CA1052613A - Process for producing color images - Google Patents
Process for producing color imagesInfo
- Publication number
- CA1052613A CA1052613A CA213,004A CA213004A CA1052613A CA 1052613 A CA1052613 A CA 1052613A CA 213004 A CA213004 A CA 213004A CA 1052613 A CA1052613 A CA 1052613A
- Authority
- CA
- Canada
- Prior art keywords
- dye
- silver halide
- hydroxy
- halide emulsion
- silver
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
- G03C8/02—Photosensitive materials characterised by the image-forming section
- G03C8/08—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/28—Silver dye bleach processes; Materials therefor; Preparing or processing such materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/156—Precursor compound
- Y10S430/159—Development dye releaser, DDR
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
Abstract
PROCESS FOR PRODUCING COLOR IMAGES
Abstract Color images are prepared by:
1) treating an imagewise exposed photosensitive element comprising a nondiffusible redox dye releaser, such as a p-sulfonamidoaniline or p-sulfonamidophenol which is alkali-cleavable upon oxidation to release a diffusible dye such as an azo dye, with processing composition to form an imagewise distribution of diffusible, bleachable dye which diffuses out of the element, 2) bleaching to decolorize any imagewise released dye which has not diffused out of the element, and 3) removing the metallic silver and silver halide.
Abstract Color images are prepared by:
1) treating an imagewise exposed photosensitive element comprising a nondiffusible redox dye releaser, such as a p-sulfonamidoaniline or p-sulfonamidophenol which is alkali-cleavable upon oxidation to release a diffusible dye such as an azo dye, with processing composition to form an imagewise distribution of diffusible, bleachable dye which diffuses out of the element, 2) bleaching to decolorize any imagewise released dye which has not diffused out of the element, and 3) removing the metallic silver and silver halide.
Description
105'~3 1`hii kl~erltlon l~el-jtes to p!lotogl~aphy, and more parti-cularl~; to color F)hoto~l~ap}ly ~mploying clye image-providing rnaterials comprising nondiffusible redox dye releasers such as r ~-su~fonamidoanilincs and ~-sulfonamidophenols which are alkali-cleava~le upon oxida-tion to release a diffusible, bleachable dye, such as an azo dye from the benzene nucleus. A silver-dye bleach bath is employed with such materials in ordcr to produce color images, such as a positive transparency or a motion-picture ~ilm.
The silver-dye bleach ~rocess has been known for many 10 years. Such a process employs a photographic material comprising at least one photosensitive silver halide emulsion layer which is associated with a preformed bleachable dye. A typical multicolor silver-dye bleach element is composed of three silver halide layers respectively sensitized to red, green, and blue radiation, and having associated therewith, respectively, a bleachable cyan, ~-magenta and yellow dye. The processing of such an element for obtaining a positive multicolored photographic reproduction generally includes exposing said element to a light pattern, developing it to a negative silver image in a black-and-white 20 silver halide developer solution, treating it in a dye bleach bath which oxidizes the silver image to a silver salt and concurrently decolorizes the associated pattern of dye, and, finally removing the residual silver salt by f`ixing and washing. A dye image is left which is photographically the inverse of the initial silver image. General descriptions of this well known silver-dye bleach process are found in U.S. Patent 3,498,787 of Wilson et al, issued March 3, 1970; U.S. Patent 3,414,411 of Michel et al, issued December 3, 1968; U.S. Patent 3,503,7L~l of Wilson et al, issued March 31, 1970; Canadian Patent 790,533 of Wilson et al, issued July 23, 1968; and an article entitled "Some Features of the
The silver-dye bleach ~rocess has been known for many 10 years. Such a process employs a photographic material comprising at least one photosensitive silver halide emulsion layer which is associated with a preformed bleachable dye. A typical multicolor silver-dye bleach element is composed of three silver halide layers respectively sensitized to red, green, and blue radiation, and having associated therewith, respectively, a bleachable cyan, ~-magenta and yellow dye. The processing of such an element for obtaining a positive multicolored photographic reproduction generally includes exposing said element to a light pattern, developing it to a negative silver image in a black-and-white 20 silver halide developer solution, treating it in a dye bleach bath which oxidizes the silver image to a silver salt and concurrently decolorizes the associated pattern of dye, and, finally removing the residual silver salt by f`ixing and washing. A dye image is left which is photographically the inverse of the initial silver image. General descriptions of this well known silver-dye bleach process are found in U.S. Patent 3,498,787 of Wilson et al, issued March 3, 1970; U.S. Patent 3,414,411 of Michel et al, issued December 3, 1968; U.S. Patent 3,503,7L~l of Wilson et al, issued March 31, 1970; Canadian Patent 790,533 of Wilson et al, issued July 23, 1968; and an article entitled "Some Features of the
- 2 - ~
-q~
. " . . . . . . . ..
105;~4~13 Silver-Dye Bleach Process" by A. Meyer, The Journal of Photo-graphic Science, Volume 13, 90-97 (1965).
Belgian Patents 788,268, issued February 28, 1973;
796,040, issued August 27, 1973; 796,041, issued August 27, 1973 and 796,042, issued August 27, 1973, relate to various nondiffusible ~-sulfonamidoanilines and _-sulfonamidophenols and their use in photographic elements containing such com-pounds. In a preferred embodiment of my invention, I have found that a color image, such as a positive transparency, may be obtained by employing certain of these compounds in photographic elements which are subjected to a silver-dye bleach process.
There is a disclosure in the above-mentioned Belgian Patent No. 788,268 of obtaining a color transparency by treating the residual dye image in a photographic element after an imagewise distribution of dye has diffused out of the element. There is no disclosure in this application, however, of employing a silver-dye bleach bath which I have found greatly enhances the color image which is obtained.
This is especially noticeable in greatly improved DminS which are obtained in accordance with the present invention.
~' 105;~ 3 ,1 According to my invention, a process for producing a co:Lor image comprises:
I) imagewise exposing a photosensitive element comprising a support having thereon at least one photosensitive silver halide emulsion layer, the emulsion layer having associated therewith a nondiffusible redox dye releaser;
II) treating the photosensitive element with an alkaline pro-cessing composition in the presence of a silver halide developing agent to effect development of each of the exposed silver halide emulsion layers, there~y oxidizing . the developing agent and formin~ a metallic silver image;
a) the oxidized developing agent thereby cross-oxidizing the redox dye releaser;
b) the oxidized redox dye releaser then cleaving, thus forming an imagewise distribution of diffusible dye : which diffuses out of said element;
III) bleaching the element to decolorize or destroy any imagewise-released dye which has not diffused out of said element; and IV) removing the metallic silver and silver halide from the element;
whereby a dye image is obtained in the element which is the reverse of said metallic silver image.
~ .
,,'~ , - .
., ~ . .
, . .
105;~613 The nondiffusible redox dye releasers useful in my invention are, generally speaking, compol~ds which will redox with oxidized developing agent to release a dye, such as by alkaline hydrolysis. Such redox dye releasers are described in U. S. Patent 3,725,062 of Anderson and Lum, issued Apr.il 3 1973; u. S. Patent 3~698~897 of Gompf and Lum, issued October 17 1972; u. S. Patent 3~628~952 of Puschel et al, issued December 21 1971; u. s. Patent 3~443~939 of Bloom et al, issùed May 13~ 1969;
U. S. Patent 3a443~94 of Bloom et al, issued May 13~ 1969;
and the following Belgian Patents: 788~268~ issued February 28~`
1973; 796,o40, issued August 27~ 1973; 796~041~ issued August 27 1973; and 796~042~ issued August 27~ 1973.
- In an especially preferred embodiment of my invention, .a process for producing a color image comprises:
I) imagewise exposing a photosensitive element comprising a support having thereon at least one photosensitive silver halide emulsion layer, the emulsion layer having associated therewith a nondiffusible ~-sulfonamidoaniline or P-sulfonamidophenol which is alkali-cleavable upon oxida-tion to release a diffusible dye from the be~zene nucleus and having formula I:
Ballast~
: wherein a) Z is a bleachable dye having a predominant spectral a.bsorption within the region of the visible ~5'~613 spect;Illm to WiliC}l the associa-ted silver halide emulsion :is sensitive or a dye precursor;
b) Ballast is an organic ballasting radical of such molccular size and configuration (e.g., simple organic groups or pol~neric groups) as to render the sulfonamido compound nondiffusible during develop-ment in an alkaline processing composition;
c) G is OR or NHRl wherein R is hydrogen or a h.ydrolyz-able moiety and ~1 is a hydrogen or a substituted or unsubsti.tuted alkyl group of 1 to 22 carbon atoms, such as methyl, ethyl, hydroxyethyl, propyl, butyl, secondary . butyl, tert-butyl cyclopropyl, 4-chlorobutyl, cyclobutyl, 4-nitroamyl, hexyl, cyclohexyl, octyl, decyl, octa-decyl, dodecyl, benzyl, phenethyl, etc., (when Rl is an alkyl group of greater than 6 carbon atoms, it can serve as a partial or sole Ballast group); and d) n is a positive integer of 1 to 2 and is 2 when G is OR or when Rl is hydrogen or an .alkyl group of less . than o carbon atoms;
II) treating the photosensitive element with an alkaline process-ing composition in the presence of a silver halide developin&
agent to: 1) cause any dye precursor present to become a . dye having a predominant spectral absorption wit`nin the :. region of the visible spectrum to which the associated silver halide emulsion is sensitive, the dye being bleach-able; and 2) to effect development of each of the exposed .. silver halide emulsion layers, thereby oxidizing the develop-ing a~ent and forming a metallic silver image;
:. a) the oxidized developing agent thereby cross-oxidizin~
: 30 the sulfonamido compound;
h) -the oxidized sulfon~nido compound then cleaving, thus . -- 6 --105;~613 i`ol~?lin~ al~ i!nage~:isc~ distril~ut;ion oï dlrl`usible dye which (liffll~,es out; Or t,he elemcnl,;
[11) ~leachlng the element to decolorize or destroy any imagewise-released dye ~JhLcll ilas no~ diffused out of said element;
a.ld LV) removing the metallic silver and silver halide from the element;
whereby a dye image is obtained in the element which is the reverse Or the metallic silver ima~e.
The photosensitive element in the above-described processes can be trcated with an alkaline processing composition to effect or initiate development in any manner. A preferred rnethod for applying processing compositionis by employing a bath which contains the composition. The alkaline composition could also be ernplo~tJed in a rupturable container such as those used in diffusion transfer processes. In that case, the composition is applied to the element by passing it and a spreader sheet through pressure-appl~ying mernbers to rupture the container and spread the composi-tion therebetween. In general, the processing composi-tion employed in my system contains the developing agent for development, although the cornposition could also just be an alkaline solution when -the developer is incorporated in the photosensitive elernent, in which case the alkaline solu-tion serves to activate the incorporated developer.
In the formula listed above for the compounds which are alkali-cleavable upon oxidation, R is preferably hydrogen, although it could be an~y hydrolyzable entity well~known to those skilled in the art, e.g., acetyl, mono-, di- or trichloroacetyl radicals, perfluoracyl, pyruvyl, alkoxyacyl, ni-trobenzoyl, cyanbenzoyl, 3o sulfonyl, sulfinyl, etc.
The nature Or the ballast group in the formula for the compounds described above (Ballast) is no-t critical as long as it 105J~613 confers nondiffusibility to the compounds. Typical ballast groups include long-chain alkyl radicals linked directly or in-directly to the compound as well as aromatic radicals of the t 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 substituted or unsubstituted alkyl group of 8 to 22 carbon atoms, an amide t~
radical having 8 to 30 carbon atoms, a keto radical having J
8 to 30 carbon atoms, etc, and may even comprise a polymer 10 backbone or a dye or dye precursor. Exemplary co.mpounds having such ballast groups are shown below.
NHRl NHRl ~= CH2=~ 1 ~S02-Z ~HS02-Z
G G
alkylen ~
~J _(6-12 carbon ~J
T atoms) T
NHS02_Z NHS02-Z , etc.
wherein G, Rl and Z have the same defin1tions as in the formula I above.
In addition to Ballast, the benzene nucleus in the above formula I may have groups or atoms attached thereto such as the halogens, alkyl, aryl, alkoxy, aryloxy, nitro, amine, alkylamino, aryl~mino, amido, cyano, alkylmercapto, keto, carboalkoxy, hetero-cyclic groups, etc. In addition, such groups may combine togetherwith the carbon atoms to which they are attached on the ring to form another ring which may be saturated or unsaturated including a carbocyclic ring, a heterocyclic ring, etc. Preferably an aromatic ring is directly fused to the benzene nucleus which would form, for example, a naphthol. Such a ~-sulfonamidonaphthol is ....... --. . . ~ . . _ .
~ 05;~613 ~onsidered to be a s~ecies of` a p-sulfonamidophenol and thus included within the definition. The same is true for p-sulfon-amidoanilines employed in the invention.
As previously mentioned, Z in the above formula I repre-sents a bleachable dye having a predominant spectral absorption within the region of the visible spectrum to which the associated silver halide emulsion is sensitive, or a dye precursor. Such bleachable dyes are preferably azo dyes although other bleachable dyes, such as formazan dyes described in U.S. Patent 3,503,741, would also be useful. Dye precursors can also be employed in my Ii invention so long as they provide a bleachable dye at some stage of the process, preferably during development. Dye precursor moieties which could be used include leuco dyes, "shifted" dyes which shift hypsochromically or bathochromically when subjected to a different environment such as a change in pH, reaction with a material to form a complex, etc. m ese compounds may contain a solubilizing group if desired. Examples of such dye groups include the fol3owing:
4-Hydroxy azobenzene , ~ - N=N ~ OH
~,
-q~
. " . . . . . . . ..
105;~4~13 Silver-Dye Bleach Process" by A. Meyer, The Journal of Photo-graphic Science, Volume 13, 90-97 (1965).
Belgian Patents 788,268, issued February 28, 1973;
796,040, issued August 27, 1973; 796,041, issued August 27, 1973 and 796,042, issued August 27, 1973, relate to various nondiffusible ~-sulfonamidoanilines and _-sulfonamidophenols and their use in photographic elements containing such com-pounds. In a preferred embodiment of my invention, I have found that a color image, such as a positive transparency, may be obtained by employing certain of these compounds in photographic elements which are subjected to a silver-dye bleach process.
There is a disclosure in the above-mentioned Belgian Patent No. 788,268 of obtaining a color transparency by treating the residual dye image in a photographic element after an imagewise distribution of dye has diffused out of the element. There is no disclosure in this application, however, of employing a silver-dye bleach bath which I have found greatly enhances the color image which is obtained.
This is especially noticeable in greatly improved DminS which are obtained in accordance with the present invention.
~' 105;~ 3 ,1 According to my invention, a process for producing a co:Lor image comprises:
I) imagewise exposing a photosensitive element comprising a support having thereon at least one photosensitive silver halide emulsion layer, the emulsion layer having associated therewith a nondiffusible redox dye releaser;
II) treating the photosensitive element with an alkaline pro-cessing composition in the presence of a silver halide developing agent to effect development of each of the exposed silver halide emulsion layers, there~y oxidizing . the developing agent and formin~ a metallic silver image;
a) the oxidized developing agent thereby cross-oxidizing the redox dye releaser;
b) the oxidized redox dye releaser then cleaving, thus forming an imagewise distribution of diffusible dye : which diffuses out of said element;
III) bleaching the element to decolorize or destroy any imagewise-released dye which has not diffused out of said element; and IV) removing the metallic silver and silver halide from the element;
whereby a dye image is obtained in the element which is the reverse of said metallic silver image.
~ .
,,'~ , - .
., ~ . .
, . .
105;~613 The nondiffusible redox dye releasers useful in my invention are, generally speaking, compol~ds which will redox with oxidized developing agent to release a dye, such as by alkaline hydrolysis. Such redox dye releasers are described in U. S. Patent 3,725,062 of Anderson and Lum, issued Apr.il 3 1973; u. S. Patent 3~698~897 of Gompf and Lum, issued October 17 1972; u. S. Patent 3~628~952 of Puschel et al, issued December 21 1971; u. s. Patent 3~443~939 of Bloom et al, issùed May 13~ 1969;
U. S. Patent 3a443~94 of Bloom et al, issued May 13~ 1969;
and the following Belgian Patents: 788~268~ issued February 28~`
1973; 796,o40, issued August 27~ 1973; 796~041~ issued August 27 1973; and 796~042~ issued August 27~ 1973.
- In an especially preferred embodiment of my invention, .a process for producing a color image comprises:
I) imagewise exposing a photosensitive element comprising a support having thereon at least one photosensitive silver halide emulsion layer, the emulsion layer having associated therewith a nondiffusible ~-sulfonamidoaniline or P-sulfonamidophenol which is alkali-cleavable upon oxida-tion to release a diffusible dye from the be~zene nucleus and having formula I:
Ballast~
: wherein a) Z is a bleachable dye having a predominant spectral a.bsorption within the region of the visible ~5'~613 spect;Illm to WiliC}l the associa-ted silver halide emulsion :is sensitive or a dye precursor;
b) Ballast is an organic ballasting radical of such molccular size and configuration (e.g., simple organic groups or pol~neric groups) as to render the sulfonamido compound nondiffusible during develop-ment in an alkaline processing composition;
c) G is OR or NHRl wherein R is hydrogen or a h.ydrolyz-able moiety and ~1 is a hydrogen or a substituted or unsubsti.tuted alkyl group of 1 to 22 carbon atoms, such as methyl, ethyl, hydroxyethyl, propyl, butyl, secondary . butyl, tert-butyl cyclopropyl, 4-chlorobutyl, cyclobutyl, 4-nitroamyl, hexyl, cyclohexyl, octyl, decyl, octa-decyl, dodecyl, benzyl, phenethyl, etc., (when Rl is an alkyl group of greater than 6 carbon atoms, it can serve as a partial or sole Ballast group); and d) n is a positive integer of 1 to 2 and is 2 when G is OR or when Rl is hydrogen or an .alkyl group of less . than o carbon atoms;
II) treating the photosensitive element with an alkaline process-ing composition in the presence of a silver halide developin&
agent to: 1) cause any dye precursor present to become a . dye having a predominant spectral absorption wit`nin the :. region of the visible spectrum to which the associated silver halide emulsion is sensitive, the dye being bleach-able; and 2) to effect development of each of the exposed .. silver halide emulsion layers, thereby oxidizing the develop-ing a~ent and forming a metallic silver image;
:. a) the oxidized developing agent thereby cross-oxidizin~
: 30 the sulfonamido compound;
h) -the oxidized sulfon~nido compound then cleaving, thus . -- 6 --105;~613 i`ol~?lin~ al~ i!nage~:isc~ distril~ut;ion oï dlrl`usible dye which (liffll~,es out; Or t,he elemcnl,;
[11) ~leachlng the element to decolorize or destroy any imagewise-released dye ~JhLcll ilas no~ diffused out of said element;
a.ld LV) removing the metallic silver and silver halide from the element;
whereby a dye image is obtained in the element which is the reverse Or the metallic silver ima~e.
The photosensitive element in the above-described processes can be trcated with an alkaline processing composition to effect or initiate development in any manner. A preferred rnethod for applying processing compositionis by employing a bath which contains the composition. The alkaline composition could also be ernplo~tJed in a rupturable container such as those used in diffusion transfer processes. In that case, the composition is applied to the element by passing it and a spreader sheet through pressure-appl~ying mernbers to rupture the container and spread the composi-tion therebetween. In general, the processing composi-tion employed in my system contains the developing agent for development, although the cornposition could also just be an alkaline solution when -the developer is incorporated in the photosensitive elernent, in which case the alkaline solu-tion serves to activate the incorporated developer.
In the formula listed above for the compounds which are alkali-cleavable upon oxidation, R is preferably hydrogen, although it could be an~y hydrolyzable entity well~known to those skilled in the art, e.g., acetyl, mono-, di- or trichloroacetyl radicals, perfluoracyl, pyruvyl, alkoxyacyl, ni-trobenzoyl, cyanbenzoyl, 3o sulfonyl, sulfinyl, etc.
The nature Or the ballast group in the formula for the compounds described above (Ballast) is no-t critical as long as it 105J~613 confers nondiffusibility to the compounds. Typical ballast groups include long-chain alkyl radicals linked directly or in-directly to the compound as well as aromatic radicals of the t 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 substituted or unsubstituted alkyl group of 8 to 22 carbon atoms, an amide t~
radical having 8 to 30 carbon atoms, a keto radical having J
8 to 30 carbon atoms, etc, and may even comprise a polymer 10 backbone or a dye or dye precursor. Exemplary co.mpounds having such ballast groups are shown below.
NHRl NHRl ~= CH2=~ 1 ~S02-Z ~HS02-Z
G G
alkylen ~
~J _(6-12 carbon ~J
T atoms) T
NHS02_Z NHS02-Z , etc.
wherein G, Rl and Z have the same defin1tions as in the formula I above.
In addition to Ballast, the benzene nucleus in the above formula I may have groups or atoms attached thereto such as the halogens, alkyl, aryl, alkoxy, aryloxy, nitro, amine, alkylamino, aryl~mino, amido, cyano, alkylmercapto, keto, carboalkoxy, hetero-cyclic groups, etc. In addition, such groups may combine togetherwith the carbon atoms to which they are attached on the ring to form another ring which may be saturated or unsaturated including a carbocyclic ring, a heterocyclic ring, etc. Preferably an aromatic ring is directly fused to the benzene nucleus which would form, for example, a naphthol. Such a ~-sulfonamidonaphthol is ....... --. . . ~ . . _ .
~ 05;~613 ~onsidered to be a s~ecies of` a p-sulfonamidophenol and thus included within the definition. The same is true for p-sulfon-amidoanilines employed in the invention.
As previously mentioned, Z in the above formula I repre-sents a bleachable dye having a predominant spectral absorption within the region of the visible spectrum to which the associated silver halide emulsion is sensitive, or a dye precursor. Such bleachable dyes are preferably azo dyes although other bleachable dyes, such as formazan dyes described in U.S. Patent 3,503,741, would also be useful. Dye precursors can also be employed in my Ii invention so long as they provide a bleachable dye at some stage of the process, preferably during development. Dye precursor moieties which could be used include leuco dyes, "shifted" dyes which shift hypsochromically or bathochromically when subjected to a different environment such as a change in pH, reaction with a material to form a complex, etc. m ese compounds may contain a solubilizing group if desired. Examples of such dye groups include the fol3owing:
4-Hydroxy azobenzene , ~ - N=N ~ OH
~,
3 methyl-4-hydroxy azobenzene ¦-HO ~ - N=N
p-sulfhydryl azobenzene HS ~ - N=N ~
!
_ 9 _ i __ . . ,. _ , . . ,. ;
:105~613 CZ~ ~ CH3 N--N ~
HO-C~I2 ~ --N=N ~ < C2~I5 ( CH2 ) 2-NH-S02-CH3 OH
llO ~ N=N ~
OCH(CH3)2 HO ~ N - Dl N
~ 3 When dye precursor moieties are employed in my invention instead of dyes, they are converted to dyes by means well-known to those skilled in the art, e.g., oxidation, either in the photosen-sitive element, in the processing composition or at some stage in the process to form a visible dye. Such techniques are disclosed, for example, in British Patents 1,157,501; 1,157,502; 1,157,503;
1,157,50~; 1,157,505; 1,157,506; 1,151,507; 1,157,508; 1,157,509;
1,157,510 and U.S. Patents 2,774,668; 2,698,798; 2,698,244;
2,661,293; 2,559,643; etc.
Expecially preferred compounds which can be employed in the process of my invention include the following:
105;~6i3 ' ~
~,mpound No. 1 4-[4-(3-chloro-4-hydroxyphenylazo)benzene-__ sulfonamido]-N-[4-(2,4-di-t-pentylphenoxy)butyl]-1-hydroxy-2-napthamide OH C~Hll CONH(CII2)L~-0 ~ 5 11 NHS02~ ~Cl Compound No. 2 N-[4-(2,4-di-t-pentylphenoxy3butyl]-1-hydroxy-4-~3-[4-ethoxycarbonyloxy-8-methanesulfonamido-1-naphthylazo]benzenesulfonamido~-2-naphthamide OH C~Hll t CoNH(cH2)4-o ~ C5H11 t NHS02 . OCOOC2H5 N=N ~
. 2 3 Compound No. 3 1-hydroxy-N-[4-(2,4-di-t-pentylphenoxy)-butyl ]-4-~3-[5-acetoxy-6-(2-methylsulfonyl-4-nitrophenylazo)-1-naphthylsulfamoyl]benzenesulfonamido~-2-naphthamide OH
CoNH(cH2)4o ~ 5 11 SO N=N ~ _ ~o ~ . ~
lOS;~ 3 Compound No. 4 N-[4-(2,4-di-t-pentylphenoxy)butyl]-1-hydroxy-4-~ S-hydroxy-6-(2-methylsulfonyl-4-nitrophenylazo)-l-naphthylsulfamoyl]benzenesulfonamido~-2-naphthamide ~H
CO~l(C~l2)~o ~ - C5Hll-t NHSO2 ~ S2~ N ~ _ NO2 OH
Compound No. 5 3-Pentadecyl-4-(p-phenylazobenzenesulfon-amido)phenol OH
: NHSO2 ~ - N=N- ~
Corn~ound No. 6 1-Hy~roxy-4-(p-phenylazobenzenesulfonamido)-2[~-(2,4-di-tert-amylphenoxy)-n-butyl]-naphtharnide OH C5Hll t ~ CoNH(cH2)4o ~ - C5Hll-t NHS02 ~--N=N--~
Compound No. 7 8-Acetamido-3,6-disulfo-2-~p-[(4-hydroxy-. .
2-pentadecyl)-phenylsulfamoyl]-phenylazo}-naphthol mono-pyridinium salt - A~
105;~ 3 OH
H3lCl5 ~ ~H ~COCH
SO3~' ~ _ [ ~ [
Compound No. 8 2-~p-14-Hydroxy-2-pentadecyl)-phenylsulfamoyl]-phenylaz~ -4-isopropoxynaphthol OH
H3lC15 _ ~ OH
NHSO2 ~ N=N ~
Corr,pound No. 9 4-~P- L4 ~ - (N,N-Dimethyl~mino)-phenylazo]-oenzenesulfonamido~-3-pentadecylphenol OH
H31C15 ~
NHS02 ~ N=N ~ < CH3 Compound No. 10 l-Hydroxy-4-[4-(l-hydroxy-4-isopropoxy-2-naphthylazo)-benzensulfonamido ]-2-l4-(2,4-di-tert-pentylphenoxy)-butyl~-naphthamide OH
~CCT~I(CLL2)L~o~ 5 11 N=l`T--~
OCH(CH3)2 ~ ~, i . , _ . . . _ _ _ - : ~
105;~613 Compound No. 11 1-Hydroxy-4-[3-(1-phenyl-3-methylcarbamyl-
p-sulfhydryl azobenzene HS ~ - N=N ~
!
_ 9 _ i __ . . ,. _ , . . ,. ;
:105~613 CZ~ ~ CH3 N--N ~
HO-C~I2 ~ --N=N ~ < C2~I5 ( CH2 ) 2-NH-S02-CH3 OH
llO ~ N=N ~
OCH(CH3)2 HO ~ N - Dl N
~ 3 When dye precursor moieties are employed in my invention instead of dyes, they are converted to dyes by means well-known to those skilled in the art, e.g., oxidation, either in the photosen-sitive element, in the processing composition or at some stage in the process to form a visible dye. Such techniques are disclosed, for example, in British Patents 1,157,501; 1,157,502; 1,157,503;
1,157,50~; 1,157,505; 1,157,506; 1,151,507; 1,157,508; 1,157,509;
1,157,510 and U.S. Patents 2,774,668; 2,698,798; 2,698,244;
2,661,293; 2,559,643; etc.
Expecially preferred compounds which can be employed in the process of my invention include the following:
105;~6i3 ' ~
~,mpound No. 1 4-[4-(3-chloro-4-hydroxyphenylazo)benzene-__ sulfonamido]-N-[4-(2,4-di-t-pentylphenoxy)butyl]-1-hydroxy-2-napthamide OH C~Hll CONH(CII2)L~-0 ~ 5 11 NHS02~ ~Cl Compound No. 2 N-[4-(2,4-di-t-pentylphenoxy3butyl]-1-hydroxy-4-~3-[4-ethoxycarbonyloxy-8-methanesulfonamido-1-naphthylazo]benzenesulfonamido~-2-naphthamide OH C~Hll t CoNH(cH2)4-o ~ C5H11 t NHS02 . OCOOC2H5 N=N ~
. 2 3 Compound No. 3 1-hydroxy-N-[4-(2,4-di-t-pentylphenoxy)-butyl ]-4-~3-[5-acetoxy-6-(2-methylsulfonyl-4-nitrophenylazo)-1-naphthylsulfamoyl]benzenesulfonamido~-2-naphthamide OH
CoNH(cH2)4o ~ 5 11 SO N=N ~ _ ~o ~ . ~
lOS;~ 3 Compound No. 4 N-[4-(2,4-di-t-pentylphenoxy)butyl]-1-hydroxy-4-~ S-hydroxy-6-(2-methylsulfonyl-4-nitrophenylazo)-l-naphthylsulfamoyl]benzenesulfonamido~-2-naphthamide ~H
CO~l(C~l2)~o ~ - C5Hll-t NHSO2 ~ S2~ N ~ _ NO2 OH
Compound No. 5 3-Pentadecyl-4-(p-phenylazobenzenesulfon-amido)phenol OH
: NHSO2 ~ - N=N- ~
Corn~ound No. 6 1-Hy~roxy-4-(p-phenylazobenzenesulfonamido)-2[~-(2,4-di-tert-amylphenoxy)-n-butyl]-naphtharnide OH C5Hll t ~ CoNH(cH2)4o ~ - C5Hll-t NHS02 ~--N=N--~
Compound No. 7 8-Acetamido-3,6-disulfo-2-~p-[(4-hydroxy-. .
2-pentadecyl)-phenylsulfamoyl]-phenylazo}-naphthol mono-pyridinium salt - A~
105;~ 3 OH
H3lCl5 ~ ~H ~COCH
SO3~' ~ _ [ ~ [
Compound No. 8 2-~p-14-Hydroxy-2-pentadecyl)-phenylsulfamoyl]-phenylaz~ -4-isopropoxynaphthol OH
H3lC15 _ ~ OH
NHSO2 ~ N=N ~
Corr,pound No. 9 4-~P- L4 ~ - (N,N-Dimethyl~mino)-phenylazo]-oenzenesulfonamido~-3-pentadecylphenol OH
H31C15 ~
NHS02 ~ N=N ~ < CH3 Compound No. 10 l-Hydroxy-4-[4-(l-hydroxy-4-isopropoxy-2-naphthylazo)-benzensulfonamido ]-2-l4-(2,4-di-tert-pentylphenoxy)-butyl~-naphthamide OH
~CCT~I(CLL2)L~o~ 5 11 N=l`T--~
OCH(CH3)2 ~ ~, i . , _ . . . _ _ _ - : ~
105;~613 Compound No. 11 1-Hydroxy-4-[3-(1-phenyl-3-methylcarbamyl-
4-pyrazolin-5-onylazo)-benzenesulfonamido]-2-[4-(2,4-di-tert-pentylphenoxy)-butyl]-naphthamide OH
- co~r~l(CH2)40 ~ - C5Hll t [~LN=N~
N
Compound Mo. 12 4-[p-(4'-Dimethylaminophenylazo)-benzene-sulfonamido]-N-n-dodecylaniline H N C12H25 n , ~ .
NHSO2 ~ N=N ~ N(CH3)2 Compound Mo. 13 3-Pentadecyl-4-(p-phenylazobenzenesul-.
: fonanido)-aniline N~I2 31 15 ~ HSO - ~ - N=N ~
: Com~ound No. 14 1-(N-n-Dodecylamino)-4-(p-phenylazo-benzenesulfonamido)-naphthalene H~MC12H25~n ; I~SO2 ~ - N=N
- 105'~613 Comnoun~l llc)._:l5 2-~p-[(~l-c~nirlo-2-pentadecyl)-berlzen sulf~myl~-phenylazo~-4-isopropoxynaphthol r!~l2 3l 15 ~'~ISO ~ - N=N- ~
OCH(CH3)2 Compound No. 16 4-~p-[4'-(N',N'-dimethylamino)-phenylazo]-benzenesulronamido~-3-octyl-N-ethylaniline ; NHSO2- ~ N=N - ~ N(CH3)2 Compound No. 17 5-{p-[4'-(N,N-Dimethylamino)-phenylazo]-benzenesulfonamido}-8-(N'-n-dodecylamino)-quinoline NHSO2 ~ - N=N ~ - N(CH3)2 Compound No. 18 Yellow Dye-Releasin~
- OH
~ : ~ CONH(CH2)40 ~ C5Hll t : NHSO2 C5 11 t N,N -N
. CONHCH3 .
- ~05~613 Com~ound No. lc3 ~'F~erlta D~ye-l~eleasin~
OH
[~--CONlI(CH2)40~)--C5Hll-t NHS02- ~ 5 11 t ,~
\NHSO
- N=N
¦ OH
NHCOCH~ -Corn~ound No. 20 Magenta Dye-Releasing : ()H
CCONH(cH2)40 ~ - C5Hll-t NHS02- ~ C5Hll t .
;` ' ~< ' O OCH
C N=N ~
Compound No. 21 Magenta Dye-Releas ng OH
4 ~ 5 11 t Of the above compounds, especially good results are obtained with Compound Nos. 1-4.
The process of the present invention may be used to produce positive ima~es in single- or multicolors. In a three-. . . . . . . . _ _ _ - .
- ~OS~6~3 '`OlOI` ~ ;e`n~ i`aCil :~:i l'Jci` il.ll..ide elllU.lSiO!I !a.yer of` ~he l~not;o-; n itive e-~ e-~1.t will have associa'~ecl ther~Witil in an es~?ecially pre~.erre(l cm~odi~ent of my invelltioll a sulfonamido compound ilerein ~he (~/e possesses a predcrllinant spectral absorption within ~he re~ o~ ~he visible sl?ec-tIum to which said silver halide emulsiorl is ellsi~ive, i.e., the blue-sensitive silver halide emu:lslon layer will have a yellow sulfonarnido cornpound associated therewith, the green-sensitive sllver llalide emulsiorl layer will have a magellt3 sullonamido compound associated therewith, and the red-sensitive silver halide emulsion layer will have a cyan sulfonamido compound associated therewith. The sulf`onamido compound associated with each silver halide emulsion layer may be contained either in the silver halide emulsion layer itself or in a layer contiguous the silver halide emulsion layer.
The concentration of the sulfonarnido cornpounds, which are alkali-cleavaole upon oxidation, employed in a preferred process of the present invention rnay be varied over a wide range depending upon the particular compound employed and the results which are desired. For example, the sulfonamido compounds employed in the present invention may be coated in layers by using coating solutions containing between about 0.5 and about 8 percent by weight of the sulfonamido cornpound distributed in a hydrophilic Iilrn-forming natural material or synthetic polymer, such as gelatin, polyvinyl alcohol, etc., which is adapted to be permeated by an aqueous alkaline processing composition.
Any sllver halide developing agent can be employed in the process Or my invention as long as it cross-oxidizes with the redox dye releaser compounds descr:ibed hereirl. The developer may be employed in the photosensitive element to be activated by the alkaline processing composition. Specific exalnples of developers which can be employed in my invention include:
. . _ . _ . . .
1052~13 ` t,~ly 1 r.lln i.!lO~ llOi.
0~ }~ yl-3- ~ ra.701 i.<lolle ) i):iniezonc (L-~henyl-~ l-dimetllyl-3-py~a~olidoIle) ~,i`l,1`,',i~'-tetramethyl-~-phellylellediàmine p~len 1 S
'~r~ ?~-cli.~ vl n-,~henylen~diatnine 3-rnethyl-r~,~!-diethyl-p-phenylenediamille 3-methoxy-N-ethyl-N-ethoxy-p-phenylenediamine, etc.
'~he ~laclr-and-~1hite develo2ers in this list are preferred, how-ever, since they usually develop the emulsion faster.
The alkaline processing composition employed in the ~rocess of this invention is the conventional aqueous solution of an alkaline material, e.~., sodium hydroxide, sodium carbonate, an amine such as diethylamine, potassium hydroxide, etc.;
preferably possessing a pH in excess of 12 and preferably con-taining a developin~ agent as described above. If desired, a thickener can be added to the processing composition to increase the viscosity of the composition and make it more adaptable for continuous processing. The viscous composition can then be removed ~y squeegeeing or water spraying.
The dye-bleach bath employed in the process of my inven-tion is composed of any of the conventional materials heretofore used for such purpose. Reference is made, for example, to the materials d:isclosed in U.S. Patents 3,41l~,411; 3,503,741;
. , .
3,498,78~ and Canadian Patent 790,533 referred to above. A
catalyst is usually employed in such a bath such as a phenazine, a quinoxaline or an anthraquinone. Other catalysts are disclosed in U.S. Patents 2,183,395 and 2,270,118. The catalyst may be incorporated in the emulsion, the alkaline processing composition, the dyc-~leach bath, etc. These compounds bleach (i.e., oxidize) the me-taIlic silver to silver ion and, in so doing, are reduced.
The reduced catalyst then reduces the image dye. This redox reaction decolorizes the image dye and oxidizes the catalyst back to its original state.
. _ . .. . . . . . ._ . _ ,.
~ `
iOS'~t;i3 The removal of metallic silver and silver halide from a photographic element is accomplished by employing a conventional bleach bath, fix bath, bleach-fix bath, etc. These materials are well known to those skilled in the art; e.g., Kodak F-5 Fix bath, ferric ethylenediamine tetraacetic acid and ammonium thiosulfate bleach-fix bath, etc. Other bleach baths are disclosed in U.S.
Patents 1,315,464; 1,946,640; 3,342,589; J.S. Mot. Pict. Eng., 17, 1931 (pp 1023-1027); and other bleach-fix baths are disclosed in German Patent 866,605 and U.S. Patents 2,748,000 and 3,706,561.
It is also possible in accordance with my invention to combine the dye-bleach step with the bleach-fix step. This reduces the number of separate steps involved in processing and is quite advantageous. In such a case, a competing oxidant is employed such as Taylor yellow dye:
0 I~la ',0 I;~
3~ [ 3 SG31~a In accordance with the process of my invention, the film unit is exposed and the alkaline processing composition is applied to the film unit. The processing composition then per-meates the various layers to initiate development of the exposed photosensitive silver halide emulsion layers. The developing agent develops each of the silver halide emulsion layers in the exposed areas, reducing silver halide to silver metal, and causing the developing agent to become oxidized imagewise. The oxidized developing agent then cross-oxidizes the redox dye releaser com-pounds, the oxidized ~orm of which undergoes a base-catalyzed .., ~
reaction to ~clelse the pl~eforlned clyes or ~he d~e ~recursors ima~,e~.iise as a ~unction o~ the imagewise ex~osure of eacll of the silver halide emulsion layers. At least a portion of the imagrewise distributions of diffusible dyes or dye precursors ~1rruses out of ~he photogra~hic element. The diffusible moiety is transferable in the alkaline processlng composition either by virtue of its self-dii'fusivity or by having attached to it one or morc solubilizing groups such as COOI-I, S03H, OH, SH, etc.
The process of my inventlon is readi]y adaptable to a difiusion transfer format and such is considered to be within the scope of my invention. In such an application, the vàrious materials employed in the processing steps described herein can be employed in rupturable containers or incorporated in the photosensitive element or spreader sheet. The various process steps of rny invention may thus be combined or performed in a different order than that set out above. In such a format, the diff'usible dye which diffuses out of the element would be I deposited on an image-receiving sheet which may or may not be I the ~Ime as the spreader shcet mentioned above. This image-receiving sheet would then be peeled apart from the rest of the film unit so that the positive dye image in the photographic element may be vie~led.
The various silver halide emulsion layers of a color film assembly employed in the process 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, - followed by the green-sensitive and red-sensitive silver halide emulsion layers. lf desired, a yellow dye layer or a Carey Lea silver layer can be present between the blue-sensitive and green-sensitive silver halide emulsion layer for absorbing or filter-ing blue radlation that may be transmitted through the blue-, ~
., ~ .
105'~6i3 S~ LVC L;~CI~. Ir ~l~sire(l~ the selectively sensitized silver ilali~e emulsiol~ layers can be disposed in a differerlt order, e.g., the blue-sensitive layer first with respect to the exposure side, follo-led by l he red-sensitive and green-sensitive layers.
The silver halide emulsions used in this invention are the convelltional, ne~ative-working silver halide emulsions and com-prise, for example, silver chloride, silver bromide, silver chloro-bromide, silver bromoiodide, silver chlorobromoiodide or mixtures thereof. The emuls:ions 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 3,320,069 issued May 16, 1967; and McBride U.S. Patent 3,271,157 issued September 6, 1966. The emulsions may bc regular-grain emulsions such as the type described in Klein and Moisar, J. ~hot. Sci., Vol. 12, No. 5, Sept./Oct., 1964 (pp 242-251).
The supports for the photographic elements employed in the process of this inventlon can be any material as long as it does not deleteriously effect the photographic properties of the film unit and is dimensionally stable. For positive trans-parencies and cine film, transparent supports are preferred such as cellulose nitrate film, cellulose acetate film, poly-(vinyl acetal)-film, polystyrene film, poly(ethylenetereph-thalate) film, polycarbonate film, poly-~-olefins such as polyethylene and polypropylene film, and related filrns or resinous materials.
The support is usually about 2 to 6 rnils in thickness.
~ .
~' , .
,: - . . . . ~ . :
105;~3 The silver halide emulsions use~ul in the process of my invention are well known to those skilled in the art and are described in Product Licensing Index, Vol. 92, December, 1971, pub:lication 9232, p. 107, paragraph I, "Emulsion types"; they may be chemically and spectrally sensitized as described on p. 107, paragraph III, "Chemical sensitization", and pp. 108-109, paragraph XV, "Spectral sensit'zation", of the above article;
they can be protected against the production of fog and can be stabilized against loss of sensitivity during keeping by employ- ' ing the materials described on p. 107, paragraph V, "Antifoggants and stabilizers", of the above article; they can contain develop-ment modifiers, hardeners, and coating aids as described on pp.
107-108, paragraph IV, "Development modifiers"; paragraph VII, "Hardeners"; and paragraph XII, "Coating aids", of the above artlcle; 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, "Vehicles", and p. 109, paragraph XVI, "Absorbing and filter dyes", of the above article; -they and other layers in the photographic elements used in this invention may 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 XVIII, ~ "Coating procedures't, of the above article.
; The following examples illustrate the process of the invention.
~' 105'~f~13 EXAM~PLE I
A multilayer, multicolor photographic element is prepared by coating the following layers in the order recited on a transparent cellulose acetate film support: ¦
1) red-sensitive, negative-working, gelatin-silver bromide emulsion (21.5 mg gelatin/dm2 and 10.8 mg silver/dm2) and compound 4 (15.1 mg/dm2 which is 1.3 x 10 4M);
2) interlayer of gelatin (10.8 mg/dm2), developing agent - 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone (1.1 mg/dm2) and 2,5-di-sec-dodecylhydroquinone (10.8 mg/dm2);
3) green-sensitive, negative-working, gelatin-silver bromide emulsion (21.5 mg gelatin/dm2 and 10.8 mg silver/dm2), compound 2 (13.5 mg/dm2 which is 1.3 x 10 4M) and diethyl lauramide (13.5 mg/dm2);
4) interlayer of gelatin (10.8 mg/dm2), developing agent 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone (1.1 mg/dm2), 2,5-di-sec-dodecylhydroquinone (10.8 mg/dm2) and Carey Lea Silver (1.1 mg/dm2);
- co~r~l(CH2)40 ~ - C5Hll t [~LN=N~
N
Compound Mo. 12 4-[p-(4'-Dimethylaminophenylazo)-benzene-sulfonamido]-N-n-dodecylaniline H N C12H25 n , ~ .
NHSO2 ~ N=N ~ N(CH3)2 Compound Mo. 13 3-Pentadecyl-4-(p-phenylazobenzenesul-.
: fonanido)-aniline N~I2 31 15 ~ HSO - ~ - N=N ~
: Com~ound No. 14 1-(N-n-Dodecylamino)-4-(p-phenylazo-benzenesulfonamido)-naphthalene H~MC12H25~n ; I~SO2 ~ - N=N
- 105'~613 Comnoun~l llc)._:l5 2-~p-[(~l-c~nirlo-2-pentadecyl)-berlzen sulf~myl~-phenylazo~-4-isopropoxynaphthol r!~l2 3l 15 ~'~ISO ~ - N=N- ~
OCH(CH3)2 Compound No. 16 4-~p-[4'-(N',N'-dimethylamino)-phenylazo]-benzenesulronamido~-3-octyl-N-ethylaniline ; NHSO2- ~ N=N - ~ N(CH3)2 Compound No. 17 5-{p-[4'-(N,N-Dimethylamino)-phenylazo]-benzenesulfonamido}-8-(N'-n-dodecylamino)-quinoline NHSO2 ~ - N=N ~ - N(CH3)2 Compound No. 18 Yellow Dye-Releasin~
- OH
~ : ~ CONH(CH2)40 ~ C5Hll t : NHSO2 C5 11 t N,N -N
. CONHCH3 .
- ~05~613 Com~ound No. lc3 ~'F~erlta D~ye-l~eleasin~
OH
[~--CONlI(CH2)40~)--C5Hll-t NHS02- ~ 5 11 t ,~
\NHSO
- N=N
¦ OH
NHCOCH~ -Corn~ound No. 20 Magenta Dye-Releasing : ()H
CCONH(cH2)40 ~ - C5Hll-t NHS02- ~ C5Hll t .
;` ' ~< ' O OCH
C N=N ~
Compound No. 21 Magenta Dye-Releas ng OH
4 ~ 5 11 t Of the above compounds, especially good results are obtained with Compound Nos. 1-4.
The process of the present invention may be used to produce positive ima~es in single- or multicolors. In a three-. . . . . . . . _ _ _ - .
- ~OS~6~3 '`OlOI` ~ ;e`n~ i`aCil :~:i l'Jci` il.ll..ide elllU.lSiO!I !a.yer of` ~he l~not;o-; n itive e-~ e-~1.t will have associa'~ecl ther~Witil in an es~?ecially pre~.erre(l cm~odi~ent of my invelltioll a sulfonamido compound ilerein ~he (~/e possesses a predcrllinant spectral absorption within ~he re~ o~ ~he visible sl?ec-tIum to which said silver halide emulsiorl is ellsi~ive, i.e., the blue-sensitive silver halide emu:lslon layer will have a yellow sulfonarnido cornpound associated therewith, the green-sensitive sllver llalide emulsiorl layer will have a magellt3 sullonamido compound associated therewith, and the red-sensitive silver halide emulsion layer will have a cyan sulfonamido compound associated therewith. The sulf`onamido compound associated with each silver halide emulsion layer may be contained either in the silver halide emulsion layer itself or in a layer contiguous the silver halide emulsion layer.
The concentration of the sulfonarnido cornpounds, which are alkali-cleavaole upon oxidation, employed in a preferred process of the present invention rnay be varied over a wide range depending upon the particular compound employed and the results which are desired. For example, the sulfonamido compounds employed in the present invention may be coated in layers by using coating solutions containing between about 0.5 and about 8 percent by weight of the sulfonamido cornpound distributed in a hydrophilic Iilrn-forming natural material or synthetic polymer, such as gelatin, polyvinyl alcohol, etc., which is adapted to be permeated by an aqueous alkaline processing composition.
Any sllver halide developing agent can be employed in the process Or my invention as long as it cross-oxidizes with the redox dye releaser compounds descr:ibed hereirl. The developer may be employed in the photosensitive element to be activated by the alkaline processing composition. Specific exalnples of developers which can be employed in my invention include:
. . _ . _ . . .
1052~13 ` t,~ly 1 r.lln i.!lO~ llOi.
0~ }~ yl-3- ~ ra.701 i.<lolle ) i):iniezonc (L-~henyl-~ l-dimetllyl-3-py~a~olidoIle) ~,i`l,1`,',i~'-tetramethyl-~-phellylellediàmine p~len 1 S
'~r~ ?~-cli.~ vl n-,~henylen~diatnine 3-rnethyl-r~,~!-diethyl-p-phenylenediamille 3-methoxy-N-ethyl-N-ethoxy-p-phenylenediamine, etc.
'~he ~laclr-and-~1hite develo2ers in this list are preferred, how-ever, since they usually develop the emulsion faster.
The alkaline processing composition employed in the ~rocess of this invention is the conventional aqueous solution of an alkaline material, e.~., sodium hydroxide, sodium carbonate, an amine such as diethylamine, potassium hydroxide, etc.;
preferably possessing a pH in excess of 12 and preferably con-taining a developin~ agent as described above. If desired, a thickener can be added to the processing composition to increase the viscosity of the composition and make it more adaptable for continuous processing. The viscous composition can then be removed ~y squeegeeing or water spraying.
The dye-bleach bath employed in the process of my inven-tion is composed of any of the conventional materials heretofore used for such purpose. Reference is made, for example, to the materials d:isclosed in U.S. Patents 3,41l~,411; 3,503,741;
. , .
3,498,78~ and Canadian Patent 790,533 referred to above. A
catalyst is usually employed in such a bath such as a phenazine, a quinoxaline or an anthraquinone. Other catalysts are disclosed in U.S. Patents 2,183,395 and 2,270,118. The catalyst may be incorporated in the emulsion, the alkaline processing composition, the dyc-~leach bath, etc. These compounds bleach (i.e., oxidize) the me-taIlic silver to silver ion and, in so doing, are reduced.
The reduced catalyst then reduces the image dye. This redox reaction decolorizes the image dye and oxidizes the catalyst back to its original state.
. _ . .. . . . . . ._ . _ ,.
~ `
iOS'~t;i3 The removal of metallic silver and silver halide from a photographic element is accomplished by employing a conventional bleach bath, fix bath, bleach-fix bath, etc. These materials are well known to those skilled in the art; e.g., Kodak F-5 Fix bath, ferric ethylenediamine tetraacetic acid and ammonium thiosulfate bleach-fix bath, etc. Other bleach baths are disclosed in U.S.
Patents 1,315,464; 1,946,640; 3,342,589; J.S. Mot. Pict. Eng., 17, 1931 (pp 1023-1027); and other bleach-fix baths are disclosed in German Patent 866,605 and U.S. Patents 2,748,000 and 3,706,561.
It is also possible in accordance with my invention to combine the dye-bleach step with the bleach-fix step. This reduces the number of separate steps involved in processing and is quite advantageous. In such a case, a competing oxidant is employed such as Taylor yellow dye:
0 I~la ',0 I;~
3~ [ 3 SG31~a In accordance with the process of my invention, the film unit is exposed and the alkaline processing composition is applied to the film unit. The processing composition then per-meates the various layers to initiate development of the exposed photosensitive silver halide emulsion layers. The developing agent develops each of the silver halide emulsion layers in the exposed areas, reducing silver halide to silver metal, and causing the developing agent to become oxidized imagewise. The oxidized developing agent then cross-oxidizes the redox dye releaser com-pounds, the oxidized ~orm of which undergoes a base-catalyzed .., ~
reaction to ~clelse the pl~eforlned clyes or ~he d~e ~recursors ima~,e~.iise as a ~unction o~ the imagewise ex~osure of eacll of the silver halide emulsion layers. At least a portion of the imagrewise distributions of diffusible dyes or dye precursors ~1rruses out of ~he photogra~hic element. The diffusible moiety is transferable in the alkaline processlng composition either by virtue of its self-dii'fusivity or by having attached to it one or morc solubilizing groups such as COOI-I, S03H, OH, SH, etc.
The process of my inventlon is readi]y adaptable to a difiusion transfer format and such is considered to be within the scope of my invention. In such an application, the vàrious materials employed in the processing steps described herein can be employed in rupturable containers or incorporated in the photosensitive element or spreader sheet. The various process steps of rny invention may thus be combined or performed in a different order than that set out above. In such a format, the diff'usible dye which diffuses out of the element would be I deposited on an image-receiving sheet which may or may not be I the ~Ime as the spreader shcet mentioned above. This image-receiving sheet would then be peeled apart from the rest of the film unit so that the positive dye image in the photographic element may be vie~led.
The various silver halide emulsion layers of a color film assembly employed in the process 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, - followed by the green-sensitive and red-sensitive silver halide emulsion layers. lf desired, a yellow dye layer or a Carey Lea silver layer can be present between the blue-sensitive and green-sensitive silver halide emulsion layer for absorbing or filter-ing blue radlation that may be transmitted through the blue-, ~
., ~ .
105'~6i3 S~ LVC L;~CI~. Ir ~l~sire(l~ the selectively sensitized silver ilali~e emulsiol~ layers can be disposed in a differerlt order, e.g., the blue-sensitive layer first with respect to the exposure side, follo-led by l he red-sensitive and green-sensitive layers.
The silver halide emulsions used in this invention are the convelltional, ne~ative-working silver halide emulsions and com-prise, for example, silver chloride, silver bromide, silver chloro-bromide, silver bromoiodide, silver chlorobromoiodide or mixtures thereof. The emuls:ions 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 3,320,069 issued May 16, 1967; and McBride U.S. Patent 3,271,157 issued September 6, 1966. The emulsions may bc regular-grain emulsions such as the type described in Klein and Moisar, J. ~hot. Sci., Vol. 12, No. 5, Sept./Oct., 1964 (pp 242-251).
The supports for the photographic elements employed in the process of this inventlon can be any material as long as it does not deleteriously effect the photographic properties of the film unit and is dimensionally stable. For positive trans-parencies and cine film, transparent supports are preferred such as cellulose nitrate film, cellulose acetate film, poly-(vinyl acetal)-film, polystyrene film, poly(ethylenetereph-thalate) film, polycarbonate film, poly-~-olefins such as polyethylene and polypropylene film, and related filrns or resinous materials.
The support is usually about 2 to 6 rnils in thickness.
~ .
~' , .
,: - . . . . ~ . :
105;~3 The silver halide emulsions use~ul in the process of my invention are well known to those skilled in the art and are described in Product Licensing Index, Vol. 92, December, 1971, pub:lication 9232, p. 107, paragraph I, "Emulsion types"; they may be chemically and spectrally sensitized as described on p. 107, paragraph III, "Chemical sensitization", and pp. 108-109, paragraph XV, "Spectral sensit'zation", of the above article;
they can be protected against the production of fog and can be stabilized against loss of sensitivity during keeping by employ- ' ing the materials described on p. 107, paragraph V, "Antifoggants and stabilizers", of the above article; they can contain develop-ment modifiers, hardeners, and coating aids as described on pp.
107-108, paragraph IV, "Development modifiers"; paragraph VII, "Hardeners"; and paragraph XII, "Coating aids", of the above artlcle; 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, "Vehicles", and p. 109, paragraph XVI, "Absorbing and filter dyes", of the above article; -they and other layers in the photographic elements used in this invention may 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 XVIII, ~ "Coating procedures't, of the above article.
; The following examples illustrate the process of the invention.
~' 105'~f~13 EXAM~PLE I
A multilayer, multicolor photographic element is prepared by coating the following layers in the order recited on a transparent cellulose acetate film support: ¦
1) red-sensitive, negative-working, gelatin-silver bromide emulsion (21.5 mg gelatin/dm2 and 10.8 mg silver/dm2) and compound 4 (15.1 mg/dm2 which is 1.3 x 10 4M);
2) interlayer of gelatin (10.8 mg/dm2), developing agent - 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone (1.1 mg/dm2) and 2,5-di-sec-dodecylhydroquinone (10.8 mg/dm2);
3) green-sensitive, negative-working, gelatin-silver bromide emulsion (21.5 mg gelatin/dm2 and 10.8 mg silver/dm2), compound 2 (13.5 mg/dm2 which is 1.3 x 10 4M) and diethyl lauramide (13.5 mg/dm2);
4) interlayer of gelatin (10.8 mg/dm2), developing agent 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone (1.1 mg/dm2), 2,5-di-sec-dodecylhydroquinone (10.8 mg/dm2) and Carey Lea Silver (1.1 mg/dm2);
5) blue-sensitive, negative-working, gelatin-silver bromide emulsion (21.5 mg gelatin/dm2 and 10.8 mg silver/dm2), - compound 1 (11 mg/dm2 which is 1.3 x 10 4M) and diethyl lauramide (11 mg/dm2); and
6) overcoat of gelatin (8.6 mg/dm2).
Samples of the above prepared element are exposed on an Eastman lb (Trademark) sensitometer using an exposure chart ; which allows additive red, green and blue exposures to achieve ; complete color separation. The exposure conditions are:
a) red light for one second~ b) blue light for 1/10 second, - and c) green light ~or 1/10 second. One sample of the exposed element is then processed as follows:
. _..... . .
-` 105~613 1) Development - ore min~ il 37'.~(, by e;n})lo~vi~ ,lle followirlG
~ctivator:
NaOH 20 g r 10 ~
Phenylmercaptotetrazole0.03 g Water to one liter 2) I-~ix - one min. ~ 22.2~ with Kodak 1~`-5 rix bath:
Soclium thiosulfate 240 g Sodium sulfite 15 g Acetic acid (28~) 48 ml Boric acid (crystals) 7.5 g ~otassium aluminum sulfate 15 g Water to one liter ,~
3) Dye_Bleach - 30 sec. @ 37.~C with:
12.1 N HCl 100 ml Th:iourea 100 g Phenazine ~.2 g Water to one liter 4) Bleach-Fix - one min. @ 37.8C with a conventional ferric 20 ethylenediamine tetracetic acid and al~nonium thiosulfate , bleach-fix bath 5) Stabilizer Rinse - ten sec. @ 22.2C with:
Na2C3 50 g/l Cetyl trimethylammonium bromide 5.0 g/l 6) Dry.
A second sample of the exposed element is processed in the same manner except that the Dye Bleach bath (step 3) is omitted. The following sensitometric results are obtained:
DENSITIES
Wi-th D,ye-Bleach ~,ath Without Dye-Bleach Bath Exposure Red Green Blue Ke~ ~reen Blue , Cyan 3.'34 .~5 ~ L~ .12 '1.10 1.32 ,, Magenta o.36 1.51 1.09 1.48 2.31 1.62 Yellow 0.18 0.47 2.09 1.27 o.85 2.25 Red 0.27 2.28 2.68 1.11 2.72 3. ol~
Green 3.33 0.98 2.32 3 98 l.2Ll 2.51 - Blue 3.36 2.2L~ 1.27 4.05 2.68 1.72 , D 0.25 0.28 0.75 1.57 0.82 1-39 Neutral Drmnax 3.43 3.23 3.07 4.00 3.20 3.07 ; 40 The above results reveal a significant improvement ,in Dmin witllout adversely affecting DrnaX when the dye-bleach bath is em~loyecl.
, ~ . .. .
iOS~13 ~XAM~L~
-A second multilayer, multicolor,,photographic element is pr~epared similar to Ex,~mple I except that compound 4 is replaced Wit~l compound 3 at an equimolar amount in layer 1. me eleme,nt is exposed and processed as in Example I except that the Dye_Bleach treatment of step 3 is for two minutes. The follow- i ing sensitometric results are obtained: ¦-DENSITIES
With D,ye-Bleach Bath Without Dye-~leach Bath 10 Exposure Red Green Blue RedGreen Blue Cyan 3~ i.l4 -1.0~ 3 '74-1.51 Magenta 0.41 1. 70 1.171: 65 2.23 1.73 Yellow 0. 25 o .48 2.341 49 1. og 2.59 i Red o.36 2.67 3.11 1 2~2.81 3.25 Green 3.60 1.46 2.81 3.601.70 2.80 Blue 3.60 2.56 1.36 3.682.78 1.69 N t 1 Dmin - 31 o .36 o .84 1.801.18 1.48 eu ra Dmax 3 65 3.50 3.363.68 3.60 3.5I
As in Example I, the above results reveal a signi-ficant improvement in Dmin without adversel~ affecting DmaX
when the Dye-Bleach bath is employed. ' ' 'i , EXAMPLE ['II -- Com~ined Dye-Bleach and Blc~sh-Fix Steps A multilayerj multicolor, photographic element is prepared similar to Example I. m e eiement is exposed as in ExampIe I and processed as follows:
- 1) Development - same as in Example I.
'~ 2) Dye-Bleach and Bleach-Fix - one min. @ 37.8C by employin~
.
the following solution:
Hydrochloric acid (12.1 N) 100 ml Thiourea 100 ~
Phenazine 0.25 g , Taylor yellow dye (see formula above) 3.0 g Water to 1 liter 3) Stabilizer Rinse - same as in Example I.
ell-defined positive images having impl~oved minimum densities similar to the results of Exam~le I were obtained in the processed photographic element.
:
- 2~ _ lOS'~6~3 i`he in~ention ha., been described Witil particular reference to certai.n preferlred embodlments thereo~ but it ~lill be urlderstood that variations and modifications can be ePrec-ted ~ithin the spirit and scope of the invention.
.
Samples of the above prepared element are exposed on an Eastman lb (Trademark) sensitometer using an exposure chart ; which allows additive red, green and blue exposures to achieve ; complete color separation. The exposure conditions are:
a) red light for one second~ b) blue light for 1/10 second, - and c) green light ~or 1/10 second. One sample of the exposed element is then processed as follows:
. _..... . .
-` 105~613 1) Development - ore min~ il 37'.~(, by e;n})lo~vi~ ,lle followirlG
~ctivator:
NaOH 20 g r 10 ~
Phenylmercaptotetrazole0.03 g Water to one liter 2) I-~ix - one min. ~ 22.2~ with Kodak 1~`-5 rix bath:
Soclium thiosulfate 240 g Sodium sulfite 15 g Acetic acid (28~) 48 ml Boric acid (crystals) 7.5 g ~otassium aluminum sulfate 15 g Water to one liter ,~
3) Dye_Bleach - 30 sec. @ 37.~C with:
12.1 N HCl 100 ml Th:iourea 100 g Phenazine ~.2 g Water to one liter 4) Bleach-Fix - one min. @ 37.8C with a conventional ferric 20 ethylenediamine tetracetic acid and al~nonium thiosulfate , bleach-fix bath 5) Stabilizer Rinse - ten sec. @ 22.2C with:
Na2C3 50 g/l Cetyl trimethylammonium bromide 5.0 g/l 6) Dry.
A second sample of the exposed element is processed in the same manner except that the Dye Bleach bath (step 3) is omitted. The following sensitometric results are obtained:
DENSITIES
Wi-th D,ye-Bleach ~,ath Without Dye-Bleach Bath Exposure Red Green Blue Ke~ ~reen Blue , Cyan 3.'34 .~5 ~ L~ .12 '1.10 1.32 ,, Magenta o.36 1.51 1.09 1.48 2.31 1.62 Yellow 0.18 0.47 2.09 1.27 o.85 2.25 Red 0.27 2.28 2.68 1.11 2.72 3. ol~
Green 3.33 0.98 2.32 3 98 l.2Ll 2.51 - Blue 3.36 2.2L~ 1.27 4.05 2.68 1.72 , D 0.25 0.28 0.75 1.57 0.82 1-39 Neutral Drmnax 3.43 3.23 3.07 4.00 3.20 3.07 ; 40 The above results reveal a significant improvement ,in Dmin witllout adversely affecting DrnaX when the dye-bleach bath is em~loyecl.
, ~ . .. .
iOS~13 ~XAM~L~
-A second multilayer, multicolor,,photographic element is pr~epared similar to Ex,~mple I except that compound 4 is replaced Wit~l compound 3 at an equimolar amount in layer 1. me eleme,nt is exposed and processed as in Example I except that the Dye_Bleach treatment of step 3 is for two minutes. The follow- i ing sensitometric results are obtained: ¦-DENSITIES
With D,ye-Bleach Bath Without Dye-~leach Bath 10 Exposure Red Green Blue RedGreen Blue Cyan 3~ i.l4 -1.0~ 3 '74-1.51 Magenta 0.41 1. 70 1.171: 65 2.23 1.73 Yellow 0. 25 o .48 2.341 49 1. og 2.59 i Red o.36 2.67 3.11 1 2~2.81 3.25 Green 3.60 1.46 2.81 3.601.70 2.80 Blue 3.60 2.56 1.36 3.682.78 1.69 N t 1 Dmin - 31 o .36 o .84 1.801.18 1.48 eu ra Dmax 3 65 3.50 3.363.68 3.60 3.5I
As in Example I, the above results reveal a signi-ficant improvement in Dmin without adversel~ affecting DmaX
when the Dye-Bleach bath is employed. ' ' 'i , EXAMPLE ['II -- Com~ined Dye-Bleach and Blc~sh-Fix Steps A multilayerj multicolor, photographic element is prepared similar to Example I. m e eiement is exposed as in ExampIe I and processed as follows:
- 1) Development - same as in Example I.
'~ 2) Dye-Bleach and Bleach-Fix - one min. @ 37.8C by employin~
.
the following solution:
Hydrochloric acid (12.1 N) 100 ml Thiourea 100 ~
Phenazine 0.25 g , Taylor yellow dye (see formula above) 3.0 g Water to 1 liter 3) Stabilizer Rinse - same as in Example I.
ell-defined positive images having impl~oved minimum densities similar to the results of Exam~le I were obtained in the processed photographic element.
:
- 2~ _ lOS'~6~3 i`he in~ention ha., been described Witil particular reference to certai.n preferlred embodlments thereo~ but it ~lill be urlderstood that variations and modifications can be ePrec-ted ~ithin the spirit and scope of the invention.
.
Claims (20)
1. In a process for producing a color image com-prising:
I) imagewise exposing a photosensitive element comprising a support having thereon at least one photosensitive silver halide emulsion layer, said emulsion layer having associa-ted therewith a nondiffusible redox dye releaser which will redox with oxidized developing agent to release a diffusible bleachable dye, said redox dye releaser being a ballasted, bleachable dye wherein the ballast group is linked to the dye through a linkage which is cleavable upon oxidation; and II) treating said photosensitive element with an alkaline processing composition in the presence of a silver halide developing agent to effect development of each of said exposed silver halide emulsion layers, thereby oxidizing said developing agent and forming a metallic silver image;
a) said oxidized developing agent thereby cross-oxidizing said redox dye releaser; and b) said oxidized redox dye releaser then cleaving, thus forming an imagewise distribution of diffusible, bleachable dye which diffuses out of said element;
the improvement comprising:
1) bleaching said element to decolorize any image-wise released dye which has not diffused out of said element; and 2) removing said metallic silver and silver halide from said element by bleaching and fixing;
whereby a dye image is obtained in said element which is the reverse of said metallic silver image.
I) imagewise exposing a photosensitive element comprising a support having thereon at least one photosensitive silver halide emulsion layer, said emulsion layer having associa-ted therewith a nondiffusible redox dye releaser which will redox with oxidized developing agent to release a diffusible bleachable dye, said redox dye releaser being a ballasted, bleachable dye wherein the ballast group is linked to the dye through a linkage which is cleavable upon oxidation; and II) treating said photosensitive element with an alkaline processing composition in the presence of a silver halide developing agent to effect development of each of said exposed silver halide emulsion layers, thereby oxidizing said developing agent and forming a metallic silver image;
a) said oxidized developing agent thereby cross-oxidizing said redox dye releaser; and b) said oxidized redox dye releaser then cleaving, thus forming an imagewise distribution of diffusible, bleachable dye which diffuses out of said element;
the improvement comprising:
1) bleaching said element to decolorize any image-wise released dye which has not diffused out of said element; and 2) removing said metallic silver and silver halide from said element by bleaching and fixing;
whereby a dye image is obtained in said element which is the reverse of said metallic silver image.
2. The process of claim 1 wherein said silver halide emulsion is negative-working.
3. The process of claim 1 wherein said support is transparent.
4. The process of claim 1 wherein said redox dye releaser is a nondiffusible p-sulfonamidoaniline or p-sulfon-amidophenol which is alkali-cleavable upon oxidation to release a diffusible dye from the benzene nucleus and having the formula:
wherein:
a) Z is a bleachable dye having a predominant spectral absorption within the region of the visible spectrum to which said associated silver halide emulsion is sensitive or a dye precursor;
b) Ballast is an organic ballasting radical of such molecular size and configuration as to render the sulfonamido compound nondiffusible during development in an alkaline processing composition;
c) G is OR or NHR1 wherein R is hydrogen or a hydrolyzable moiety and R1 is hydrogen or an alkyl group of 1 to 22 carbon atoms; and d) n is a positive integer of 1 to 2 and is 2 when G is OR or when R1 is hydrogen or an alkyl group of less than 8 carbon atoms.
wherein:
a) Z is a bleachable dye having a predominant spectral absorption within the region of the visible spectrum to which said associated silver halide emulsion is sensitive or a dye precursor;
b) Ballast is an organic ballasting radical of such molecular size and configuration as to render the sulfonamido compound nondiffusible during development in an alkaline processing composition;
c) G is OR or NHR1 wherein R is hydrogen or a hydrolyzable moiety and R1 is hydrogen or an alkyl group of 1 to 22 carbon atoms; and d) n is a positive integer of 1 to 2 and is 2 when G is OR or when R1 is hydrogen or an alkyl group of less than 8 carbon atoms.
5. The process of claim 4 wherein Z is an azo dye.
6. The process of claim 4 wherein G is OH or NH2.
7. The process of claim 4 wherein an aromatic ring is directly fused to said benzene nucleus to provide a sulfon-amidonaphthol compound.
8. The process of claim 4 wherein said photosensitive element comprises a support having thereon red-, green- and blue-sensîtive silver halide emulsion layers having associated there-with a nondiffusible p-sulfonamidoaniline or p-sulfonamidophenol which is alkali-cleavable upon oxidation to release a diffusible cyan, magenta and yellow dye, respectively, from the benzene nucleus, said dyes being azo dyes.
9. The process of claim 8 wherein said support is transparent and each of said silver halide emulsions is negative-working, whereby a positive transparency is obtained.
10. The process of claim 4 wherein said sulfonamido compound is:
N-[4-(2,4-di-t-pentylphenoxy)butyl]-1-hydroxy-4-{3-[5-hydroxy-6-(2-methylsulfonyl-4-nitrophenylazo)-1-naph-thylsulfamoyl]benzenesulfonamido}-2-naphthamide;
1-hydroxy-N-[4-di-t-pentylphenoxy)butyl]-4-{3-[5-acetoxy-6-(2-methylsulfonyl-4-nitrophenylazo)-1-naph-thylsulfamoyl]benzenesulfonamido}-2-naphthamide;
N-[4-(2,4-di-t-pentylphenoxy)butyl]-1-hydroxy-4-{3-[4-ethoxycarbonyloxy-8-methanesulfonamido-1-naphthylazo]-benzenesulfonamido}-2- naphthamide; or 4-[4-(3-chloro-4-hydroxyphenylazo)benzenesulfonamido]-N-[4-(2,4-di-t-pentylphenoxy)butyl]-1-hydroxy-2-naphthamide.
N-[4-(2,4-di-t-pentylphenoxy)butyl]-1-hydroxy-4-{3-[5-hydroxy-6-(2-methylsulfonyl-4-nitrophenylazo)-1-naph-thylsulfamoyl]benzenesulfonamido}-2-naphthamide;
1-hydroxy-N-[4-di-t-pentylphenoxy)butyl]-4-{3-[5-acetoxy-6-(2-methylsulfonyl-4-nitrophenylazo)-1-naph-thylsulfamoyl]benzenesulfonamido}-2-naphthamide;
N-[4-(2,4-di-t-pentylphenoxy)butyl]-1-hydroxy-4-{3-[4-ethoxycarbonyloxy-8-methanesulfonamido-1-naphthylazo]-benzenesulfonamido}-2- naphthamide; or 4-[4-(3-chloro-4-hydroxyphenylazo)benzenesulfonamido]-N-[4-(2,4-di-t-pentylphenoxy)butyl]-1-hydroxy-2-naphthamide.
11. A process for producing a color image comprising:
I) imagewise exposing a photosensitive element comprising a support having thereon at least one photosensitive silver halide emulsion layer, said emulsion layer having associa-ted therewith a nondiffusible p-sulfonamidoaniline or p-sulfonamidophenol which is alkali-cleavable upon oxida-tion to release a diffusible, bleachable dye from the benzene nucleus and having the formula:
wherein:
a) Z is a bleachable dye having a predominant spectral absorption within the region of the visible spectrum to which said associated silver halide emulsion is sensitive or a dye precursor;
b) Ballast is an organic ballasting radical of such molecular size and configuration as to render the sulfonamido compound nondiffusible during develop-ment in an alkaline processing composition;
c) G is OR or NHR1 wherein R is hydrogen or a hydrolyzable moiety and R1 is hydrogen or an alkyl group of 1 to 22 carbon atoms; and d) n is a positive integer of 1 to 2 and is 2 when G is OR
or when R1 is hydrogen or an alkyl group of less than 8 carbon atoms;
II) treating said photosensitive element with an alkaline processing composition in the presence of a silver halide developing agent to: 1) cause any dye precursor present to become a dye having a predominant spectral absorption within the region of the visible spectrum to which said associated silver halide emulsion is sensitive, said dye being bleach-able; and 2) to effect development of each of said exposed silver halide emulsion layers, thereby oxidizing said developing agent and forming a metallic silver image;
a) said oxidized developing agent thereby cross-oxidizing said sulfonamido compound; and b) said oxidized sulfonamido compound then cleaving, thus forming an imagewise distribution of diffusible, bleachable dye which diffuses out of said element;
III) bleaching said element to decolorize any imagewise-released dye which has not diffused out of said element; and IV) removing said metallic silver and silver halide from said element by bleaching and fixing, whereby a dye image is obtained in said element which is the reverse of said metallic silver image.
I) imagewise exposing a photosensitive element comprising a support having thereon at least one photosensitive silver halide emulsion layer, said emulsion layer having associa-ted therewith a nondiffusible p-sulfonamidoaniline or p-sulfonamidophenol which is alkali-cleavable upon oxida-tion to release a diffusible, bleachable dye from the benzene nucleus and having the formula:
wherein:
a) Z is a bleachable dye having a predominant spectral absorption within the region of the visible spectrum to which said associated silver halide emulsion is sensitive or a dye precursor;
b) Ballast is an organic ballasting radical of such molecular size and configuration as to render the sulfonamido compound nondiffusible during develop-ment in an alkaline processing composition;
c) G is OR or NHR1 wherein R is hydrogen or a hydrolyzable moiety and R1 is hydrogen or an alkyl group of 1 to 22 carbon atoms; and d) n is a positive integer of 1 to 2 and is 2 when G is OR
or when R1 is hydrogen or an alkyl group of less than 8 carbon atoms;
II) treating said photosensitive element with an alkaline processing composition in the presence of a silver halide developing agent to: 1) cause any dye precursor present to become a dye having a predominant spectral absorption within the region of the visible spectrum to which said associated silver halide emulsion is sensitive, said dye being bleach-able; and 2) to effect development of each of said exposed silver halide emulsion layers, thereby oxidizing said developing agent and forming a metallic silver image;
a) said oxidized developing agent thereby cross-oxidizing said sulfonamido compound; and b) said oxidized sulfonamido compound then cleaving, thus forming an imagewise distribution of diffusible, bleachable dye which diffuses out of said element;
III) bleaching said element to decolorize any imagewise-released dye which has not diffused out of said element; and IV) removing said metallic silver and silver halide from said element by bleaching and fixing, whereby a dye image is obtained in said element which is the reverse of said metallic silver image.
12. The process of claim 11 wherein Z is an azo dye.
13. The process of claim 11 wherein G is OH or NH2.
14. The process of claim 11 wherein an aromatic ring is directly fused to said benzene nucleus to provide a sulfon-amidonaphthol compound.
15. The process of claim 14 wherein X is an azo dye.
16. The process of claim 11 wherein said photosensi-tive element comprises a support having thereon red-, green-and blue-sensitive silver halide emulsion layers having associa-ted therewith a nondiffusible p-sulfonamidoaniline or p-sulfon-amiclophenol which is alkali-cleavable upon oxidation to release a diffusible cyan, magenta and yellow dye, respectively, from the benzene nucleus, said dyes being azo dyes.
17. The process of claim 11 wherein said silver halide emulsion is negative-working.
18. The process of claim 11 wherein said support is transparent.
19. The process of claim 16 wherein said support is transparent and each of said silver halide emulsions is negative-working, whereby a positive transparency is obtained.
20. The process of claim 19 wherein said sulfonamido compound is:
N-[4-(2,4-di-t-pentylphenoxy)butyl]-1-hydroxy-4-{3-[5-hydroxy-6-(2-methylsulfonyl-4-nitrophenylazo)-1-naph-thylsulfamoyl]benzenesulfonamido}-2-naphthamide;
1-hydroxy-N-[4-(2,4-di-t-pentylphenoxy)butyl]-4-{3-[5-acetoxy-6-(2-methylsulfonyl-4-nitrophenylazo)-1-naph-thylsulfamoyl]benzenesulfonamido}-2-naphthamide;
N-[4-(2,4-di-t-pentylphenoxy)butyl]-1-hydroxy-4-{3-[4-ethoxycarbonyloxy-8-methanesulfonamido-1-naphthylazo]-benzenesulfonamido}-2-naphthamide; or 4-[4-(3-chloro-4-hydroxyphenylazo)benzenesulfonamido]-N-[4-(2,4-di-t-pentylphenoxy)butyl]-1-hydroxy-2-naphthamide.
N-[4-(2,4-di-t-pentylphenoxy)butyl]-1-hydroxy-4-{3-[5-hydroxy-6-(2-methylsulfonyl-4-nitrophenylazo)-1-naph-thylsulfamoyl]benzenesulfonamido}-2-naphthamide;
1-hydroxy-N-[4-(2,4-di-t-pentylphenoxy)butyl]-4-{3-[5-acetoxy-6-(2-methylsulfonyl-4-nitrophenylazo)-1-naph-thylsulfamoyl]benzenesulfonamido}-2-naphthamide;
N-[4-(2,4-di-t-pentylphenoxy)butyl]-1-hydroxy-4-{3-[4-ethoxycarbonyloxy-8-methanesulfonamido-1-naphthylazo]-benzenesulfonamido}-2-naphthamide; or 4-[4-(3-chloro-4-hydroxyphenylazo)benzenesulfonamido]-N-[4-(2,4-di-t-pentylphenoxy)butyl]-1-hydroxy-2-naphthamide.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US422390A US3923510A (en) | 1973-12-06 | 1973-12-06 | Process for producing color images by bleaching redox diffusible dye releasers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1052613A true CA1052613A (en) | 1979-04-17 |
Family
ID=23674681
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA213,004A Expired CA1052613A (en) | 1973-12-06 | 1974-11-05 | Process for producing color images |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US3923510A (en) |
| JP (1) | JPS5092133A (en) |
| BE (1) | BE823080A (en) |
| CA (1) | CA1052613A (en) |
| DE (1) | DE2457307A1 (en) |
| FR (1) | FR2254046B1 (en) |
| GB (1) | GB1477376A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2368064A1 (en) * | 1976-10-15 | 1978-05-12 | Kodak Pathe | PROCESS FOR FORMING IMAGES IN |
| DE2733112A1 (en) * | 1977-07-22 | 1979-02-08 | Agfa Gevaert Ag | PHOTOGRAPHIC COLOR DIFFUSION TRANSFER PROCESS |
| DE2848455A1 (en) * | 1977-11-10 | 1979-05-17 | Eastman Kodak Co | PHOTOGRAPHIC RECORDING MATERIAL |
| FR2414745A1 (en) * | 1978-01-11 | 1979-08-10 | Kodak Pathe | Diffusion transfer photographic process - using ballasted coupler which forms diffusible gp. by reaction with primary aromatic amine developer |
| US4256826A (en) * | 1978-08-14 | 1981-03-17 | Eastman Kodak Company | Bleach-fix sheets |
| JPS59177553A (en) * | 1983-03-28 | 1984-10-08 | Fuji Photo Film Co Ltd | Silver halide color photosensitive material |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US351673A (en) * | 1886-10-26 | Device for hanging picture-frames | ||
| US2728290A (en) * | 1953-03-31 | 1955-12-27 | Eastman Kodak Co | Photographic reproduction process, including transfer of azo dyes |
| US3498787A (en) * | 1965-08-20 | 1970-03-03 | Eastman Kodak Co | Rapid dye-bleach photographic process and element comprising dye-developers |
| US3503741A (en) * | 1966-11-04 | 1970-03-31 | Eastman Kodak Co | Silver-dye-bleach process utilizing formazan dyes |
| US3443939A (en) * | 1967-07-24 | 1969-05-13 | Polaroid Corp | Differential mobility of color moiety in color transfer |
| US3698897A (en) * | 1971-07-06 | 1972-10-17 | Eastman Kodak Co | Diffusion transfer processes and film units comprising compounds which are cleavable upon oxidation in alkali media to produce diffusible dyes or dye precursors |
| US3725062A (en) * | 1971-07-06 | 1973-04-03 | Eastman Kodak Co | Color diffusion processes utilizing hydroquinones which provide dye image materials upon oxidation in alkaline conditions |
| BE789689A (en) * | 1971-10-04 | 1973-04-04 | Eastman Kodak Co | PHOTOSENSITIVE ELEMENT AND ITS APPLICATION TO COLOR PHOTOGRAPHY BY DIFFUSION-TRANSFER |
-
1973
- 1973-12-06 US US422390A patent/US3923510A/en not_active Expired - Lifetime
-
1974
- 1974-11-05 CA CA213,004A patent/CA1052613A/en not_active Expired
- 1974-12-04 DE DE19742457307 patent/DE2457307A1/en active Pending
- 1974-12-05 GB GB5266474A patent/GB1477376A/en not_active Expired
- 1974-12-05 FR FR7439764A patent/FR2254046B1/fr not_active Expired
- 1974-12-06 JP JP49139681A patent/JPS5092133A/ja active Pending
- 1974-12-06 BE BE151274A patent/BE823080A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DE2457307A1 (en) | 1975-06-19 |
| FR2254046B1 (en) | 1976-10-22 |
| BE823080A (en) | 1975-06-06 |
| US3923510A (en) | 1975-12-02 |
| JPS5092133A (en) | 1975-07-23 |
| GB1477376A (en) | 1977-06-22 |
| FR2254046A1 (en) | 1975-07-04 |
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