzene nucleus through a carbamoyl radical
(-NHCO-) or a sulfamoyl radical ~-NHS02-) in which the nitrogen
... .
is adjacent the ballast group.
In addition to the ballast, the benzene nucleus in
the above formulas may have groups or atoms attached thereto
such as the halogens, alkyl, aryl, alkoxy, aryloxy, nitro, amino,
alkylamino, arylamino, amido, cyano, alkylmercapto, keto, carbo-
alkoxy, heterocyclic groups, etc.
A suitable process for producing a photographic transfer
image in color using the compounds of our invention, for example,
those wherein Car is as shown in Formula IV comprises the steps of:
~ eating the above-described photosensitive element
with an alkaline processing composition in the presence of a
silver halide developing agent to effect development of each of
the exposed silver halide emulsion layers, thereby oxidizing the
developing agent and the oxidized developing agent in turn cross-
oxidizing the sulfonamido compound,
~L03~i4 ~:
2) forming an imagewise distribution of diffusible
dye as a function of the imagewise exposure o~ each of the silver
halide emulsion layers by cleaving each cross-oxidized sulfon-
amido compound; and
3) diffusing to a dye image-receiving layer at least
a portion of each of the imagewise distributions of diffusible
anionic dye to provide an image. ~ i
~ ne photosensitive element~in the above-described
process can be treated with an alkaline processing composition
to effect or initiate development in any manner. A preferred
method for applying processing composition is by use of a ruptur-
able container or pod which contains the composition. In general,
the processing composition employed in our system contains the
developing agent for development, although the composition could
also just be an alkaline solution where the developer is incor-
porated in the photosensitive element, in which case the alkaline
solution serves to activate the incorporated developer.
A photographic fiIm unit according to our invention
which is adapted to be processed by passing the unit between a
pair of juxtaposed pressure-applying members, comprises:
1) a photosensitive element as described above;
2) a dye image-receiving layer; and
3) means for discharging an alkaline processing
co~position within the film unit such as a ruptur-
able container which is adapted to be positioned
during processing of the film unit so that a
compressive force applied to the container by the
- pressure-applying members will effect a discharge of
the contents of the container within the film unit;
the film unit containing a silver halide developing agentO
-12-
~038~6~
The dye image-receiving layer in the above-described
film unit can be located on a separate support adapted to be
superposed on the photosensitive element after exposure thereof.
Such image-receiving elements are generally disclosed, for
.
exàmple, in U. S. Patent 3,362,819. When the means for dis-
charging the processing composition is a rupturable container,
; typically it is posi-tioned in relation to the photosensitive
element and the image-receiving element so that a compressive
force applied to the container by pressure-applying members, such
as found in a camera designed for in-camera processing, will
effect a discharge of the contents of the container between the
image-receiving element and the outermost layer of the photo-
sensitive element. After processing, the dye image-receiving
element is separated from the photosensitive element.
The dye image-receiving layer in the above-described
film unit can also be located integral with the photosensitive
element between the support and the lowermost photosensitive
silver halide emulsion layer~ One useful format for integral
receiver-negative photosensitive elements is disclosed in
Belgian Patent 757,960. In such an embodiment, the support for
the photosensitive element is transparent and is coated with
an image-receiving layer, a substantially opaque llght reflective
layer, e.g., TiO2, and then the photosensitive layer of layers
described above After exposure of the photosensitive element,
a rupturable container containing an alkaline processing composi-
- tion and an opaque process sheet are brought into superposedposition. Pressure-applying members in the camera rupture the
container and spread processing composition over the photosensi-
tive element as the film unit is withdrawn from the camera. The
processing composition develops each exposed silver halide emul
sion layer and dye images are formed as a function o-~ development
-13-
i03886~
which diffuse to the image-receiving layer to provide a right-
reading image which is viewed through the transparent support
on the opaque reflecting layer backg~und.
Another format for integral negative-receiver photo- ;
sensitive elemen-ts in which the present invention can be employed
is disclosed in Belgian Patent 757,959. In this embodiment~ the
support for the photosensitive element is transparent and is
coated with the image-receiving layer, a substantially opaque,
light-reflective layer and the photosensitive layer or layers
10 described above. A rupturable container containing an alkaline
processing composition and an opacifier is positioned adjacent
to the top layer and a transparent top sheet. The film unit is
placed in a camera, exposed through the transparent top sheet
and then passed through a pair of pressure-applying members in
the camera as it is being removed therefrom . The pressure- ~¦
applying members rupture the container and spread processing
composition and opacifier over the negative portion of the film
unit to render it light insensitive. The processing composition
develops each silver halide layer and dye images are formed as
20 a result of development which dlffuse -to the image-receiving
layer to provide a right-reading image that is viewed thrGugh
the transparent support on the opaque reflecting layer background.
Still other useful integral fo~nats in which our
sulfonamido compounds can be employed are described in U. S.
Patents 3,415,644; 3,415,645; 3,415,646; 3,647,437; and
3,635,707- -
The film unit or assembly of the present inventioncan be used to produce positive images in single- or multi-
colors. In a three-color system, each silver halide emulsion
30 layer of the film assembly will have associated therewith an
image dye-providing material possessing a predominant spectral
absorption within the region of the visible spectrum to which
-14-
~03~4 `~
said silver halide emulsion is sensitive, i.e., the blue-sensitive
silver halide emulsion layer will have a yellow image dye-providing
material associated therewith, the green-sensitive silver halide
emulsion layer will have a magenta image dye-provicling material
associated therewith, and the red-sensitive silver halide emulsion
layer will have a cyan image dye-providing material associated
therewith. The image dye-providing material associated with each
silver halide emulsion layer can be contained either in the silver
halide emulsion layer itself or in a layer contiguous to the silver
halide emulsion layer. The magenta image dye-providing material will,
of course, be a compound of this invention, and when G i8 an ester, the
compound can be contained in the silver halide emulsion.
The concentration o the compounds which preferably are
alkali-cleavable upon oxidation that are employed in the present
; invention can be varied over a wide range depending upon the
particular compound employed and the results which are desired. For
example, the image dye-providing compounds of the present invention
can be coated in layers by using coating solutions containing between
about 0.5 to about 8 percent by weight of the image dye-providing compound
distributed in a hydrophilic film-forming natural or synthetic polymer,
such as gelatin, polyvinyl alcohol, etc., which is adapted to be permeated
by aqueous alkaline processing composition. Typically, the present
compounds are incorporated in a coupler solvent Ce.g., a high boiling,
water immiscible organic solvent2 prior to distribution in the gelatin
by techniques known in the art.
- 15 -
" ~
~03~
Depending upon which Car is used on the present com-
pounds, a variety of silver halide developing agents can be
employed in our invention. If the carrier used is that of Formula
IV, any silver halide developing agent can be used as long as it
cross-oxidizes with the image dye-providing compounds used herein.
The developer can be employed in the photosensitive element to
be activated by the alkaline processing composition. Specific
examples of developers which can be employed in our invention
include: hydroquinone, N-methylaminophenol, Phenidone (l-phenyl-
3-pyrazolidone), Dimezone ~l-phenyl-4,4-dimethyl-3-pyrazolidone),
l-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, ascorbic acid,
aminophenols, N,N-diethyl-~-phenylenediamine, 3-methyl-N,N-diethyl-
~-phenylenediamine, 3-methoxy-N-ethyl-N-ethoxy- p-phenylenediamine,
etc. The black-and-white developers in this list are preferred, in
that they have a reduced propensity of staining the dye image-
receiving layer.
In a preferred embodiment of our invention, the silver
halide developer in our process becomes oxidized upon development
and reduces silver halide to silver metal. The oxidized developer
then cross-oxidizes the sulfonamido phenol dye-releasing compound.
The product of cross-oxidation then undergoes alkaline hydrolysis,
thus releasing an imagewise distribution of diffusible anionic
dye which then diffuses to the receiving layer to provide the
positive dye image. The diffusible moiety is transferrable in
alkaline processing composition either by virtue of its self-
diffusivity or by having attached to it one or more solubilizing
- groups such as COOH, S03H, So2NR5R6, OH, etc (where R5 and R6
are as described previously with at least one being hydrogen).
In using the especially preferred dye-releasing
compour,ds according to our invention, the production of diffus-
ible dye images is a function of the reduction of developable
silver halide images which may irvolve direct or reversal
-16-
~03~3864 ~
development of the silver halide emulsions with a silverhalide developing agent. If the silver halide emulsion employed
is a direct~positive silver halide emulsion, such as an internal-
image emulsion or a solarizing emulsion, which is developable in
unexposed areas, a positive image can be obtained on the dye
image-receiving layer. After exposure of the film unit, the
,.:
alkaline processing composition pçrmeates the various layers to
initiate development o* the exposed photosensitive silver halide
emulsion layers. The developing agent present in the film unit
develops each of the silver halide emulsion layers in the un-
exposed areas (since the silver halide emulsions are direct-
positive ones)~ thus causing the developing agent to become
oxidized imagewise corresponding to the une~posed areas of the
direct-positive silver halide emulsion layers. The oxidized
; developing agent then cross-oxidizes the dye-releasing compounds
and the oxidized form of the compounds then undergoes a base-
catalyzed reaction in a preferred embodiment of our invention,
to release the preformed dyes imagewise as
a function of the imagewise exposure of each of the silver
halide emulsion layers. At least a portion of the imagewise
distributions of diffusible dyes diffuse to
the image-receiving layer to form a positive image of the original
i subject. After being contacted by the alkaline processing com-
position, a pH-lowering layer in the film unit or image-receiving
unit (if such a layer is needed) lowers the pH of the film unit
of image receiving to stabilize the image.
If photographic elements are used which contain com-
pounds of this invention wherein Car is a silver halide developer
as described, for example, in U. S. Patent No. 2,983,606, when
-17-
~03~86~ ~
the liquid processing composition is applied, it permeates the
emulsion to provide a solution of the dye developer substantially
uniformly distributed in the emulsion. As the exposed silver
halide emulsion is developed, the oxidation product of the dye
developer is immobilized or precipitated in situ with the
developed sil~er, thereby providing an imagewise distribution
of unoxidized dye developer dissolved in the liquid processing
composition. This immobilization is apparently due, at least
in part, to a change in the solubility characteristics of the
dye developer upon oxidation. At least part of this imagewise
distribution of unoxidized dye-developer is transferred to a
superposed image-receiving layer to provide a transfer image.
Internal-image silver halide emulsions useful in those
embodiments wherein a dye is released as a function of oxidation
are direct-positive emulsions that form latent images predominantly
~ inside the silver halide grains, as distinguished from silver
; halide grains that form latent images predominantly on the sur-
face thereof. Such inte m al-image emulsions are described by
Davey et al in U. S. Patent 2,592,250, issued April 8, 1952, and
elsewhere in the literature. Other useful emulsions are described
in Belgian Patent No. 780,531, dated March 31, 1972. Inte m al-
image silver halide emulsions can be defined in terms of the
increased maximum density obtained when developed with "inte m al-
type" developers over that obtained when developed with "surface-
type" developers. Suitable inte m al-image emulsions are those
which, ~hen measured according to normal photographic techniques
-18-
~038~64
by coating a test portion of the silver halide emulsion on a
transparent support, exposing to a light-intensity scale having
a fixed time between 0.01 and 1 second, and developing for 3
minutes at 20~C. in Developer A below ("internal-type'l developer),
have a maximum density at least five times the maximum density
obtained when an equally exposed silver halide emulsion is developed
for 4 minutes at 20C. in Developer B described below ~"surface-
type" developer). Preferably, the maximum density in Developer A
is at least 0.5 density unit greater than the maximum density in
Developer B.
DEVELOPER A
Hydroquinone 15 g.
Monomethyl-p-aminophenol sulfate 15 g.
Sodium sulfite ~desiccated) 50 g.
Potassium bromide 10 g.
Sodium hydroxide 25 g.
Sodium thiosulfate 20 g.
Water to make one liter.
1 DEVELOPER B
¦ P-hydroxyphenylglycine 10 g.
Sodium carbonate 100 g.
Water to make one liter
The solarizing direct-positive silver halide emulsions
useful in the above-described embodiment are well-known
` 20
silver halide emulsions which have been effectively fogged
either chemically or by radiation to a point which corresponds
approximately to the maximum density of the reversal curve
as shown by Mees, The Theory of the Photographic Process,
published by the Macmillan Co., New York, New York, 1942,
pages 261-297. Typical methods ~or the preparation of
solarizing emulsions are shown by Groves British Patent
443,245, February 25, 1936, who subjected emulsions to
Roentgen rays "until an emulsion layer formed therefrom, when
developed without preliminary exposure, is blackened up to
the apex of its graduation curve"; Szaz British Patent 462,730,
March 15, 1937, the use of ei~her light or chemicals sush as
silver nitrate, organic sulfur compounds and dyes to
--19--
1C~313864
convert ordinary silver halide emulsions to solarizing direct positive
emulsions; and Arens U. S. Patent 2,005,837, June 25, 1935, the use of
silver nitrate and other compounds in conjunction with heat to effect
solarization. Kendall and Hill U. S. Patent 2,541~472, February 13,
1951, shows useful solarized emulsions particularly susceptible to
exposure with long wavelength light and initial development to produce
the Herschel effect described by Mees above, produced by adding benzo-
thiazoles and other compounds to the emulsions which are fogged either
chemically or with white light. In using the emulsions a sufficient
reversal image exposure i5 employed using minus blue light of from about
500-700 m~ wavelength preferably 520-554 m~, to substantially destroy
; the latent lmage in the silver halide grains in the region of the image
exposure. Particularly useful are the fogged direct-positive emulsions
of Berriman U. S. Patent 3,367,778; Illingsworth U. S. Patents 3,501,305,
3,501,306 and 3,501,307; and combinations thereof.
Internal-image silver halide emulsions which contain or which
are processed in the presence of fogging or nucleating agents are
particularly useful in the above-described embodiment since the use of
fogging agents is a convenient way to inject electrons into the silver
halide grains. Suitable fogging agents include the hydrazines disclosed
in Ives U. S. Patents 2,588,982 issued March 11, 1952 and 2,563,785
issued August 7, 1951; the hydrazides and hydrazones disclosed in
Whitmore U. S. Patent 3,227,552 issued January 4, 1966; or mixtures
thereof. The quantity of fogging agent employed can be widely varied
depending upon the results desired. Generally, the concentration of
fogging agent is from about 1 to about 20 mg. per square foot of photo-
sensitive layer in the photosensitive element or from about 0.1 to
- 20 -
~03886~
about 2 grams per liter of developer if it is located in the
developer.
Other embodiments in which our imaging chemistry can
be employed include the techniques described in U.S. Patents
3,227,550, 3,227,551, 3,227,552 and 3,364,022, and in British
Patent 904,364, p. 19, lines }-41, wherein our dye image-providing
materials are substituted for the nondiffusible dye-providing
couplers described therein. For example, a film unit using
development inhibitor-releasing couplers as described in U.S. Patent
3,227,551 may be employed in conjunction with the dye image-
providing materials described herein. In this method, however, the
developing agent employed must include one which oxidatively couples
to release the inhibitor compounds. These developing agents are
genera~ly selected from the class of aromatic primary amino develop-
ing agents such as ~-aminophenols or ~-phenylenediamines.
Another embodiment of our invention uses the image-
~ reversing technique disclosed in British Patent 904,364, page 19,
; lines 1-41. In this system our dye-providing compounds are used
in combination with physical development nuclei in a nuclei layer
contiguous to the photosensitive silver halide emulsion layer.
The film unit contains a silver halide solvent, preferably in a
: rupturable container with the alkaline processing composition,
and the photosensitive element contains an immobilizing coupler,
which is capable of reacting with oxidized developer to form an
immobile product. This embodiment also must include developing
agents which are reactive with the immobilizing coupler. Preferred
compounds include the primary aromatic amines described above.
me various silver halide emulsion layers of a color
film assembly of the invention can be disposed in the usual order,
i.e., the blue-sensitive silver halide emulsion layer first with
respect to the exposure side,
-21-
~038~64
followed by the green-sensitive and red-sensitive silver halide
emulsion layess. If desired, a yellow dye layer or a Carey Lea
silver layer can be present between the blua-sensitive and green-
sensitive silver halide emulsion layer for absorbing or filtering
blue radiation that may be transmitted through the blue-sensitive
layer. If desired, the selectively sensitized silver halide
emulsion layers can be disposed in a different order, e.g., the
blue-sensitive layer first with respect to the exposure side,
followed by the rad-sensitive and green-sensitive layers.
The silver halide emulsions used in this invention can
comprise, for example, silver chloride, silver bromide, silver
~ chlorobromide, silver bromoiodide, silver chlorobromoiodide or
; mixtures thereof. The emulsions can be coarse- or fine-grain and
can be prepared by any of the well-known procedures, e.g., single-
jet emulsions such as those described in Trivelli and Smith,
The Photographic Journal, Vol. LXXIX, May, 1939 (pp 330-338),
double-jet emulsions, such as Lippmann emulsions, ammoniacal
emulsions, thiocyanate or thioether ripened emulsions such as
those described in Nietz et al, U. S. Patent 2,222,264, issued
November 19, 1940; Illingsworth U. S. Patent 3,320,06g issued May
16, 1967; and Mc~ride U. S. Patent 3,271,157 issued September 6,
1966. Surface-image emulsions can be used or internal-image
emulsions can be used ~uch as those described in Davey et al U.S.
Patent 2,592,250 issued May 8, 1952; Porter et al U.S. Patent
3,206,313 issued September 14, 1965; Berriman U.S. Patent 3,367,778
issuea February 6, 1968; and Bacon et al U.S. Patent 3,447,927
issued June 3, 1969 The emulsions may be regular-grain emulsions
such as the type described in Rlein and Moisar, J. Phot. Sci., Vol.
12, No. 5, Sept./Oct., 1964, (pp. 242-251). Negative~type emulsions
may be used or direct-positive emulsions may be used such as those
described in Leermakers U. S. Patent 2,184,013 issued December 19,
1939 Kendall et al U.S.
ll
-22-
~03~864
Patent 2,541,472 issued February 13, 1951; Berriman U.S. Pa~ent
3,367,778 issued February 6, 196~; Schouwenaars British Patent
723,019 issued February 2, 1955; Illingsworth et al French Patent
1,520,821 issued March 4, 1968; Il}ingsworth U.S. Patent 3,501,307
issued March 17, 1970; Ives U.S. Patent 2,563,785 issued August 7,
1951; Xnott et al U.S. Patent 2,456,953 issued December 21, 1948;
and Land U. S. Patent 2,861,885 issued November 25, 1958.
The rupturable container employed in this invention can
be of the type disclosed in U. S. Patent Nos. 2,543,181; 2,643,886;
2,653,732; 2,723,051; 3,056,492; 3,056,491 and 3,152,515. In
general, such containers comprise a rectangular sheet o~ fluid-
and air-impervious material folded longitudinally upon itself to
form two wall~ which are sealed to one another along their longi-
tudinal and end margins to form a cavity in which processing
solution is contained.
In a color film unit according to this invention, each
silver halide emulsion layer containing a dye image-providing
material or having the dye image-providing material present in a
contiguous }ayer may be separated from the other silver halide
emulsion layers in the image-forming portion of the film unit by
materials including gelatin, calcium alginate, or any of those
disclosed in U.S. Patent No. 3,384,483, polymeric materials such
as polyvinylamides as disclosed in U.S. Patent 3,421,892, or any
of those disclosed in French Patent 2,028,236 or U. S. Patent Nos.
2,992,104; 3,043,692; 3,Q4~.,873; 3,061,428; 3,069,263; 3,069,264;
3,121,011; and 3,427,158.
Generally speaking, except where noted otherwise, the
silver halide emulsion layers in the invention comprise photo-
sensitive silver halide dispersed in gelatin and are about 0.6
to 6 microns in thickness; the dye image-providing materials are
dispersed in an aqueous alkaline
-23-
~(~,38~i4 ; ~
solution-permeable polymeric binder, such as gelatin, as a
separate layer about l to 7 microns in thickness, and the alk~ine
solution-permeable polymeric interlayers, e.g., gelatin, are
about l to 5 microns in thickness. Of course, these thicknesses
are approximate only and can be modified according to the product
desired.
Any material can be employed as the image-receiving
layer in this invention as long as the desired function of
; mordanting or otherwise fixing the dye images will be obtained.
The particular material chosen will, of course, depend upon the
dye to be mordanted. If acid dyes are to be mordanted, the
image-receiving layer can contain basic polymeric mordants such
as polymers of amino guanidine derivatives of vinyl methyl ketone
such as described in Minsk U. S. Patent 2,882,156, issued April 14,
1959, and basic polymeric mordants such as described in Cohen et al
U. S. Patent No. 3,709,690, issued January 9, 1973.
Preferred mordants are cationic mordants such as poly-
; meric compounds composed of a polymer having quaternary nitrogen
groups and at least two aromatic nuclei for each quaternary
nitrogen in the polymer cation (i.e., having at least two aromaticnuclei for each positively charged nitrogen atom), such polymeric
compounds being substantially free of carboxy groups. Useful
mordants of this type are comprised of units of the following
formula in copolymeri~ed relationship with units of at least
one other ethylenically unsaturated monomer:
R7
- CH - C - _
R (Q)
Rll- N~ - R9 X~
. R10
-24-
16)3~86~ ~
wherein R7 and R8 each represent a hydrogen atom or a lower a~kyl
radical (of 1 to about 6 carbon atoms) and R8 can additionally
be a group containing at least one aromatic nucleus~e.g.~ phenyl,
naphthyl, tolyl); Q can be a divalent alkylene radical (of 1
to about 6 carbon atoms), a divalent arylene radical, a divalen-t
aralkylene radical, a divalent arylenealkylene radical,
O O O
,~ ,. .. .
-C-OR12-, -OC-R12-, or -C-NH-R12-, wherein R12 is an alkylene
radical, or R8 can be taken together with Q to form a
~ ~; R9 R10 and Rll can be lower alkyl or aryl,
--C
~ Q
or R9 and R10 and the nitrogen atom to which they are attached
can together with Q represent the atoms and bonds necessary to
form a quaternized nitrogen-containing heterocyclic ring, and
X9 is a monovalent negative salt forming radical or atom in
ionic relationship with the positive salt forming radical, wherein
said polymer is substantially free of carboxy groups and wherein
the positive salt forming radical of said polymer comprises at
least two aryl groups for each quaternary nitrogen atom in said
polymer. These preferred polymeric cationic mordants are
20 described further in the above-mentioned U. S. Patent No.
3,709,690.
Other mordants useful in our invention include poly-
4-vinylpyridine, the 2-vinyl pyridine polymer metho-p-toluene
sulfonate and similar compounds described in Sprague et al U. S.
Patent 2,484,430, issued October 11, 1949, and cetyl trimethyl-
ammonium bromide, etc. Effective mordanting compositions are
also described in Whitmore U. S. Patent 3,271,148 and Bush U. S.
Patent 3,271,147, both issued September 6, 1966.
-25-
~038~36~ `
Furthermore, the image-receiving layer can be sufficient
by itself to mordant the dye as in the case of use of an alkaline
solution-permeable polymeric layer such as N-methoxy-methyl
polyhexylmethylene adipamide; partially hydrolyzed polyvinyl
acetate, polyvinyl alcohol with or without plasticizersj cellu-
lose acetatej gelatin, and other materials of a similar nature.
~enerally, good results are obtained when the image-receiving
layer, preferably alkaline solution-permeable, is transparent
and about 0.25 to about 0.40 mil in thickness. This thickness,
of course, can be modified depending upon the result desired.
The image-receiving layer can also contain ultraviolet absorbing
materials to protect the mordanted dye images from ~ad-lng due
to utlraviolet light, brightening agents such as the stilbenes,
coumarins, triazines, oxazoles, dye stabilizers such as the
chromanols, alkylphenols, etc. ~,
Use of a pH-lowering material in the dye image-receiving
element of a film unit according to the invention will usually
increase the stability of the transferred image. Generally, the
pH-lowering material will effect a reduction in the pH of the
image layer from about 13 or 14 to at least 11 and preferably
5-8 within a short time after imbibi~on. For example, polymeric
acids as disclosed in U. S. Patent 3,362,819 or solid acids or
metallic salts, e.g., zinc acetate, zinc sulfate, magnesium
acetate, etc, as disclosed in U. S. Patent 2,584,o30 may be
employed with good results. Such pH-lowering materials reduce
the pH of the film unit after development to terminate deyelop-
ment and substantially reduce further dye transfer and thus
stabilize the dye image.
An inert timing or spacer layer can be employed in the
; 30 practice of our invention over the pH-lowering layer which "times"
or controls the pH reduction as a function of the rate at which
-26-
.
~03~64
alkali diffuses through the inert spacer layer. Examples of
such timing layers include gelatin, polyvinyl alcohol or a~y of
those disclosed in U. S. Patent 3,455,686. The timing layer
may be effective in evening out the various reaction rates over
a wide range of temperatures, e.g., premature pH reduction is
prevented when imbibition is effected at temperatures above room
temperature, for example, at 95-100Fo The timing layer is
usually about 0.1 to about 0.7 mil in thickness. Especially good
results are obtained when the timing layer comprises a hydro-
lyzable polymer or a mixture of such polymers which are slowlyhydrolyzed by the processing composition. Examples of such
hydrolyzable polymers include polyvinyl acetate, polyamides,
cellulose esters, etc.
The alkaline processing composition employed in this
invention is the conventional aqueous solution of an alkaline
material, e.g., sodium hydroxide, sodium carbonate or an amine
such as diethylamine, preferably possessing a pH in excess of
11, and preferably containing a developing agent as described
previously. The solution also preferably contains a viscosity-
increasing compound such as a high-molecular~weight polymer,
e.g., a water-soluble ether inert to alkaline solutions such as
hydroxyethyl cellulose or alkali metal salts of carboxymethyl
; cellulose such as sodium carboxymethyl cellulose. A concentration
of viscosity-increasing compound of about 1 to about 5~ by weight
of the processing composition is preferred which will impart
thereto a viscosity of about 100 cps. to about 200,000 cps. In
certain embodiments of our invention, an opacifying agent, e.g.,
TiO2, carbon black, etc, may be added to the processing composition.
While the alkaline processing composition used in this
invention can be employed in a rupturable container, as described
previously, to conveniently facilitate the introduction of pro-
1038~6~
cessing composition into the film unit, other methods of insertingprocessing composition into the film unit could also be employed,
e.g., interjecting processing solution with communicating members
similar to hypodermic syringes which are attached either to a
camera or camera cartridge.
The alkaline solution-permeable, substantially opaque,
light-reflective layer employed in certain embodiments of photo-
graphic film units of our invention can generally comprise any
opacifier dispersed in a binder as long as it has the desired
properties. Particularly desirable are white light-reflective
layers since they would be esthetically pleasing backgrounds
on which to view a transferred dye image and would also possess
the optical properties desired for re~lection of incident radia-
tion. Suitable opacifying agents include titanium dioxide,
barium sulfate, zinc oxide, barium stearate, silver flake,
silicates, alumina, zirconium oxide, zirconium acetyl acetate,
sodium zirconium sulfate, kaolin, mica, or mixtures thereof in
widely varying amounts depending upon the degree of opacity
desired. The opacifying agents may be dispersed in any binder
such as an alkaline solution-permeable polymeric matrix such
as, for example, gelatin, polyvinyl alcohol, and the like.
Brightening agents such as the stilbenes, coumarins, triazines
and oxazoles can also be added to the light-reflective layer,
if desired. Wn~en it is desired to increase the opacifying capacity
of the light-reflective layer, dark-colored opacifying agents,
e.g., carbon black, nigrosine dyes, etc, may be added to it, or
coated in a separate layer adjacent to the light-reflective layer.
The supports for the photographic elements of this
invention can be any material as long as it does not deleteriously
3 effect the photographic properties of the film unit and is dimen-
sionally stable. Typical flexible sheet materials include
cellulose nitrate film, cellulose acetate film, poly(viny; acetal)
-28-
1~3~ 4
fi~m, polystyrene film, poly(ethyleneterephthalate) film, poly-
carbonate film, poly-a-olefins such as polyethylene and poly-
propylene film, and related films or resinous materials. The
support is usually about 2 to 6 mils in thickness.
While the invention has been described with reference
to layers of silver halide emulsions and dye image-providing
materials, dotwise coating, such as would be obtained using a
gravure printing technique, could also be employed. In this
technique, small dots of blue-, green- and red-sensitive emulsions
have associated therewith, respec-tively, dots of yellow, magenta
and cyan color-providing substances. After development, the trans-
ferred d~es would tend to ~use together -Lnto a con~inuous tone.
The sil~er halide emulsions useful in our invention
are well known to those skilled in the art and are described in
Product Licensing Index, Vol. 92, December, 1971, publication
9232, p. 107, paragraph I, "Emulsion types"; they may be chemi-
cally and spectrally sensitized as described on Rage 107, para-
graph III, "Chemical sensitization", and pp. 108-109, paragraph
X~, "Spectral sensitization", o~ the above article; they can be
p~otected against the production of fog and can be stabilized
against loss of sensitivity during keeping by employing the
materials described on p. 107, paragraph V, "Antifoggants and
~- stabilizers", of the above article; they can contain development
modi~iers, hardeners, and coating aids as described on pp. 107-
108, paragraph IV, "Development modifiers"; paragraph VII, "Har-
deners"; and paragraph XII, "Coating aids", of the above article;
they and other layers in the photographic elements used in this
invention can contain plasticizers, vehicles and filter dyes
described on p. 108, paragraph XI, "Plasticizers and lubricants",
and paragraph VIII, "Vehiclesi', and p. 109, paragraph XVI,
"Absorbing and filter dyes", of the above article; they and other
-29-
r.,~
~L03886~L .
layers in the photographic elements used in this invention m~.y
contain addenda which are incorporated by using the procedures
described on p. 109, paragraph XVII, "Methods of addition", of
the above article; and they can be coated by using the various
techniques described on p. 109, paragraph ~VIII, "Coat:Lng pro-
cedùres", of the above article, the disclosures of which are
hereby incorporated by referenceO
It will be appreciated that there remains in the photo-
graphic element after transfer has taken place an imagewise
distrlbution of dye in addition to developed silver. A color
image comprls~ng residual nondif~usible compound may be obta~.ned
in this element if the residual silver and silver halide are
removed by any conventional manner well known to those skilled
in the photographic art, such as a bleach bath followed by a
fix bath, a bleach-fix bath, etc. The imagewise distribution
of dye may also diffuse out of the element into these baths~ if
desired, rather than to an image-receiving element. If a
negative-working silver halide emulsion is employed in such
photosensitive element, then a positive color image, such as a
color transparency or motion-picture film, may be produced in
this manner. If a direct-positive silver halide e~ulsion is
` e~ployed in such photosensitive element, then a negative color
image may be produced.
The following examples are provided for a further
understanding of the invention. The structures of all of the
c~mpounds were confirmed by their infrared and NMR spectra and
in some cases by elemental analysis. The notation C5Hll-t is
an abbreviation for t-pentyl.
~0388G4
Example 1 - Preparation of Compound No. 1
ilO~II=N~SOaN=CH-II( CH3) 2
CH3CONH ¢0~ SO2NH
[~0~ (CHa),,-O~sHll-t
I OH
To 90 ml. of dry pyridine, under nitrogen, at 0C. was
added 2.95 g. (o.o6 mol) of 4-amino-N-C4-(2,4-di-tert-pentyl-
phenoxy)butyl]-l-hydroxy-2-naphthamide. To this solution 2.9 g.
(o .o6 mol) of 4-acetamido-8-~5-N-(dimethylaminomethylene)sulf-
amoylphenylazo]-5-hydroxy-1-naphthalenesulfonyl chloride was
added. The reaction mixture was stîrred at room temperature
for ninety minutes and then poured into a mixture of ice and
concentrated hydrochloric acid. The resulting solid was collected
on a filter funnel and dried to yield 5.8 g. (> 100~). It was
purified by chromatography using a silica ~column, with ethyl
acetate being used to elute the product. The yield was 30~,
m.p. 237C. PREPARATION OF INTERMEDIATES: The sulfonyl
chloride compound above was prepared from the sodium salt of the
corresponding sulfonic acid compound by adding 3.0 g. (0.01 mol)
of N,N-dimethylformamide to a slurry of 4.85 g. (0.01 mol) of
sodium 4-acetamido-5-hydroxy-6-(4-sulfamoylphenylazo)-1-naphtha-
lenesulfonate in 600 ml. of thionyl chlorideg The mixture was
stirred for 90 minutes at room temperature and filtered. The
filtrate was poured onto ice, the solid collected on a filter
funnel and dried to yield 1.3 g. (24~), m.p. 140C. The sodium
salt of the dye above was obtained as follows: 300 ml. of lN
, , ,
-31-
~L03~86~ ;
hydrochloric acid was added to a solution of 17.2 g. (0.1 mol)
of sulfanilamide in 100 ml. of 1~ sodium hydroxide. The solu-
tion was cooled to 0C and a solution of 6.9 g. (0.1 mol) of
sodium nitrite in 80 ml. of water was added at <3C. This
mixture was then added to a solution of 8-acetamido-1-acetoxy-
5-naphthalenesulfonic acid, pyridine salt in 300 ml. of lN
sodium hydroxide at < 3C. The reaction mixture was stirred
for one hour, solid collected on a filter funnel and dried to
yield 35.2 g. (72~), m.p. 7300C. The pyridine salt above was
obtained by the acetylation of "S acid" in acetic anhydride and
pyridine at 80C.
Example 2 - PreParation of Compound No. 2
OCH3
;~ HO ~ -N=N ~
CH~CON~ ~ SO2NH SO2N=CH-N(CH3)2
1 C5HlL-t
~ CO~H~(cH2)~-O ~ -CsHL -t
This compound was prepared in a manner similar to
that used in Example 1. The yield was 20~, m.p. 163-6C.
The 4-acetamido-8-~5-(N-dime-thylaminomethylene)sulfamoyl-2-
methoxyphenylazo]-5-hydroxy-1-naphthalenesulfonyl chlori.de was
-~ prepared in a manner similar to that used in Example 1.
-32-
~03~3864 ' ~
Example 3 - Preparation of Compound No. 3
OCH~
H ~ N-N- ~
~ SO2N=CH-N(CH3)2
C~H5CO~ ~ SO2NH
@$LCON~l-(cH~4-o~asHl~-t
OH
The method used in Example 1 was utilized to prepare
this compound. The yield was 26~, m.p. 168-72C dec. m e 4- ;
benzamido-8-[5-N-(dimethylaminomethylene)sulfamoyl-2-methoxy-
phenylazo]-5-hydroxy-1-naphthalenesulfonyl chloride was prepared
by the method used for Example 1 in 68~ yield. Sodium 4-
benzamido-5-hydroxy-8-(2-methoxy-5-æulfamoylphenylazo)-1-
naphthalenesulfonate was also prepared similarly to Example 1
~! lo in 35% yield.
Example 4 - Preparation of Compound No. 4
:
~O~N=I~SO2NHSO2
C~H5CONH- ~ -SO2NH
~ CONH-(CH2)~-O ~ CsHlL-t
.. . . .
,~
The method used for Example 1 was used to prepare
this compound. The yield was 15~, m.p. 155-60C dec. The sulfonyl
chloride was prepared from 1.0 g. (.0014 mol.) of 4-benzamido-8-
[4-(N-benzenesulfonylsulfamoyl)phenylazo]-5-hydroxy-1-naphthalene-
sulfonic acid, sodium salt which was stirred overnight in 25 ml.
1038864
of chlorobenzene containing o.8 g. of phosphorous pentachloride.
The solid was collected on a filter funnel and dried to yield
1.0 g. (100~). The sodium 4-benzamido-8-~4-(benzenesulfonyl-
sulfamoyl)phenylazo]-5-hydroxy-1-naphthalene sulfonate was pre-
pared in a manner similar to Example 1 in 15~ yield.
Example 5 - Preparation of Compound No. 5
CONH( CH2) 4,-0~C5H~ t
~: ~ }IO~N=N~S02~1~_011 Cs~l~~t
CH3COI~H~S02NH ~)
--CO~H-( CH2 ) " -0- ~CsH l ~,- t
Cs l-t
......
To a solution of 1.95 g. (.004 mol) of ~-amino-N-
[4-~2~4-di-tert-pentylphenoxy)butyl~-1-hydroxy-2-naphthamide in
50 ml. of dry pyridine at 0C, under nitrogen, was added 1.95 g.
', (.004 mol) of 4-acetamido-8-(4-chlorosulfonylphenylazo)-5-
hydroxy-l-naphthalenesulfonyl chloride. The solution was stirred
at 0C for one hour, poured into 75 ml. of concentrated hydro-
chloric acid and 75 ml. of ice. The solid was collected on a
filter funnel and dried. It was then chromatographed on a silica
column, eluting with ethyl acetate to remo~e the product. The
eluents were concentrated to dryness and the resulting solid
reprecipitated from chloroform with hexane. The solid was
collected on a filter funnel and dried to yield 1.1 g. (39%),
m.p. 220-2C dec. The 4-acetamido-8-(4-chlorosulfonylphenylazo)-
5-hydroxy-1-naphthalenesulfonyl chloride was prepared by heating
a solution of 9.7 g. (.02 mol) of sodium 4-acetamido-5-hydroxy-
-3l~-
~38864
6-(4-sulfamoylphenylazo)-l-naphthalenesulfonate in 150 ml. of
chlorosulfonic acid on a steam bath for ninety minutes. The
solution was cooled and poured onto ice. 'rhe solid was collected
on a filter funnel and dried to yield 9.4 g. (94~). The sodium
4-acetamido-5-hydroxy-8-~4-sulfamoylphenylazo)-1-naphthalene-
sulfonate was prepared as in Example l.
.. . . . ~ . ...... . .... .. . . _ _ . . . . .
Example 6 - Preparation of Compound No. 6
CH30 CONH-(CH2)~-0 ~ sHll-t
HO ~ -N~N ~ -SO2NH ~ OH C t
CH3CO~ ~ SO2~
C01~ t CH2 ~ 4-0~5Hll-t
~ OH Hll-t
. . .
This compound was prepared in a manner similar to that
used for Example 5. The yield was 74~, m.p. 138-42C. The 4-
acetamido-8-(5-chlorosulfonyl-2-methoxyphenylazo)-5-hydroxy-1-
naphthalenesulfonyl chloride was prepared according to the method
of Example 5. The sodium 4-acetamido-5-hydroxy-8-(5-sulfamoyl-
2-methoxyphenylazo)-1-naphthalenesulfonate was prepared in a
manner similar to that used in Example 1.
Example 7 - Preparation of Compound No. 7
.~
HO ~ -N=N ~ SozNHCtCH3) 3
CH3GOi~H ~ ,SOz
.
--CONH-(C~I2)~-O ~ CsHll-t
OH C5Hll-t
- -35-
~03~3S1~4 ~
The method shown for Example 1 was also u6ed to prepare
this example in 40~ yield, m.p. 169-72C dec. The 4-acetamido-8-
[4-(N-t-butyl)sulfamoylphenylazo~-5-hydroxy-1-naphthalenesuIfonyl
chloride was prepared, in 89% yield, similarly to Example 1.
Sodium 4-acetamido-8-[4-(N-t-butyl)sulfamo~ylphenylazo]-5~hydroxy-
l-naphthalenesulfonic acid was prepared in a manner similar to
Example 1. The yield was 395~.
Exam~le 8 - Preparation of Compound No. 8
S ~ OH
NH
~CONH(CH2)~,-O~CsN~1-t
Cs}~ l L - t
: ,
To a solution of 2.50 g. (3.8 n~nol) of 4-m-aminobenzene-
sulfonamido-N-~4-(2,4-di-tert-pentylphenoxy)butyl]-1-hydroxy-2-
naphthamide in 20 ml. of trifluoroacetic acid (under nitrogen)
in an ice-methanol bath was added a cold solution of 0.28 g.
(4 mmol) of sodium nitrite in 3 ml. of water. The green-yellow
diazonium solution, which formed immediately, was poured into a
stirred solution (under nitrogen) of 0.62 g. (3.8 mmol) of 1,8-
dihydroxynaphthalene in 10 ml. pyridine and 50 ml. mixed acid
(1:5 propionic/acetic acids). The magenta-colored mixture was
stirred at 0 for 45 minutes and then poured into 600 g. of
20 ice water. The crude product was filtered, washed with water,
and dried. It weighed 3.32 g. The crude material was recrystal-
lized once from a mixture of tetrahydrofuran, methanol, and
water and again from ethyl acetate/hexane to give 2.35 g.
m.p. 232-234C.
_36-
103~864
Example 9 - Pre~aration of Compound No. 9
SO~ ~ N=N ~ H
NH . <~
[~L-CONH-( CH2 ) 4_0~>~5H~l- t ,
OH CsHll-t
~, To a solution of 1.3 g. (2.0 mmol) of 4-p-aminobenzene-
sulfonamido-N-~4-(2,4-di-tert-pentylphenoxy)butyl]-1-hydroxy-2-
naphthamide in 10 ml. of trifluoroacetic acid (under nitrogen)
was added a cold solution of 0.14 g. (2 mmol) of sodium nltrite
in 1 ml. of water. The deep brown-green diazonium solution thus
formed was poured into a solution of l-naphthol 6-sulfonamide in
9 ml. pyridine/45 ml. of 1:5 propionic/acetic acid. Because
coupling occurred rather slowly, the red-orange solution was
stirred 1.5 hours and then poured into 400 g. of ice water.
The resulting orange solid was filtered, washed with water and
air dried. The crude product was recrystallized from ethanol/
tetrahydrofuran/hexane and again ~rom tetrahydro~uran/hexane -to
give 1.07 g. (61~) of magenta dye, m.p. 164-166C.
Example 10 - Preparation of Compound No. 10
CONH(CH,)~-O~CsHll~'i
SO2NH
-37-
~ID38~
A solution of 6.45 g. ~10 mmol) ~-m-aminobenzenesulfon-
amido-N-[4-(2,4-di-t-pentylphenoxy)butyl]-1-hydroxy-2-naphthamide
in 100 ml. tetrahydrofuran was cooled to 3C and treated dropwise
with 1.2 g. of isopentyl nitrite. The mixture was stirred one-
` ; half hour and then poured slowly into a co:Ld solution of 1.6 g.
(10 mmol) of 1,5-naphthalenediol in 250 ml. of 20~o solution of
propionic acid in acetic acid followed by 10 drops of pyridine.
' The mix~ure was left in the refrigerator overnight, filtered,
and diluted with water to give a tar, which was solidified by
heating in glacial acetic acid followed by cooling. The solid
was filtered off, washed with water and air dried. On standing
an additional product precipitated from the supernatant, yielding
a total of 6.5 g. (80%). The product was recrystallized from
acetic acid to give 2.8 g. of orange powder, m.p. 232-5.
Example 11 - Preparation of Compound No. 11 ;~
, . S02~N=N~_oH i'~
NH ~ ~
-CO~H-(CHæ)4~0~ ~ CsHl-t
OH C5 ~1- t
`~ A solution of O.65 g. (1 mmol) of 4-m-aminobenzene-
sulfonamido-N-[4-(2,4-di-t-pentylphenoxy)butyl]~l-hydroxy-2-
naphthamide and 0.14 ml. of isopentyl nitrite in 10 ml. of tetra-
20 hydrofuran was added to a solution of 0.175 g. (1 mmol) of 1-
naphthol in 25 ml. of a 5:1 mixture of acetic acid and propionic
acid at 0C. The reaction mixture was stirred for one hour
during which time a red solid precipitated. The solid was col-
lected and washed with aqueous acetic acid. This provlded o.6 g.
of pure product in 72~ yield, m.p. 212-215.
_38-
.
~03~864
Example 12 - Photographic Testing
The dye-releasing redox (DRR) compounds were tested
for reactivity and diffusibility of their released dyes to a
receiving element. Each DRR compound was ais solved in an equal
weight of diethylauramide and finely dispersed in gelatin. me
dispersion was added to a o.8 ~m monodispersed negative-working
gelatino-silver bromide emulsion which was coated on a polyester
film 9upport, the coverage of DRR being about 1.1 x 10 5 moles/dm2;
silver - 9.2 mg/dm2; and gelatin - 32 mgjdm2. An overcoat layer
of 8.6 g/dm of gelatin, hardened by formaldehyde was then
applied.
A. Image discrimination - A sample of the above coating was
exposed through a step-wedge and then laminated to a mordant-
containing receiving element with a viscous processing composi-
; tion (goo) by passing the "sandwich" between a pair of juxtaposed
pressure-applying rollers. The receiving element consisted of
a paper support on which was coated a mixture of gelatin
(21 mg/dm2) and a mordant, poly~styrene-co-N-benzyl-N,N-dimethyl-
N-(3-maleimidopropyl)ammonium chloride] (21 mg/dm2). The goo
contained per liter of solution: 20 g. sodium hydroxide,
0.75 g. 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone, 10 g.
potassium bromide, and 25 g. hydroxyethylcellulose. After
60 seconds, the receiver was peeled apart and washed in water
to adjust the pH to about 7. Good image density in the exposed
areas was obtained with practically no transfer of dye in
the unexposed areas. The Dmax and Dmin for each transfer is
given under image discrimination in the table.
B. Spectrophotometry - The spectra of the released dyes when
adsorbed to the mordant on a transparent support were measured
spectrophotometrically. The maximum wavelength ( A max) and
-3g-
1038~364
the bandwidth in nm at one-half the density at the ~ max of the
curve for each dye is also given in the table. This "half
band width" along with the ~ max is indicative of hue, the
brightness and purity of color being greater, the smaller the
half band width.
C. Dye-transfer in receiving element - Another sample of an
emulsion coating containing the DRR compound was fogged by
exposure to light and processed by passing it as a "sandwich"
with an image receiving element and viscous developing composi-
tion (goo) between a pair of juxtaposed pressure-applying rollers.
The developer layer thickness of the resulting laminate ranged
from about .075 to .10 mm. The recei~ing element had -the
following structure (the coverages in mg/dm2 are shown ln
parenthesis):
Carbon (27) ~ Gelatin (17)
TiO2 (215) ~ Gelatin (21)
.
Mordant* (21) + Gelatin 111)
Cellulose acetate support
The "goo" contained 20 g. sodium hydroxlde, 0.75 g. 4-hydroxy-
20 methyl-4-methyl-1-phenyl-3-pyrazolidone, 10 g. potassium bromide
and 25 g. hydroxyethylcellulose, all per liter of solution.
Upon application of the goo to the fogged emulsion layer, the
dyes are released and diffuse through the carbon and titania
layers to the mordant layer. The density of the dyes on the
mordant layer was read through the support by means of a reflec-
tion densitometer after intervals of 30, 60 and 120 seconds at
24C. The increase in density as indicated by the values in the
table, is a measure of the rate of release and also of the
diffusivity of the dyes.
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40-
~3886~
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1038864
Example 13 - Preparation of Compound No. 12
OH
-N ~ 52NH ~ OH
CONH-(CH2)4-O ~ C5Hll t
~ ' C5Hll-t
- CH
A solution of 1 mole 5-amino-1-naphthol in dr~ pyridine
was stirred at 0C and treated portionwise with 1 mole o~ p-
toluenesulfonyl chloride. When anaylsis showed that the 5-amino-
; l-naphthol was consumed the reaction mixture was poured onto a
sufficient quantity of aqueous hydrogen chloride to neutralize
the excess pyridine and allow separation of the product as a
fine powder which was filtered, washed with water, and recrystal-
lized from ethanol to obtain (96~ yield) analytically pure
5-p-toluenesulfonamido-1-naphthol having a melting point of
182-194C. Next, 2.58 g. (4000 mmol) of 4-(m-aminophenylsulfon-
amido)-N-~4-(2,4~di-tert-pentylphenoxy)butyl]-1-hydroxy-2-
naphthamide were dissolved in 10 ml. dry pyridine and treated
with 50 ml. 5:1 acid and 10 ml. concentrated hydrochloric acid.
The clear solution was cooled to 0C. and treated with a solu-
tion of 284 mg. (4.00 mmol) sodium nitrite in 3 ml. of ice water.
The resulting orange solution was added rapidly to a solution
of 1.25 g. (4.00 mmol) of the above sulfonamidonaphthol dissolved
20 in 8 ml. dry pyridine and 50 ml. 5:1 acid, and cooled to 5C.
The orange dye formed immediately. After 40 minutes at 5-10,
the dye was precipitated by adding 300 ml. ice water and adjusting
the pH to 2 with concentrated HCl. The orange powder obtained
- 1~2 -
~03~36q~
by filtration was washed with 8 liters of water and dried to
gi~e 3.31 g. Compound 12. This compound was tested in a manner
similar to that of Example 12A and the released dye was found
to have a A max of 555 nm. The Dmax of transferred image was
0.97-
E le 14 - Pre aration of C ound No. 13
xamp _p omp
OH
~ .
NH N=N ~ SO H
C=O ~_J 3
S02~U ~ OH
C=O
(CH2)4 ~ C5Hll t
C5Hll-t . .
A solution of 8.1 g. (.05 mmol) 5-amino-1-naphthol,
6.1 g. (.05 mmol) N,N-dimethylaniline, and in 100 ml. tetrahydro-
furan was added dropwise at -10-0C to a solution of 12.1 g.
(.05 mmol) m-chlorosulfonylbenzoyl chloride in tetrahydrofuran
(200 ml.). The addition required 1 hour. The reaction was
nearly complete after the addition but was stirred at -10C
~or 2 hours, treated with .05 mole of Compound A, 4-amino-N-
~-4-(2,4-di-tert-pentylphenoxy)butyl]-1-hydroxy-2-naphthamide~
and .05 mole pyridine, and stirred at 25C until ~ompound A had
reacted. The reaction mixture was poured into 2 liters of
water and the dark oil which separated induced to crystallize by
adding 200 ml. 10~ hydrogen chloride solution. The crude product
was filtered, washed with water, and air dried to give 42.96 g.
of crude product (102~ yield). Recrystallization from 500 ml.
-43-
1~3886~a
boiling benzene gave, after filtration and a slow recrystalliza-
tion 39 g. of product 2 (92~) having m.p. 21~-219C with satis-
factory IR and NMR analyses. Next, a solution of 8.28 g. (.Ol
mol) Compound 2 in 4.0 g. 50~ sodium hydroxide solution and
50 ml. water was added at 0 to a solution of diazotized sulfanilic
acid (.O1 mol) prepared in the usual manner at 0C. Coupling
at 0C was conducted for 1 hour at pH 10 by proper adjustment
of the pH with sodium carbonate solution. The red solution was
acidified with 10~ hydrogen chloride solution, filtered, and
washed thoroughly with cold water. The crude dye-providing com-
pound weighed 9.24 g. (92~) when dried and was purified suffi-
clently for image transfer testing by repeated trituration from
boiling acetonitrile. After washing thoroughly with cold aceto-
nitrile and diethyl ether, it was thoroughly vacuum dried. The
resultant Compound 13 was tested as in Example 12A and the
transferred magenta dye image was found to have a Dmax of about
2.2.
Example 15 - Preparation of Compound No. 14
OH
N=N ~
NH S2-NH
52 ` ~ CONH-(CH2)4-o ~ C5H11 t
3 OH C5H
1~4
.
~ ~ .
~03~64
10.3 g. (.025 mol) of N-[5-hydroxy-6-(m-fluorosulfonyl-
phenylazo)-l-naphthyl~methanesulfonamide was added to 8.o g.
(.Og5 mol) of sodium bicar~onate and 12.2 g. (.025 mol) of
4-amino-N-~4-(2~4-di-tert-pentylphenoxy)butyl]-1-hydroxy-2-
naphthamide in 80 ml. of dimethylsulfoxide, under nitrogen. The
mixture was heated on a steam bath for ninety minutes and poured
into 1 liter of ice water containing 25 ml. of concentrated
hydrochloric acid. The solid was collected on a filter funnel
and dried. After one slurry in L~oO ml. of hot toluene and one
slurry in 100 ml. of acetic acid, the yield of dye was 12.0 g.
(55%). PREPARATION OF INTERMEDIATES: A cooled solutlon Of
2.0 g. (0.29 mol) of sodium nitrite ln 12 ml. of water was added
portionwise, at ~ 5C to a solution of 6.o5 g. (.029 mol) of
3-aminobenzenesulfonyl fluoride in 50 ml. of 10% hydrochloric
acid. This solution was added at 10C to a cooled solution of
6 .o8 g. ( .026 mol) of N-(5-hydroxy-1-naphthyl)methanesulfonamide
in 75 ml. of a mixture of 1 part by volume propionic acid to
5 parts acetic acid and 18 ml. of pyridine. The final solution
was stirred at < 10C for ninety minutes and poured into 1
liter of ice water. The pH of the aqueous solution was adjusted
to 2, the solid collected on a filter funnel and dried to yield
10.3 g. (93~). For the preparation of the above sulfonamide,
20.0 g. (.125 mol) of 5-amino-1-naphthol was dissolved in 63 ml.
of acetone cont~ining 10 ml. (.13 mol) of pyridine. To this
mixture 16.0 g. (.14 mol) of methanesulfonyl chloride was added
dropwise. The temperature gradually rose to 55C and solution
was effected. The solution was stirred for forty-five minutes
and poured into 650 ml. of water containing 15 g. ~.375 mol) of
sodium hydroxide. The temperature rose to 60C. The solution
30 was cooled, and acidified with concentrated hydrochloric acid.
The solid was collected on a filter funnel, washed with water,
and dried to yield 25.7 g. (87~), m.p. 1l~3-7C. Compound No. 1
-45-
1(~38~36~ ~
was tested as in Exa~ple 12C and found to have transferred dye
image densities of 1.86, 2.3 and 2.4 after 30, 60 and 120 seconds,
respectively.
Example 16
Dyes such as those released from the previously
discussed carriers (Car-) during alkaline processing were pre-
pared and dissolved in 30 ml. of a 0.5N sodium hydroxide solu-
tion containing 30 g/l of hydroxyethylcellulose~ Each solution
was spread between a cellulose acetate cover sheet and a receiving
10 element so that the alkaline dye composition was 0.1 mm thick.
The receiving element was as described in Example 12 only having
an additional layer o~ gelatin (43 mg/dm2) coated over the
carbon-gelatin layer. The spectra of the dyes when adsorbed
to the mordant were determined as in Example 12. The following
Table II shows the general formula of the dyes tested and the
. _ . . ... . . .
results obtained.
... . _ . . . . . . .
Table II
N= N ~ OH
1038~6~L
Table II (continued)
Z R El Q
4 S2NH2 H 5-S02NH2 8-NHCoCH3 531
3-S02NH2 H ~ ,. 522
4-So2NH2 2-Cl -'' 543
3-S02NH2 6-Cl " " 528
3-S02NH2 4-Cl " ~ 52
3-S02NH2 6-oCH3 " ~ - 519
2-S02NH2 H n 510
2-S02NHCH3 .. 538
4-So2NH(cocH3) H .~ . n 542
2 S2CH3 H n
4-CN H ~ n 550
2-CN H ~ ,. 549
" - 524
2-CF H:
3 " " 520
2-Cl H
4-so2~H2 H H 5-OH 571
20 3-S02NH2 H H " 55600
3-S02NH2 6-C1 532
3-S02NH2 H H 8-oH
4-So2NH2 H H 5 NHS02CH3 563
3-S02NH2 x H " 552
4-So2~H2 H 3-S02NH2 H . 518
3-S02NH2 H 6-S03Na 8-NHCoCH3 533
4-So2NH2 H 5-S03Na " 54
3-S02NH2 H 3-S02NH2 520
.
' ' ' ' '
- :~L03~864
Table II (continued)
_ Rl El Q ~ (nm)
: 4-So2NH2 2-C1 8-N~CoCH3 535
4-So2NH2 2-C1 3-SO~Na 5-NHCOCH3 53
3-S02N~I2 H H 8-~HS02CH3 517
4-So2NH2 ~ 5-so2N~ 8-~HCoCE3 533
; S2NH2
2-S02CH3 ~ 6-S2NH2 H 576
4-So2CH3 H 6-S2N~I2 H 576
.....
10 Example 17_- Preparatlon of Compo~d No. 15
OCO2CH2CH3 '
CONH(CH2)4-O ~ C5Hll t
S2 ~ S02NH C5Ell t
CH3
The above Compound 15 was prepared in a manner similar
to Example 15 only using N-~5-ethoxycarbonyloxy-6-(m-chloro-
sulfonylphenylazo)-l-naphthyl]methanesulfamide which was prepared
from the 5-hydroxy counterpart (made as in Example 15) by reac-
tion with ethyl chloroformate. Compound 15 was tested as in
Example 15 and found to have a A max in the coating of 440 nm
. and a ~ max of transferred dye of 555 nm and densities of 1.87
;~ ~30 seconds), 2.5 (60 seconds) and 2.6 (120 seconds).
I -48-
..
:
7 '~ . 1'.~
~L03~864
m e invention has been described in detail with par-
ticular reference to certain preferred embodiments thereof, but
it will be understood that variations and modifications can be
effected within the spirit and scope of the invention.
`:
_~9_
