CA1160881A - Release of photographic reagents with oxidized 3-pyrazolidone developing agents - Google Patents
Release of photographic reagents with oxidized 3-pyrazolidone developing agentsInfo
- Publication number
- CA1160881A CA1160881A CA000386830A CA386830A CA1160881A CA 1160881 A CA1160881 A CA 1160881A CA 000386830 A CA000386830 A CA 000386830A CA 386830 A CA386830 A CA 386830A CA 1160881 A CA1160881 A CA 1160881A
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- Canada
- Prior art keywords
- aryl
- alkyl
- photographic
- dye
- heterocyclyl
- Prior art date
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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
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/305—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers
- G03C7/30511—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers characterised by the releasing group
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Photographic reagents can be released from cer-tain photographic reagent releasing compounds by causing them to be oxidized by oxidized 3-pyrazolidone developing agents. Particularly useful photographic reagent releasing compounds are a-substituted ketones or imines in which a photographic reagent is joined to the a-carbon atom through a hetero atom which is cleaved from the a-carbon atom, under alkaline conditions, by means of oxidized 3-pyrazolidone developing agent. Photo-graphic assemblages containing photographic reagent releasing compounds and processes of releasing photo-graphic reagents in photographic elements and assemblages are described.
Photographic reagents can be released from cer-tain photographic reagent releasing compounds by causing them to be oxidized by oxidized 3-pyrazolidone developing agents. Particularly useful photographic reagent releasing compounds are a-substituted ketones or imines in which a photographic reagent is joined to the a-carbon atom through a hetero atom which is cleaved from the a-carbon atom, under alkaline conditions, by means of oxidized 3-pyrazolidone developing agent. Photo-graphic assemblages containing photographic reagent releasing compounds and processes of releasing photo-graphic reagents in photographic elements and assemblages are described.
Description
RELEASE OF PHOTOGRAPHIC REAGENTS WITH
_ 3-PYRAZOLIDO~E DEVELOPING AGENTS
This invention relates to processes for releasing photoglaphic rea~ents by causing certain photographic reagent releasing compounds to react with oxidized 3-pyrazolidone developing agent, and to photographic asse~blages containing a photographic reagent releasing compound and a 3-pyrazolidone developing agent.
The release of photographic reagent, ~uch ~6 development inhibitor, from a coupler during photographic processing is known. These couplers contain a development inhibitor moiety in the coupling position and have come to be known in the art as "DIR couplers". Development inhibitor is released from a DIR coupler as a consequence of the coupling reaction between the coupler and oxidized color developing agent by which dye is formed~ In this reaction the coupler reacts with oxidized color developing agent to form a leuco dye and the development inhibitor is then eliminated from the coupling position.
Representative DIR coupler6 are described for e~ample in ~uch patents as U.S. Patents 3,148~062, 3,227,554, 3,617,291, 3,733,201, 3,933,500 and 4~095,984.
In addition to DIR coupler6, compounds have been described which react with oxidized color developing agent to form a colorless reaction product and which release 8 developmPnt inhibitor or other photographic reagent.
These compounds have been referred to as DIR compounds, to distinguish them from DIR couplers. Representative DIR
compounds are described in such patents and published patent applications as U.S. Patents 3,632 t 345. 3,928,041, 3,938,996, 3,958,993, 3,961,959, 4,010,035, 4,029,503, 4,046,574, 4,049,455, 4,052,213, 4,063,950, 4,075,021, 4,121,934, 4,157,916, 4,171,223, 4,186,012 and 4,187,110, U.K. Patent Specifications 1,445,797, 1,504,094, 1,536,341 and 2,032,914A; German Published Patent Application~
(DT-OS) 2,448,063, 2,552,505, 2,610,546 and 2,617,310; and Belgian Patent 839,083.
_ 3-PYRAZOLIDO~E DEVELOPING AGENTS
This invention relates to processes for releasing photoglaphic rea~ents by causing certain photographic reagent releasing compounds to react with oxidized 3-pyrazolidone developing agent, and to photographic asse~blages containing a photographic reagent releasing compound and a 3-pyrazolidone developing agent.
The release of photographic reagent, ~uch ~6 development inhibitor, from a coupler during photographic processing is known. These couplers contain a development inhibitor moiety in the coupling position and have come to be known in the art as "DIR couplers". Development inhibitor is released from a DIR coupler as a consequence of the coupling reaction between the coupler and oxidized color developing agent by which dye is formed~ In this reaction the coupler reacts with oxidized color developing agent to form a leuco dye and the development inhibitor is then eliminated from the coupling position.
Representative DIR coupler6 are described for e~ample in ~uch patents as U.S. Patents 3,148~062, 3,227,554, 3,617,291, 3,733,201, 3,933,500 and 4~095,984.
In addition to DIR coupler6, compounds have been described which react with oxidized color developing agent to form a colorless reaction product and which release 8 developmPnt inhibitor or other photographic reagent.
These compounds have been referred to as DIR compounds, to distinguish them from DIR couplers. Representative DIR
compounds are described in such patents and published patent applications as U.S. Patents 3,632 t 345. 3,928,041, 3,938,996, 3,958,993, 3,961,959, 4,010,035, 4,029,503, 4,046,574, 4,049,455, 4,052,213, 4,063,950, 4,075,021, 4,121,934, 4,157,916, 4,171,223, 4,186,012 and 4,187,110, U.K. Patent Specifications 1,445,797, 1,504,094, 1,536,341 and 2,032,914A; German Published Patent Application~
(DT-OS) 2,448,063, 2,552,505, 2,610,546 and 2,617,310; and Belgian Patent 839,083.
-2-~ eretofore it had been believed that oxidized color developing agent was required to cause release of development inhibitor, or other photographic reagent, from a DIR compound. While a number of patents have described the use of black and white developing agents with elements containing DIR compounds, the black and white developing agents are described as auxiliary developing agent~ or are employed in process steps unrelated to release of development inhibitor. The disclosures of these patent~
show that the patentees believe that a black and white developing agent would not cause release of development inhibitor. Thus, U.S. Patent 4,046,574 in column 7 describes black and white developing agents, includi~g
show that the patentees believe that a black and white developing agent would not cause release of development inhibitor. Thus, U.S. Patent 4,046,574 in column 7 describes black and white developing agents, includi~g
3-pyrazolidones, as auxiliary developing agents for US2 with photographic elements in which a develop~ent inhibitor is released from a DIR compound upon reaetion with oxidized color developing agent. In fsct, examples 1 snd 7 of U.S. Patent 3,632,345, one of the early ~IR
compound patents, show that a common black and white developing agent, hydroquinone, does not release development inhibitor from a DIR compound.
Belgian Patent 839,083, in the paragraph bridging pages 5 and 6, summarizes the general understanding of the art regarding DIR couplers and compounds, namely that develop~ent inhibitor is released from DIR couplers and compounds by reaction with oxidized color developing a~ent~ and that only with a third group of compound~, those in which development inhibitor i6 released from a hydroquinone developing agent, is it possible to obtain release without a color developing agent.
The use of oxidized color developing agent to release development inhibîtor from DIR compounds is disadvantageous in those photographic materials and processes in which color developing agents are not normally employed. For example, formation of a black and white image in a 6ilver halide element does not n~rmally require a color developing agent. Similarly, there are ~ 3--color materials and processes whic~ do not require color developing agents for formation of a colored image. One such process is employed in forming images by color d-ffusion transfer with immobile compounds which release a mobile dye. In these materials and processes black and whi~e developing agents, and in particular 3 pyrazolidone developing agents, are used as the sole or principal developing agent. Not only is the color developing agent an additional, otherwise unnecessary, component of ehe material or processing composition, but in some instances it could cause stain in the processed material.
Thus, there exists a need for a way to release a development inhibitor, or other photographic reagents, during photographic processing in the absence of colGr developing agents.
I have surprisingly found that development inhibitors and other photographic reagents can be released from certain photographic reagent releasing compounds by means of oxidized 3-pyrazolidone developing agents. This is unexpected since 3-pyrazolidones are understood to be black and white developing agents, not color developing agents. Thus, in accordance with s~y discovery, a coupling reaction is not required to release development inhibitor, or other photographic reagents, from photographic reagent releasing compounds in accordance with this invention.
Rather, photographic reagents can be released by direct oxidation of photographic reagent releasing compounds of this invention by oxidized 3-pyrazolidone developing agent. It is believed that release involves a direct cleavage reaction similar to that described by Trost snd Massiot on pages 4407-8 of JACS, 99, 4403-1~ (1977).
In one aspect this invention relates to a process of releasing a p~otographic reagent from a photographic reagent releasing compound by causing the compound to react, under alkaline conditions, with oxidized 3-pyrazolidone developing agent.
In another aspect this invention relates to a photographic assemblage adapted for production of a dye image and release of photographic reagent by means of oxidized 3-pyrazolidone developing agent under slkaline conditions, the assemblage comprising a) a support bearing a silver halide emulsion having associated therewith a dye image providing material which provides an imagewi6e pattern of diffusible dye as a function of silver halide development, b) 2 photographic reagent releasing compound comprising an ~-substituted ketone or imine in which the photographic reagen~ is joined to the ~-carbon atom through a hetero atom which is cleavable from the ~-carbon atom under alkaline conditions, c) a dye image receiving layer; d) an alkaline processing composition and means for discharging same within the assemblage; and e3 2 3-pyrazolidone developing agent which in its oxidized form is capable of oxidizing the photographic reagent releasing compound to cleave the hetero atom Erom the a-carbon atom and thereby release the photographic reagent.
As used herein the term photographic reagent releasing compound (occasionally reEerred to hereinafte~
by the acronym PRR compound) defines a compound which, upon reaction with oxidized 3-pyrazolidone developing agent, wlll release a photographic reagent and form a colorless, or ~ransiently colored, reaction product. The photographic reagent releasing compounds will also form a colorless or transiently colored reaction product upon Teaction with oxidized color developing agent.
Particularly useful PRR compounds are ~-substituted ketones or imines in which a photographic reagent i6 joined to the ~-earbon atom, i.e. the carbon atom adjacent the keto or imino group, via a hetero atom te.g.
S, N, O, Se). The hetero atom forms a part of the photographic reagent or a part of a timing group which links the photographic reagent to the remainder of the compound. Oxidation of the PRR compound by oxîdized 3-pyraæolidone developing agent leads to cleavage of the hetero atom from the ~-carbon atom and thereby releases the photographic reagent.
The photographic reagent released in accordance with this invention is preferably a development inhibitor (e.g. mercap~otetrazoles, selenotetrazoles, mercaptoben~othiazoleæ 9 merCRptobellZoXaZoles ~
mercaptobenzyimidazoles, benzotriazoles, benzodiazoles, etc.), although it can be any reagent which is usefully released in a photographic element during processing, such as a bleach inhlbitor (e.g. moderately ballasted mercaptotetrazoles, mercaptobenzimidazoles 9 mercaptoqulnolines, mercaptodiazoles, mercaptothiadiazoles, mercap~othiatriazoles, etc.), a silver halide solvent or complexing agents (e.g.
triazenethiones, thiazol~nethiones, etc.) 9 a fogging or nucleating agent (e.g. hydrazines, hydrazides, etc.), or an auxiliary developing agent ~e.g. hydroquinones). Su~h photographic reagents contain a hetero a~om which can serve as the point of attachmen1: to ~he ~-carbon atom of the ~-substituted ~etone or im~ne. Alternatively, the photographic rea8ent can be ~oined to the ~-carbon atom via a timlng group from which it is displaced following release from the PRR compound.
Sultable photographic reagent releasing ~ompounds useful in this invention are known in the art and are described in the patents and published patent applications cited above in connection with the discussion of DIR
compounds. In ~ddition, other suitable photographic reagent releasing compounds in which the photographic reagent is linked to the ~ carbon atom via a timing group are described in my U.S. Pa~ent 4,248,962 issued February 3, l98l.
Included among the photographic reagent releasing compounds useful in the present invention ~re those represented by the following structures:
Q R' Il I
I. R2-C-CH ~--Nu-X-E ~ Y Z, and \ C=Q
II. / ~
Rl (Nu X E ~ Y-Z
wherein:
Q is oxo (=O) or imino (=NR~, where R~ i~
hydroxy or amino;
Y is sulfur (-S-), oxygen (-O-) or amino Rs (-N-), where Rs is hydrogen, alkyl, aryl or a covalent bond in a heterocyclic ring formed by Y and Z;
Z represents the atoms which, together with Y, form a photographic reagent;
n is O or l;
Nu-X-E is a timing group which, upon displacement from the carbon atom to which it is attached, undergoe6 an intramolecular nucleophilic displacement reaction to release Y-Z, where Nu is a nucleophilic group, E i~ sn electrophilic group ~nd X is a linking group for 6patially relating Nu and E, upon displacement from thc c~rhon atom to undergo an intramolecular nucleophilic displacement reaction;
R' is hydrogen, halogen, alkyl, aryl, heterocyclyl, -~-Nu-X-E~ nY-Z or o-R6, where R6 i~
alkyl, aryl, heterocyclyl, acyl ( -~-R7) or ~ulfonyl (-S~ R~ here R7 is alkyl, aryl or heterocyclyl;
Ra i S alkyl, aryl, heterocyclyl, cyao, amino (-N(RR32), ~ulfonyl S-S02 Ra ), 8ul fo (-SO20Ra), sulfonamido (-S02N(RB )2 ), onium (-N+(R )3 ) or OR , where R i5 hydrogen, alkyl, aryl or heterocyclyl, or two RB ~roups can com~ine with a nitrogen atom to which they are attached to form a heterocyclic ~itrogen ring; and R3 represents the atoms to complete a ~aturated or unsaturated, carbocyclic or heterocyclic ring or ring system containing st least one 5- to 7-membered ring.
The alkyl groups represented by R', ~ , Rs, R6, R7 and Ra can be selected from unsubstituted or substituted, straight chain, branched chain or cyclic alkyl groups containing a total of 1 to 30 carbon ~toms.
Useful substituents include one or more of the following groups: hydroxy, halogen, nitro, cyano, thiocyano, alkoxy, aryl, aryloxy, amino, carboxy, acyl, alkoxycarbvnyl, aryloxycarbonyl, carbamoyl, acylamino, sulfo, alkylsulfonyl, arylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, sulfamoyl, sulfonamido and heterocyclyl.
The aryl groups represented by Rl, R2, Rs, R6, R7 and R8 can be selected from unsubsituted or substituted aryl groups containing a total of 6 to 30 carbon atoms. Useful substituents include one or ~ore of the following groups: hydroxy, halogen, oitro, cyano, thiocyano, alkyl, alkoxy, aryloxy, am;no, c~rboxy, acyl alkoxycarbonyl, aryloxycarbonyl, carbamoyl, acylamino, sulfo, alkylsulfonyl, arylsulfonyl, alkoxysulfonyl, aryloxysulonyl, sulfamoyl, sulfonamido ~nd heterocyclyl.
The heterocyclyl groups represented by Rl, R2, R6, R' and RB can be selected from heterocyclic rings and ring systems containing such hetero atoms as nitro&en, oxygen, sulfur and 6elenium comprising at least one 5- to 7-membered ~eterocyclic ring. The rin~
system can cont~in fused aryl rings and can be unsubstituted or ~ubstituted with groups described above as suitable substituent6 for alkyl ~nd aryl ~roups.
The carbocyclic and heterocyclic rin~s and ring systems completed by R3 comprise at least one ~- to 7-membered ring containing carbon, nitrogen, oxygen, sulfur and/or se~enium atoms. At least one of the rings i~ a cyclic ketone, or an imine analog thereof.
Representative rings and ring systems include cyclopentanone, cyclopentanonimine, cyclohexanone, cyclohexadione, cyclohexenone, piperidone, lactone, pyrrolidone, hydanto~n, indanone, indanonimine, benzocyclohexanone, benzocycloheptone and oxyindole. The rings can be unsubstituted or substituted with groups S described abo~e as suitable substltuen~s for alkyl and aryl groups.
The amino groups represented by R4 can be unsubstituted or subst~uted with such groups as alkyl, aryl, alkylcarbonyl, arylcarbonyl and aminocarbonyl.
The photographic reagent represented by Y-Z can be any group which is deslrably released in a photographic elemen~ in an imagewise fashion to interact with other components of the element, such as a development inhibitor, a bleach inhibltor, a silver hal~de solvent Or a complexing agen~ a fogging or nucleating agent3 or developing agent. Representative photographic reagents are described above.
The timlng group representet by Nu-X-E is described in more detail in my U.S. Patent 4,248,962 issued February 3, 1981. The nucleophilic group, Nu, contains an electron rich oxygen, sulfur or nitrogen atom. The electrophilic group, E, contains an electron deficient c~rbonyl, thiocarbonyl, phosphinyl or thiophos-phinyl molety. The linking ~roup, X, is a divalent aliphatic, aromatic or heterocyclic group which provides favorable spatiAl relationship for nucleophilic attack of the nucleophilic center in Nu on the electrophilic center in E. With compounds containing such a timing group oxida~ion of the PRR compound leads to cleavage of the bond between the tim~ng group and the ~-carbon atom and thereafter an intramolecular nucleophilic displacement reaction within the timing group leads to release of the photographic reagent from the timing group. For further deeails and representative timing groups reference is made ~o the abov~-mentioned U.S. Patent 49248,962.
~ ALg~
_9_ Preferred photographic reagent releasing compounds useful in this invention are represented by the structural formulae:
R9-C-CH-(-Nu-X-E ~ Y-~, and R' o IV Rl~ Nu-X-E ~ Y-Z
~,./
wherein:
n, Nu-X-E, Y-Z and R' are as defined above;
R9 is alkyl, sryl or heterocyclyl, as de~ined above; and Rl is R9, sulfamoyl ((Rl~)2 NS~
6ulfonamido (Rll S02 NRI l_) , carbamoyl ((Rl I )2 NC0-), or acylamino (RllCONR~-) where R~ is hydrogen, alkyl, aryl or heterocyclyl as defi~ed above.
Particularly preferred are compounds of structures III and IV wherein:
n i6 0;
Y-Z i6 a development inhibitor;
Rl is hydrogen;
~9 is aryl, especially su~stituted phenyl ~uch as sulfamoylphenyl and slkoxyphenyl; and Rl i6 sulfamoyl, sulfonamido, carbamoyl or ~cylamino.
Exemplary photographic reagent rel2asing compounds are shown below:
~5 b. ¦ ! ,~\; ~ ~ ~ D ~
V
C ¦ I
~ F~ U~
~ 0~ c p a ~ ~, I O ~, o =
3 ~ z O I ~ ~D
~ I .
h .
~a ,~
~ l ~ ~ N
~ / \; D J~ ~ z a v /~ I
o ~ I o// V
O C r ~
~` I I :1 N N
O ~ Z
o ~a g 3 Ll~
E i I
Y ~
I
~1 ~ O I
N
-- N
O
Z
O
~ I
~j ¦ I
ZZ C~ If 6~
\L~ I I I
-~ 1 c c c r~
tC ~D O
O Z C) C7 I l I
Z ~1 Z
3 \ /
O N ~ ~ IS`\
E~
~) Z Z--O fD
N i I 0=0 N
~ O I I ~ \ O
.--1 Z Z Z O il~ Z I N
// \ I r-- // \ O I
11 1 I I 11 Z\
O C~ O
\ I I ~D ~) Z~
J~
// \ I
i I C \\ / \ U~
O
!~
N
C~ I
O Z
O
Z ~
z i-' ~ t_ t~
i,.
O
--15-- ~ t7J~L
O
U~
o =
X
c: L
~ I I
n~ tr~ I') --- I I C
~ ~D ~O I
m ~ o ~) ~
t~ N N
r-l I
~ Z Z
~ ~ O
E
-16 ~
_ I
~¦ I = I I I
// ~ ~/ ~
Z ~ Z O
\\ / \~
1 z z_ o z z~ ~ z z~
\\1,/ \\~_// \y \\~o// \y v~ u~ tn c ~rJ
4I tO
v ~ ~o 5 CL ~ 6 c~
~ ~ 3 V
-17~ ;3~
0 ~
r~ o o C~ ~) ~1:
~D h -- - ~ Z c~Z
// \ / ~ I I I I I
O
11 1 1 1 / \ I
O ~ Z Z_ Z Z
a) ~ z 1 E
~d h o p r~
S
J~
S . ~- _ C~
~:1 a,) ~O u) ul ~1 m O l l I
. ~ ~ . ~ o ¢ ~ // \ I // \ I // \ I
\ 1~ O ~ ~ O _ Q~~_ ~ I 11 _ I 11 _ I 11 _ tl~/ I ~1 I O ~ I I
t~ O = ~~ / \ U) ~ / \ qD ~ / \ u~
a)\ I ~ o ~ o ~=~ I I I
a) / \ o o o S \\ // '~
C~-- /
r~n~
S
U~ Z Z Z
,~ 5 O O O
o E
H
H
~ . O
z ~ ~D ~ CO
r -18~
Aùditional photographic reagent releasing compounds useful in this invention are shown below.
29 ~ ~C---S---CH---C--N\
~/ ~ 11 C2H5 N~ I
I ~
~a j 50-C 1 2H2s ~\ / ICI C 2 \N---O
31 n-C 2H 5-NH-502-Q ~-CO-CH2-S-C~
o /~
Q~ ~I
32 C H NH 50 5~ ~--CO-CH -S-C~
\o~
C 2 H 2 5 - ~ - N H - 5 0 2--3~S ~ o - C O- C H 2 - S - C~ ll 3 4n - C H - o~ ~ - C O - Ç H - S -n - C H - O - 5~ - C O- C H - S ~ 3 ~'R ~ R
11 \N---NH CONH-N t~ ,~
38,c5 Hl 1 ~ N---~ 1 1 \o=o/ 2 ~ S-o\
~/ \
39 t~ L ~ o
compound patents, show that a common black and white developing agent, hydroquinone, does not release development inhibitor from a DIR compound.
Belgian Patent 839,083, in the paragraph bridging pages 5 and 6, summarizes the general understanding of the art regarding DIR couplers and compounds, namely that develop~ent inhibitor is released from DIR couplers and compounds by reaction with oxidized color developing a~ent~ and that only with a third group of compound~, those in which development inhibitor i6 released from a hydroquinone developing agent, is it possible to obtain release without a color developing agent.
The use of oxidized color developing agent to release development inhibîtor from DIR compounds is disadvantageous in those photographic materials and processes in which color developing agents are not normally employed. For example, formation of a black and white image in a 6ilver halide element does not n~rmally require a color developing agent. Similarly, there are ~ 3--color materials and processes whic~ do not require color developing agents for formation of a colored image. One such process is employed in forming images by color d-ffusion transfer with immobile compounds which release a mobile dye. In these materials and processes black and whi~e developing agents, and in particular 3 pyrazolidone developing agents, are used as the sole or principal developing agent. Not only is the color developing agent an additional, otherwise unnecessary, component of ehe material or processing composition, but in some instances it could cause stain in the processed material.
Thus, there exists a need for a way to release a development inhibitor, or other photographic reagents, during photographic processing in the absence of colGr developing agents.
I have surprisingly found that development inhibitors and other photographic reagents can be released from certain photographic reagent releasing compounds by means of oxidized 3-pyrazolidone developing agents. This is unexpected since 3-pyrazolidones are understood to be black and white developing agents, not color developing agents. Thus, in accordance with s~y discovery, a coupling reaction is not required to release development inhibitor, or other photographic reagents, from photographic reagent releasing compounds in accordance with this invention.
Rather, photographic reagents can be released by direct oxidation of photographic reagent releasing compounds of this invention by oxidized 3-pyrazolidone developing agent. It is believed that release involves a direct cleavage reaction similar to that described by Trost snd Massiot on pages 4407-8 of JACS, 99, 4403-1~ (1977).
In one aspect this invention relates to a process of releasing a p~otographic reagent from a photographic reagent releasing compound by causing the compound to react, under alkaline conditions, with oxidized 3-pyrazolidone developing agent.
In another aspect this invention relates to a photographic assemblage adapted for production of a dye image and release of photographic reagent by means of oxidized 3-pyrazolidone developing agent under slkaline conditions, the assemblage comprising a) a support bearing a silver halide emulsion having associated therewith a dye image providing material which provides an imagewi6e pattern of diffusible dye as a function of silver halide development, b) 2 photographic reagent releasing compound comprising an ~-substituted ketone or imine in which the photographic reagen~ is joined to the ~-carbon atom through a hetero atom which is cleavable from the ~-carbon atom under alkaline conditions, c) a dye image receiving layer; d) an alkaline processing composition and means for discharging same within the assemblage; and e3 2 3-pyrazolidone developing agent which in its oxidized form is capable of oxidizing the photographic reagent releasing compound to cleave the hetero atom Erom the a-carbon atom and thereby release the photographic reagent.
As used herein the term photographic reagent releasing compound (occasionally reEerred to hereinafte~
by the acronym PRR compound) defines a compound which, upon reaction with oxidized 3-pyrazolidone developing agent, wlll release a photographic reagent and form a colorless, or ~ransiently colored, reaction product. The photographic reagent releasing compounds will also form a colorless or transiently colored reaction product upon Teaction with oxidized color developing agent.
Particularly useful PRR compounds are ~-substituted ketones or imines in which a photographic reagent i6 joined to the ~-earbon atom, i.e. the carbon atom adjacent the keto or imino group, via a hetero atom te.g.
S, N, O, Se). The hetero atom forms a part of the photographic reagent or a part of a timing group which links the photographic reagent to the remainder of the compound. Oxidation of the PRR compound by oxîdized 3-pyraæolidone developing agent leads to cleavage of the hetero atom from the ~-carbon atom and thereby releases the photographic reagent.
The photographic reagent released in accordance with this invention is preferably a development inhibitor (e.g. mercap~otetrazoles, selenotetrazoles, mercaptoben~othiazoleæ 9 merCRptobellZoXaZoles ~
mercaptobenzyimidazoles, benzotriazoles, benzodiazoles, etc.), although it can be any reagent which is usefully released in a photographic element during processing, such as a bleach inhlbitor (e.g. moderately ballasted mercaptotetrazoles, mercaptobenzimidazoles 9 mercaptoqulnolines, mercaptodiazoles, mercaptothiadiazoles, mercap~othiatriazoles, etc.), a silver halide solvent or complexing agents (e.g.
triazenethiones, thiazol~nethiones, etc.) 9 a fogging or nucleating agent (e.g. hydrazines, hydrazides, etc.), or an auxiliary developing agent ~e.g. hydroquinones). Su~h photographic reagents contain a hetero a~om which can serve as the point of attachmen1: to ~he ~-carbon atom of the ~-substituted ~etone or im~ne. Alternatively, the photographic rea8ent can be ~oined to the ~-carbon atom via a timlng group from which it is displaced following release from the PRR compound.
Sultable photographic reagent releasing ~ompounds useful in this invention are known in the art and are described in the patents and published patent applications cited above in connection with the discussion of DIR
compounds. In ~ddition, other suitable photographic reagent releasing compounds in which the photographic reagent is linked to the ~ carbon atom via a timing group are described in my U.S. Pa~ent 4,248,962 issued February 3, l98l.
Included among the photographic reagent releasing compounds useful in the present invention ~re those represented by the following structures:
Q R' Il I
I. R2-C-CH ~--Nu-X-E ~ Y Z, and \ C=Q
II. / ~
Rl (Nu X E ~ Y-Z
wherein:
Q is oxo (=O) or imino (=NR~, where R~ i~
hydroxy or amino;
Y is sulfur (-S-), oxygen (-O-) or amino Rs (-N-), where Rs is hydrogen, alkyl, aryl or a covalent bond in a heterocyclic ring formed by Y and Z;
Z represents the atoms which, together with Y, form a photographic reagent;
n is O or l;
Nu-X-E is a timing group which, upon displacement from the carbon atom to which it is attached, undergoe6 an intramolecular nucleophilic displacement reaction to release Y-Z, where Nu is a nucleophilic group, E i~ sn electrophilic group ~nd X is a linking group for 6patially relating Nu and E, upon displacement from thc c~rhon atom to undergo an intramolecular nucleophilic displacement reaction;
R' is hydrogen, halogen, alkyl, aryl, heterocyclyl, -~-Nu-X-E~ nY-Z or o-R6, where R6 i~
alkyl, aryl, heterocyclyl, acyl ( -~-R7) or ~ulfonyl (-S~ R~ here R7 is alkyl, aryl or heterocyclyl;
Ra i S alkyl, aryl, heterocyclyl, cyao, amino (-N(RR32), ~ulfonyl S-S02 Ra ), 8ul fo (-SO20Ra), sulfonamido (-S02N(RB )2 ), onium (-N+(R )3 ) or OR , where R i5 hydrogen, alkyl, aryl or heterocyclyl, or two RB ~roups can com~ine with a nitrogen atom to which they are attached to form a heterocyclic ~itrogen ring; and R3 represents the atoms to complete a ~aturated or unsaturated, carbocyclic or heterocyclic ring or ring system containing st least one 5- to 7-membered ring.
The alkyl groups represented by R', ~ , Rs, R6, R7 and Ra can be selected from unsubstituted or substituted, straight chain, branched chain or cyclic alkyl groups containing a total of 1 to 30 carbon ~toms.
Useful substituents include one or more of the following groups: hydroxy, halogen, nitro, cyano, thiocyano, alkoxy, aryl, aryloxy, amino, carboxy, acyl, alkoxycarbvnyl, aryloxycarbonyl, carbamoyl, acylamino, sulfo, alkylsulfonyl, arylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, sulfamoyl, sulfonamido and heterocyclyl.
The aryl groups represented by Rl, R2, Rs, R6, R7 and R8 can be selected from unsubsituted or substituted aryl groups containing a total of 6 to 30 carbon atoms. Useful substituents include one or ~ore of the following groups: hydroxy, halogen, oitro, cyano, thiocyano, alkyl, alkoxy, aryloxy, am;no, c~rboxy, acyl alkoxycarbonyl, aryloxycarbonyl, carbamoyl, acylamino, sulfo, alkylsulfonyl, arylsulfonyl, alkoxysulfonyl, aryloxysulonyl, sulfamoyl, sulfonamido ~nd heterocyclyl.
The heterocyclyl groups represented by Rl, R2, R6, R' and RB can be selected from heterocyclic rings and ring systems containing such hetero atoms as nitro&en, oxygen, sulfur and 6elenium comprising at least one 5- to 7-membered ~eterocyclic ring. The rin~
system can cont~in fused aryl rings and can be unsubstituted or ~ubstituted with groups described above as suitable substituent6 for alkyl ~nd aryl ~roups.
The carbocyclic and heterocyclic rin~s and ring systems completed by R3 comprise at least one ~- to 7-membered ring containing carbon, nitrogen, oxygen, sulfur and/or se~enium atoms. At least one of the rings i~ a cyclic ketone, or an imine analog thereof.
Representative rings and ring systems include cyclopentanone, cyclopentanonimine, cyclohexanone, cyclohexadione, cyclohexenone, piperidone, lactone, pyrrolidone, hydanto~n, indanone, indanonimine, benzocyclohexanone, benzocycloheptone and oxyindole. The rings can be unsubstituted or substituted with groups S described abo~e as suitable substltuen~s for alkyl and aryl groups.
The amino groups represented by R4 can be unsubstituted or subst~uted with such groups as alkyl, aryl, alkylcarbonyl, arylcarbonyl and aminocarbonyl.
The photographic reagent represented by Y-Z can be any group which is deslrably released in a photographic elemen~ in an imagewise fashion to interact with other components of the element, such as a development inhibitor, a bleach inhibltor, a silver hal~de solvent Or a complexing agen~ a fogging or nucleating agent3 or developing agent. Representative photographic reagents are described above.
The timlng group representet by Nu-X-E is described in more detail in my U.S. Patent 4,248,962 issued February 3, 1981. The nucleophilic group, Nu, contains an electron rich oxygen, sulfur or nitrogen atom. The electrophilic group, E, contains an electron deficient c~rbonyl, thiocarbonyl, phosphinyl or thiophos-phinyl molety. The linking ~roup, X, is a divalent aliphatic, aromatic or heterocyclic group which provides favorable spatiAl relationship for nucleophilic attack of the nucleophilic center in Nu on the electrophilic center in E. With compounds containing such a timing group oxida~ion of the PRR compound leads to cleavage of the bond between the tim~ng group and the ~-carbon atom and thereafter an intramolecular nucleophilic displacement reaction within the timing group leads to release of the photographic reagent from the timing group. For further deeails and representative timing groups reference is made ~o the abov~-mentioned U.S. Patent 49248,962.
~ ALg~
_9_ Preferred photographic reagent releasing compounds useful in this invention are represented by the structural formulae:
R9-C-CH-(-Nu-X-E ~ Y-~, and R' o IV Rl~ Nu-X-E ~ Y-Z
~,./
wherein:
n, Nu-X-E, Y-Z and R' are as defined above;
R9 is alkyl, sryl or heterocyclyl, as de~ined above; and Rl is R9, sulfamoyl ((Rl~)2 NS~
6ulfonamido (Rll S02 NRI l_) , carbamoyl ((Rl I )2 NC0-), or acylamino (RllCONR~-) where R~ is hydrogen, alkyl, aryl or heterocyclyl as defi~ed above.
Particularly preferred are compounds of structures III and IV wherein:
n i6 0;
Y-Z i6 a development inhibitor;
Rl is hydrogen;
~9 is aryl, especially su~stituted phenyl ~uch as sulfamoylphenyl and slkoxyphenyl; and Rl i6 sulfamoyl, sulfonamido, carbamoyl or ~cylamino.
Exemplary photographic reagent rel2asing compounds are shown below:
~5 b. ¦ ! ,~\; ~ ~ ~ D ~
V
C ¦ I
~ F~ U~
~ 0~ c p a ~ ~, I O ~, o =
3 ~ z O I ~ ~D
~ I .
h .
~a ,~
~ l ~ ~ N
~ / \; D J~ ~ z a v /~ I
o ~ I o// V
O C r ~
~` I I :1 N N
O ~ Z
o ~a g 3 Ll~
E i I
Y ~
I
~1 ~ O I
N
-- N
O
Z
O
~ I
~j ¦ I
ZZ C~ If 6~
\L~ I I I
-~ 1 c c c r~
tC ~D O
O Z C) C7 I l I
Z ~1 Z
3 \ /
O N ~ ~ IS`\
E~
~) Z Z--O fD
N i I 0=0 N
~ O I I ~ \ O
.--1 Z Z Z O il~ Z I N
// \ I r-- // \ O I
11 1 I I 11 Z\
O C~ O
\ I I ~D ~) Z~
J~
// \ I
i I C \\ / \ U~
O
!~
N
C~ I
O Z
O
Z ~
z i-' ~ t_ t~
i,.
O
--15-- ~ t7J~L
O
U~
o =
X
c: L
~ I I
n~ tr~ I') --- I I C
~ ~D ~O I
m ~ o ~) ~
t~ N N
r-l I
~ Z Z
~ ~ O
E
-16 ~
_ I
~¦ I = I I I
// ~ ~/ ~
Z ~ Z O
\\ / \~
1 z z_ o z z~ ~ z z~
\\1,/ \\~_// \y \\~o// \y v~ u~ tn c ~rJ
4I tO
v ~ ~o 5 CL ~ 6 c~
~ ~ 3 V
-17~ ;3~
0 ~
r~ o o C~ ~) ~1:
~D h -- - ~ Z c~Z
// \ / ~ I I I I I
O
11 1 1 1 / \ I
O ~ Z Z_ Z Z
a) ~ z 1 E
~d h o p r~
S
J~
S . ~- _ C~
~:1 a,) ~O u) ul ~1 m O l l I
. ~ ~ . ~ o ¢ ~ // \ I // \ I // \ I
\ 1~ O ~ ~ O _ Q~~_ ~ I 11 _ I 11 _ I 11 _ tl~/ I ~1 I O ~ I I
t~ O = ~~ / \ U) ~ / \ qD ~ / \ u~
a)\ I ~ o ~ o ~=~ I I I
a) / \ o o o S \\ // '~
C~-- /
r~n~
S
U~ Z Z Z
,~ 5 O O O
o E
H
H
~ . O
z ~ ~D ~ CO
r -18~
Aùditional photographic reagent releasing compounds useful in this invention are shown below.
29 ~ ~C---S---CH---C--N\
~/ ~ 11 C2H5 N~ I
I ~
~a j 50-C 1 2H2s ~\ / ICI C 2 \N---O
31 n-C 2H 5-NH-502-Q ~-CO-CH2-S-C~
o /~
Q~ ~I
32 C H NH 50 5~ ~--CO-CH -S-C~
\o~
C 2 H 2 5 - ~ - N H - 5 0 2--3~S ~ o - C O- C H 2 - S - C~ ll 3 4n - C H - o~ ~ - C O - Ç H - S -n - C H - O - 5~ - C O- C H - S ~ 3 ~'R ~ R
11 \N---NH CONH-N t~ ,~
38,c5 Hl 1 ~ N---~ 1 1 \o=o/ 2 ~ S-o\
~/ \
39 t~ L ~ o
4~ 0~ \e NOH
41 n_c12H2é \~1 5 n-C H/~ / \S\~ b~
~ s/~
t~ ~ ~s C~OH2~-n ~\
s~ I~
~l o ~ I -n 4 6 ~ n ~I~"~_s, ~, ~ Y,~,c, Nl I -t 4 8 ~-OC ~ 2H ~ 5 n NHCOC~ 5H2,1-n I' `n - -- ~ /N\
O
"~t NHCOCtl O-l~
~ ,D~ N\ll O //
ll~
~ ;s -~
co (CH2) 3--I
~-/ \Cl 5 ~ n S~
~\N/ s~
41 n_c12H2é \~1 5 n-C H/~ / \S\~ b~
~ s/~
t~ ~ ~s C~OH2~-n ~\
s~ I~
~l o ~ I -n 4 6 ~ n ~I~"~_s, ~, ~ Y,~,c, Nl I -t 4 8 ~-OC ~ 2H ~ 5 n NHCOC~ 5H2,1-n I' `n - -- ~ /N\
O
"~t NHCOCtl O-l~
~ ,D~ N\ll O //
ll~
~ ;s -~
co (CH2) 3--I
~-/ \Cl 5 ~ n S~
~\N/ s~
5 3 ~ H - - - S - - -o= ~, -o o/
~o/
s\ 9~
~S ~9~ ~
o~ "
C1~3\1~
CO ~
~=-=2 c H -n 57 OC~H",~-n H- S -O
-2~ -CH --C~ H-S_~
Il 8 5 N /
COC~ ~ H27 -n ll 6 5 ~ H-S-~
C o C C 6 H 5 /CsH ~ ~ t t C ~1--t
~o/
s\ 9~
~S ~9~ ~
o~ "
C1~3\1~
CO ~
~=-=2 c H -n 57 OC~H",~-n H- S -O
-2~ -CH --C~ H-S_~
Il 8 5 N /
COC~ ~ H27 -n ll 6 5 ~ H-S-~
C o C C 6 H 5 /CsH ~ ~ t t C ~1--t
6 1 1 61 ~; H~ 7 ~n N~ \ /N ---6 2 ~s Hl ~ -t #_--2 ~o_o~
\n/~\S 11 O H
63 ~ Cl ~ 7 -r~
0~ 0 ~s ~
O H
64 C~ ~H2l -n ~\N/ \~ ~ \N
n-C H -~ -C-CH -N/ N //S
g=~
rl-C14Hy~90 \ _ / 1~ /N ~ `G
-` -26~
eo \\~_// \\ //
f ~\ f Z _ Z \ 0 Z Z ~
,7 `~ ,7 ~o~
o o \ ~ " ~
\\ /
O ~_) = O
// \ ~ I iI / X
C~ = O Z 1-Z
O :1: y I
C~' -27~
/
.
ll 0 ~ 6, // I
d~3 Z
Z -- C~
9=~
, / \
0 o o Il ~ //
f O 11 ~7 0 ~ ~ .
Z . ~
U~ Z _ C~ ~ o . I I
f \
Z I 11 /~ \ I I / \
1 1 // z Z~
z = I // \~ /
C.) -- O O = O I \ / ;f ~ I O ~ = O
l l L') 9 1~ \ / \
~/ ~/
o ~ d Z ~ . , / \I ~ C~
-- () ~
~) L) I -~ C~
P ~::
O ~ ~U
,. ..~ .
\ //
._ ~/
// \ 11 o o "
// Z
Z \ ~-// \ ,~ \
\ / ~ Z// \ O
\ /~/
Il Z
Z
Z \ I
,7 . ~ ~ ~, o ~ .
Z I 11 , ~ "
o , _., ,, ~, I C
Z o ~, = o ~ Do// \
T o / \~ ~ O \\ f ~) = 0 0--4 ~ ~9~ I O
\\ / ~ I Z Z
o) I t / /
O
~)' I \\ //
O U~
~r) 3 Lf\
r-, . ~ `
: . .
-29~ L~
\n/~\S 11 O H
63 ~ Cl ~ 7 -r~
0~ 0 ~s ~
O H
64 C~ ~H2l -n ~\N/ \~ ~ \N
n-C H -~ -C-CH -N/ N //S
g=~
rl-C14Hy~90 \ _ / 1~ /N ~ `G
-` -26~
eo \\~_// \\ //
f ~\ f Z _ Z \ 0 Z Z ~
,7 `~ ,7 ~o~
o o \ ~ " ~
\\ /
O ~_) = O
// \ ~ I iI / X
C~ = O Z 1-Z
O :1: y I
C~' -27~
/
.
ll 0 ~ 6, // I
d~3 Z
Z -- C~
9=~
, / \
0 o o Il ~ //
f O 11 ~7 0 ~ ~ .
Z . ~
U~ Z _ C~ ~ o . I I
f \
Z I 11 /~ \ I I / \
1 1 // z Z~
z = I // \~ /
C.) -- O O = O I \ / ;f ~ I O ~ = O
l l L') 9 1~ \ / \
~/ ~/
o ~ d Z ~ . , / \I ~ C~
-- () ~
~) L) I -~ C~
P ~::
O ~ ~U
,. ..~ .
\ //
._ ~/
// \ 11 o o "
// Z
Z \ ~-// \ ,~ \
\ / ~ Z// \ O
\ /~/
Il Z
Z
Z \ I
,7 . ~ ~ ~, o ~ .
Z I 11 , ~ "
o , _., ,, ~, I C
Z o ~, = o ~ Do// \
T o / \~ ~ O \\ f ~) = 0 0--4 ~ ~9~ I O
\\ / ~ I Z Z
o) I t / /
O
~)' I \\ //
O U~
~r) 3 Lf\
r-, . ~ `
: . .
-29~ L~
7 6 ~ C H - C O- O - C ~ 6 H S 3 -n N~ e ~--N~o\ /O\ ~ PL llg N~ I
N~ \N-~N===N
78 ICO Cl ~Hz7 "~- - CH - CO- O- C z H 5 N ~ \ _ /
N===N
7 9 ~ o~
s N ~N ~ _ N===N
_30 ~0 NH
C5H1, The photographic reagent releasing compounds em-ployed in this invention are known compounds and can be prepared ~y procedures descri~ed in the patents and ap-plications identified above relating to DIR compounds.
The 3-pyrazolidone developing a~ent e~ployed in accordance with this invention can be any 3-pyraz~lidone developing agent known in t~e art, it being ~ppre~iated that in its oxidized orm the particular 3 pyrazolidone employed must be capa~le of oxidizing the particular PRR
compound employed. Useful 3-pyrazolidone developi~g agents include: 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-di-methyl-3-pyrazolidone, 4 hydroxyme~thyl-4-methyl-1-(3,4-di-methylphenyl)-3-pyrazolidone, 1-m~tolyl-3-pyrazolidone, 1-~-tolyl-3-pyrazolidone, 4-hydroxymethyl-4-methyl-1-p-tolyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, l-phenyl-5-methyl-3-pyrazolidone, l-phenyl-4,4-~i6-(~ydroxymethyl)-3-pyrazolidone, 1,4-dimethyl-3-pyra-zolidone, 4-methyl-3-pyrazolidone, 4,4-dimeehyl-3-pyra-zolidone, 1-(3-chlorophenyl)~4-methyl-3-pyrazolidone, 1-(4-chlorophenyl?-4-methyl-3-pyrazolidone, 1-(3-chloro-phenyl)-3-pyrazolidone, 1-(4-chlorophenyl)-3-pyrazolidone, 1-(4-tolyl)-4-methyl-3-pyrazolidone, l-t2-tolyl)-4-methyl-3-pyrazolidone~ 1-(4-tolyl~-3-pyrazolidone, l-t3-t-olyl)-3-pyrazolidone, 1-(3-tolyl)-4,4-dimethyl-3-pyra-zolidone, 1-(2-trifluoroethyl)-4,4-dimethyl-3-pyra-zolidone, 5-methyl-3-pyrazolidone and the like.
The 3-pyrazolidone developing agent can be the sole developing agent employed in the process or contained in the assem~lage or there can ~e more than one 3-pyrazo~idone developing agent. In addition, in some circumstances it may be desirable to employ an auxiliary black and white developing agent, such as a hydroquinone, in combination with the 3-pyrazolidone developing agent.
To take maximum advantage of this invention the assemblage should be free of, and the process should ~e practiced in the absence of, a chromogenic or color developing agent. Color developing agen~s are understood in the art to be compounds which will react with and be oxidized by developable silver halide and which, in their oxidized form, will couple with dye-forming couplers to form a dye. They include para-phenylenediamines and para-aminophenols. In some embodiments of this invention the film unit may contain a compound which is structurally similar to a color developing agent but which, ~s incorporated in ehe film unit, serves a different function, e.g., compounds which are ~cavengers for oxidized developing a~ent.
In practicing the process of the present invention the photographic reagent releasing compound is caused to react with oxidized 3-pyrazolidone developing 2~ agent under alkaline conditions, prefera~ly at a pH of 13 to 14. An alkaline environment can be provided by a processing CompositiDn comprising an aqueous alkaline solution of a base, ~uch as an alkali metal hydroxide or carbonate, e.g. ~odium hydroxide or sodium carbonate or an 3 amine, e,g., diethylamine.
Either or both of the photographic reagent releasing compound and the 3-pyrazolidone developing agent can be contained either in the alkaline processing ~ J~ t~
soluti~n or in a photographic element to be processed. I
the ph~tographic reagent releasing compound is contsined in the alkaline processing composition, it should be a compound which is capable of migrating through the alkalî-permeable layers of photographic elements. If the 3-pyrazolidone developing agent i6 contained in a photographic element it should be in a location where it will come into reactive association with developable silver halide when an alkali environment is provided. If the photographic reagent releasing compound is contained in a photographic element, it should be in a location where it will come into reactive association with oxidized 3-pyrazolidone developing agent when an alkaline environment is provided. When the photographic reagent releasing compound is contained in the photographic element, it preferably is of sufficient bulk ~o as to be substantially immobile in the alkali-permeable layer6 of the element.
Any means known in the photographic art for providing oxidized 3-pyrazolidone developing agent can be employed in the process of the present invention. A
convenient means is to cause the 3-pyrazolidone developing agent to resct with developable silver halide under alkaline conditions. The silver halide can be of any convenient conventional type, such as disclosed, for example, in Research Disclosure, Item 17643, Section I, December 1978. (Research Disclosure is published ~y Industrial Opportunities Ltd., Homewell Havant Hamps~ire, PO9 lEF United Kingdom.) The silver halide can be either negative-working or positive-working and can form either a ~urface or internal latent image upon exposure.
As described in the above referenced Research Disclosure Item 17643, silver halide emulsions can be chemically sensitized (Section III), be spectrally ~ensitized or desensitized (Section IV), be hardened ~Section X), include stabilizers and antifoggants (seceion VI), and contain other conventional photographic addenda.
Reaction of the photographic reagent releasing compound with oxidized 3-pyrazolidone developing ~gent makes available an imagewise pattern of photographic reagent as a direct function of a silver halide development. This pattern can be used in any of ~he way6 known to those skilled in the art for making u6e of a photographic reagent in photographic elements snd assemblages. For example, if the reagent is a development inhibitor, it can be used to suppres6 development of silver halide. If the photographic reagent is æ bleach inhibitor, it can be used to inhibit bleaching of silver halide durinK a subsequent processing 6tep. If the photographic reagent is a silver halide solvent or complexing agent, it can be used to enhance removal of silver halide from the element or film unit during a subsequent processing step or to assist migration of silver halide in the element or film unit. If the photographic reagent is an auxiliary developing agent it can be used to assist develop~ent of ~ilver halide. If ~0 the photographic reagent is a ~pectral sensitizing dye it can be used to render ~ilver halide~ differentially 6ensitive to exposure to electromagnetic radi~tion which occurs contemporaneous with or 6ub~;equent to release of the reagent. Still other ways in whic~ the released photographie reagent can be employed io photograpbic elements, assemblages and proce~es will be apparent to those skilled in the art.
It is expected that the pre~ent invention will find maximum utility in color diffusion transfer film units which are not ba~ed on coupler chemistry. With such materials the present invention provides a convenient mean6 for releasing 8 development inhibitor or other photographic reagent while Avoiding the need for an auxiliary color developing agent. Accordingly, the remainder of th;6 discussion will be directed toward~
color diffusion transfer assemblages of the invention.
The silver halide emulsion or emulsions can be any of the emulsions described above. The assemblages can be designed to yield single color or multicolor images.
In film units d~signed to provide multicolor images the silver hallde emulsions are arranged in units each sensitiv~ to a different one of the three primary regions of the visible spectrum and have associated therewith a dye image providLng material that provides an image dye which absorbs radiation in one of the three primary lQ regions of the vislble spectrum. Each unit can be comprised of a single emulsion layer or of multiple emulsion layers sensitive to a given region of the spectrum. The various layers, including the layers of the image-forming units, can be arranged ~n various orders as known in the art. In an alternative format, the emulsions sensitive to each of the three primary regions of the spectrum can be disposed as a single segmented layer, e.g., as by the use of microvessels as described in Whitmore U.S. Patent 4,362,806 is~ued December 7, 1982.
Depending upon the dye image providing ma~erial employed, it can be incorporated in the silver halide emulsion layer or in a separate layer associated with the emulsion layer. Similarly, the photographic reagent releasing compound and the 3-pyrazolidone developing agent can be incorporated in the s~lver halide emulsion layer, in a layer asæociated therewith, or, as indicated above, these latter components can be incorporated in the alkaline processing composition used to develop the film unit.
The dye image providing material can be any of a number known in the art. Useful materials contain a dye moiety and a monitoring moiety. The monitoring moiety, in the presence of an alkaline processing solution and as a function of silver halide development, is responsible for a change ln mobility of the dye moiety. Dye image providing materials can be initially mob~le, and rendered J~ t ~ ~ t,~
immo~ile as a function of ~ilver halide development, 86 described in U.S. Patent 2,9B3,606. Alternatively, dye image providing materials can be initially immobile and rendered mobile, in t~e presence of an alkaline processin~ solution, as a function of silver halide development. This latter class of materials are referred to as redox dye releasing compounds. In such compounds, the monitoring group is a carrier from which the dye is released as a direct functior. of silver halide development or an an inverse function of silver halide development.
Compounds which release dye as an inverse function of silver halide development are referred to as negative-working release compounds while compounds ~hich release dye as an inverse function of silver halide development are referred to as positive-working release compounds.
A preferred class of negative-working release compounds are the ortho or para sulfonamidophenol6 and naphthols described in U.S. Patents 4,054,312, 4,055,4~8 ~nd 4,076,529. In these compounds the dye moiety is attached to 8 ~ulfonamido group which i6 ortho or para to the phenolic hydroxy group and is released by hydrolysis after oxidation of the sulfonamido compound during development.
A preferred class of positive-working release compounds are the nitr~benzene and quinone compounds described in U,S. Patent 4,139,379, In these compound~
the dye moiety is attached to an electrophilic cleavage group, such as a carbamate group, ortho to the nitro group or the quinone oxygen, and is released upon reduction of the compound ~y an electron donor compound contained in the element or the processing composition, unless the electron donor is oxidized during development.
Other useful positive-working release compounds are the hydroquinones described in U.S. Patent 3,980,479 and the benzisoxazolone compounds described in U.S. Patent 4,199,354.
Further details regarding the above release compounds, the manner in which they func~ion, and the procedures by which they can be prepared are contained in the patents referred to above.
In addition to the layers referred to above, the elements and assemblages can contain additional layers conventional in photographic elements and film units, such as spacer layers 9 filter layers, antihala~ion lsyers, scavenger layers, pH lowering layers (sometimes referred to as acid layers and neutralizing layers), timing layers, opaque light-reflecting layers, opaque light-absorbing layers, and the like. Useful supports include polymeric films, paper ~including polymer-coated paper), glass and the like.
To obtain a dye image with assemblages of the present invention, an alkaline environment is provided to permit the development of developable silver halide and consequent release of photographic rea8ent and change in mobility of the dye image providing material. This results in an imagewise pattern of photographic reagent as a direct function of silver halide development and an imagewise pa~tern of diffusible dye either as a direct or an inverse function of silver halide development.
The difusible dye can be transferred to an image receiving layer and employed as a transfer image.
Alternatively, it can merely be removed from the assemblage. Whether the diffusible dye is employed to form a ~ransfer image or not, the remaining dye image providing material, from which dye has not been released, can be employed to form either a retained image or a transfer image by techniques well known to those skilled in the art.
The effect which the imagewise pattern of released photographic reagent will have on image formation will depend upon 1) the photographic reagent released, 2) ~he type of silver halide employed and 3) the type of dye image providing material employed.
The alkaline processing composition can be an aqueous alkaline solution as described above. It ean be a com~onent of the assemblage and introduced into reactive association with other components of the film unit from ruptura~le container which is adapted to be positioned during processing of the assemblage ~o that a compressive force applied to the container by pressure-applying members will rupture the container and effect fl di~charge of the containers contents within the assemblage.
Preferred rupturable containers are described in U~S.
Patents 2,543,1Bl; 2,643,886; 2,653,732; ~,723,051;
3,056,492; 3,056,491 and 3,152,515. However, other methods of introducing the alkaline processing composition can be employed.
The dye image receiving layer can be on ~
separate support which is brought into contact with the emulsion layer(s~ during or subsequent to processing.
However, it preferably forms an integral part of the assemblage.
Any material can be employed ~s the ~mage receiving layer in the assemblages of this inveneion as long as it will mordant, or otherwise fix, the dye which diEfuses to it. The particular material chosen will, of course, depend upon the dyes to be mordanted. The image receiving layer can contsin ultraviolet absorbers to protect the dye images from fading due to ultraviolet light, brighteners and ~imilar materials to protect or enhance photographic dye ima~es, and the like.
~arious formats for diffusion tran~fer assemblages are known in the art. The layer arrangement employed with them can be used in the assemblages of this invention. In one useful format, the dye image receiving layer is located on a separate ~upport adapted to be superposed on the photogr~phic element after exposure thereof. Such image receiving layers are generally disclosed, ~or example, in U.S~ Patene 3,362,819.
~$~ s~
-3~-In another useful format, the dye image receiving layer is located integral with the pho~ographic elPmen~
and is positioned between ~he ~upport and the lowermost silver halide emulsion layer. One such format i~
disclosed in Belgian Paten~ 757,460. In such 8 format, the support for the photographic element i8 transparent and bears in order, an image receiving layer, a substantially opaque light-reflective layer, and then t~e photosensitive layer or layers. After imagewise exposure, a rupturable container containing the alkaline processing composition and an opaque process sheet are brought into superposed position position. Pressure-applying member~
in the camera rupture the container and spread processing composition over the photographic element 8S the assemblage is withdrawn from the camera. The processing composition develops each exposed silver halide emulsion layer and dye images, formed as a function of development, diffuse to the image receiving layer to provide right-reading image which is viewed through the ~0 transparent support on the opaque reflecting l~yer backgrounds. For other details co~cerning the format of this pareicular integral film unit, reference i~ made to the above-mentioned Belgian Paten~ 757,960.
Another format is disclos~sd in Belgian Patent 757,959. In this embodiment, the ~upport for the photographic element is transparent and bears, in order, the image reeeiving layer, ~ substantially opaque, light-reflective layer and the photosensitive layer or layers. A rupturable cont~iner, containing an alkaline processing composition and an opacifier, i~ positioned between the uppermost emulsion layer and a transparent top sheet which has t~ereon a neutralizing layer and a timing layer. The assemblage is placed in a camera, exposed through the transparent top sheet and ehen passed through ~ pair of pressure-applying members in the camera as it i~
being removed therefrom. The pressure-applying ~embers rupture ~he container and ~pread processin~ composition and opacifier over the pho~o~raphic layers to commence development and protect the photosensitive layer~ from further light exposure. The processing composition develops each silver halide layer and dye images, formed as a result of development, diffuse to the image receiving layer to provide a right-reading image which is viewed thro~gh the transparent support vn the opaque reflecting layer background. For further details concerning the format of this particular i~tegral assemblage, reference is made to the above-mentioned Belgian ~atent 757,95g.
Still other useful formats in which ~his invention can be employed are described in U.S. Patents 3,415,644; 3,415,645; 3,415,646; 3,647,437; 3,635,707; and 3,993,48~.
The term "nondiffusible" used herein has the meaning commonly applied to the term in photograpby and denotes materials that for all practical purposes do not migrate nor wander through organic colloid layers such as gelatin in an alkaline med;um, in photographic elements and preferably when processed in a medium having ~ pH ~f 11 or greater~ The same meansing is to be attached to the term l'immobile." The term "diffusible" has the converse meaning and denotes the materials having the property of diffusi~g effectively thro~gh the colloid layers of photographic elements in an alkaline medium.
"Mobile" has the same meaning.
The term "associated therewith" ~s us~d herein i~ intended to mean that the materials can be in either the same or different layers ~o long as the materials are accesssible to one another during processing.
The following examples illustrate the release of development inhibitor as a direct unction of cilver halide development with a 3-pyrazolidone developing 2gent, The photographic elements employed are image transfer materials designed to provide a retained image.
They contain negative working ~ilver halide and a redox dye releaser which releases a diffusible dye as a direct function of silver halide development. During processing released dye diffuses out of the element into the process;ng solution leaving in the element an imagewise distribution of redox dye releaser whi~h is either initially colored or converted to its colored form during processing. Thus, there i6 retained in the element, as ~n inverse function of silver halide developmentJ colored redox dye releaser which provide~ the final image.
The specific control elements employed in the exa~ples have a relatively high contrast and consequently a relatively short exposure latitude. By providing imagewise release of development inhibitor as a direct function of silver halide developmen~, development i8 inhibited to a greater extent in high exposure areas than in low exposure areas. This results in a lowering of contrast and a consequent extension of exposure latitude.
In the following examples, in which the control and inventive elements were processed to yield essentially the same minimum and maximum densities, sn extension of exposure latitude in the inventive element, compared with the control element, illustrates the imagewise release of development inhibition by oxidized 3-pyrazolidone developing agent and one of the advantageous effects obtained thereby.
Example 1 A color photographic element having the following schematic structure (A) was prepared. The ~umerical values denote quantities in (g/~ ).
Gelatin - 1.08 Red-sensitive silver halide, as silver -1.08 / redox dye releaser (see below) -1.13 in diethyllauramide - 0.57 /
gelatin - 2.16 .
Poly(ethylene terephthalate3 Film Support __ _ A second color photographic element ~B) was prepared which differed only in that it also contained 0.09 g/m2 of PRR compound No. 1 dispersed in 0.05 g/~
of diethyllauramide.
The redox dye releaser in these elements had the structure:
OH
~ /CN(Cl2H2s)2 i1 .~ \o !l ~-/ /SO2NHC(CH3 )3 N=N~ OH
CH3 S02 NH~
A sample of each element was ~ensitometrically exposed for 0.1 0econd through a 0-6 graduated neutral density test object, developed for 60 seconds in 8 developer ~olution having the following composition:
28 g Potassium Hydroxide 2.0 g Potassium Sulfite 7.5 ~ Potassium Bromide 0.1 g 5-Methylbenzotriazole 1.0 g 4-Hydroxymethyl-4-Me~hyl-l-Phenyl-3-Pyrazolidone .O g ll-Aminoundecanoic Acid Water to 1 liter, pH 13.46 then ~ixed, washed, buffered to pH 10 and dried. There was obtained in each element a negative silver image and a positive dye image of the test object. The coverage o~
silver, as a function of exposure, ~as measured by X-ray fluorescence analysis and 6ilver v~. log exposure curves were generated for the negative silver images. The results are reported in Table I below.
A second sample of each element was exposed and processed as described above, except that the element6 were bleach-fixed to remove all silver. Positive dye images of the test object were ob~ained from which density vs. log exposure curves were generated. The results ~re reported in Table I below.
TABLE I
Silver Image Dye Image Agmin Agmax Exposure Exposure2 Element (~/m2 ) (~/m2 ) Lati~ude_ min Dmax Latit~de A(control) 0 0.26 0.38 0.1 3.2 0.49 B(invention) Q 0.26 0.62 0.1 3.3 0.72 ~ Reported as the difference in log E between the poin~s on the curves which correspond to lO percent and 90 percent of A~max 2 Reported as the difference in log E between the points on the curves which correspond to 0.2 density unit6 above Dmin and 0~2 density units below D~,ax.
This data shows a 6ignificant extension of exposure latitude as a result of imagewise release of development inhibitor by oxidized 3-pyrazolidone developing agent.
Example 2 Four photographic elements were prepared having the following common schematic structure. The numerical values denote quantitie~ in gl~ .
b~ C'Si~ ~
Didodecylhydroq~inone (oxidized develop-ing agent scavenger) ~ 0.43 / Gelstin -1.03 _ 5 Fast green-sensitive ~ilver bromo-iodide, as ~ilver - 0.65 / Gelatin -1.36 / Redox dye releaser (6ee below) - 0.76 / PRR Compound (see below) -7.35 millimole~
_ ______________________ Slow green-sensitive silver bromo-iodide, as silver - 0.65 / Gelatin -1.36 / Redox dye releaser (see below) 0.76 / PRR Compound (see below) -7 35 millimoles_ _ _ Gelatin - 1 03 ~idodecylhydroquinone (oxidized develop-ing agent scavenger) - 0.43 / ~elatin -1.03 _ Gray silver ~ntihalat:ion layer - 0.27 /
Gelatin -_1.03 //////////// ~ilm Support ///////////
.
The redox dye releaser in each of the elements has the structure:
OH
CON(~l ~3 ~3 7 )2 il i hH C~ SO2NH-~
SO2_~ N--N~ Qcoc(cH3)3 \SO2NH(CH2) 2 NHS02CH3 A sample of each element was exposed for l/50 Eecond through a 0-3 neutrsl graduated-density test object and a Wratten 99 filter.
The exposed elements were developed for the time indicated in Table II, below, with a developer solution having the following composition:
38.8 g Trisodium phosphate 2.5 g Potassium bromide 1.0 g Sodium sulfite 2.0 g ll-Aminoundecanoic acid 0.5 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone Water to 1 liter pH adjusted to 13.0 with 50% sodium hydroxide.
The elements were then washed, bleach-fixed, washed, stabilized and dried. A positive dye image wa~
obtained in each element from which density vs. log exposure curves were generated. The results are reported in Table II, below.
TABLE II
_ _ Element PRR Compound No. Dlmin Dmax Exposure C(control) None 0.2 3.0 1.05 D 1 0.2 3.2 1.30 E S 0.2 3.2 1.1~
F 6 002 3.3 1.59 -2 Reported as the difference in log E between the points on the curves which correspond to 0.2 density units above Dmin and 0.2 density unit~ below DmaX.
This data shows that each of the compounds tested provides ~n extension of exposure latitude as a result of imagewise release of development inhibitor by oxidized 3-pyrazolidone developin~ agent.
This invention has been described in detail with particular reference to eertain preferred embodiment6 thereof but it will be understood that variations and modifications can be effected within the ~pirit and ~cope 5 of the invention.
N~ \N-~N===N
78 ICO Cl ~Hz7 "~- - CH - CO- O- C z H 5 N ~ \ _ /
N===N
7 9 ~ o~
s N ~N ~ _ N===N
_30 ~0 NH
C5H1, The photographic reagent releasing compounds em-ployed in this invention are known compounds and can be prepared ~y procedures descri~ed in the patents and ap-plications identified above relating to DIR compounds.
The 3-pyrazolidone developing a~ent e~ployed in accordance with this invention can be any 3-pyraz~lidone developing agent known in t~e art, it being ~ppre~iated that in its oxidized orm the particular 3 pyrazolidone employed must be capa~le of oxidizing the particular PRR
compound employed. Useful 3-pyrazolidone developi~g agents include: 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-di-methyl-3-pyrazolidone, 4 hydroxyme~thyl-4-methyl-1-(3,4-di-methylphenyl)-3-pyrazolidone, 1-m~tolyl-3-pyrazolidone, 1-~-tolyl-3-pyrazolidone, 4-hydroxymethyl-4-methyl-1-p-tolyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, l-phenyl-5-methyl-3-pyrazolidone, l-phenyl-4,4-~i6-(~ydroxymethyl)-3-pyrazolidone, 1,4-dimethyl-3-pyra-zolidone, 4-methyl-3-pyrazolidone, 4,4-dimeehyl-3-pyra-zolidone, 1-(3-chlorophenyl)~4-methyl-3-pyrazolidone, 1-(4-chlorophenyl?-4-methyl-3-pyrazolidone, 1-(3-chloro-phenyl)-3-pyrazolidone, 1-(4-chlorophenyl)-3-pyrazolidone, 1-(4-tolyl)-4-methyl-3-pyrazolidone, l-t2-tolyl)-4-methyl-3-pyrazolidone~ 1-(4-tolyl~-3-pyrazolidone, l-t3-t-olyl)-3-pyrazolidone, 1-(3-tolyl)-4,4-dimethyl-3-pyra-zolidone, 1-(2-trifluoroethyl)-4,4-dimethyl-3-pyra-zolidone, 5-methyl-3-pyrazolidone and the like.
The 3-pyrazolidone developing agent can be the sole developing agent employed in the process or contained in the assem~lage or there can ~e more than one 3-pyrazo~idone developing agent. In addition, in some circumstances it may be desirable to employ an auxiliary black and white developing agent, such as a hydroquinone, in combination with the 3-pyrazolidone developing agent.
To take maximum advantage of this invention the assemblage should be free of, and the process should ~e practiced in the absence of, a chromogenic or color developing agent. Color developing agen~s are understood in the art to be compounds which will react with and be oxidized by developable silver halide and which, in their oxidized form, will couple with dye-forming couplers to form a dye. They include para-phenylenediamines and para-aminophenols. In some embodiments of this invention the film unit may contain a compound which is structurally similar to a color developing agent but which, ~s incorporated in ehe film unit, serves a different function, e.g., compounds which are ~cavengers for oxidized developing a~ent.
In practicing the process of the present invention the photographic reagent releasing compound is caused to react with oxidized 3-pyrazolidone developing 2~ agent under alkaline conditions, prefera~ly at a pH of 13 to 14. An alkaline environment can be provided by a processing CompositiDn comprising an aqueous alkaline solution of a base, ~uch as an alkali metal hydroxide or carbonate, e.g. ~odium hydroxide or sodium carbonate or an 3 amine, e,g., diethylamine.
Either or both of the photographic reagent releasing compound and the 3-pyrazolidone developing agent can be contained either in the alkaline processing ~ J~ t~
soluti~n or in a photographic element to be processed. I
the ph~tographic reagent releasing compound is contsined in the alkaline processing composition, it should be a compound which is capable of migrating through the alkalî-permeable layers of photographic elements. If the 3-pyrazolidone developing agent i6 contained in a photographic element it should be in a location where it will come into reactive association with developable silver halide when an alkali environment is provided. If the photographic reagent releasing compound is contained in a photographic element, it should be in a location where it will come into reactive association with oxidized 3-pyrazolidone developing agent when an alkaline environment is provided. When the photographic reagent releasing compound is contained in the photographic element, it preferably is of sufficient bulk ~o as to be substantially immobile in the alkali-permeable layer6 of the element.
Any means known in the photographic art for providing oxidized 3-pyrazolidone developing agent can be employed in the process of the present invention. A
convenient means is to cause the 3-pyrazolidone developing agent to resct with developable silver halide under alkaline conditions. The silver halide can be of any convenient conventional type, such as disclosed, for example, in Research Disclosure, Item 17643, Section I, December 1978. (Research Disclosure is published ~y Industrial Opportunities Ltd., Homewell Havant Hamps~ire, PO9 lEF United Kingdom.) The silver halide can be either negative-working or positive-working and can form either a ~urface or internal latent image upon exposure.
As described in the above referenced Research Disclosure Item 17643, silver halide emulsions can be chemically sensitized (Section III), be spectrally ~ensitized or desensitized (Section IV), be hardened ~Section X), include stabilizers and antifoggants (seceion VI), and contain other conventional photographic addenda.
Reaction of the photographic reagent releasing compound with oxidized 3-pyrazolidone developing ~gent makes available an imagewise pattern of photographic reagent as a direct function of a silver halide development. This pattern can be used in any of ~he way6 known to those skilled in the art for making u6e of a photographic reagent in photographic elements snd assemblages. For example, if the reagent is a development inhibitor, it can be used to suppres6 development of silver halide. If the photographic reagent is æ bleach inhibitor, it can be used to inhibit bleaching of silver halide durinK a subsequent processing 6tep. If the photographic reagent is a silver halide solvent or complexing agent, it can be used to enhance removal of silver halide from the element or film unit during a subsequent processing step or to assist migration of silver halide in the element or film unit. If the photographic reagent is an auxiliary developing agent it can be used to assist develop~ent of ~ilver halide. If ~0 the photographic reagent is a ~pectral sensitizing dye it can be used to render ~ilver halide~ differentially 6ensitive to exposure to electromagnetic radi~tion which occurs contemporaneous with or 6ub~;equent to release of the reagent. Still other ways in whic~ the released photographie reagent can be employed io photograpbic elements, assemblages and proce~es will be apparent to those skilled in the art.
It is expected that the pre~ent invention will find maximum utility in color diffusion transfer film units which are not ba~ed on coupler chemistry. With such materials the present invention provides a convenient mean6 for releasing 8 development inhibitor or other photographic reagent while Avoiding the need for an auxiliary color developing agent. Accordingly, the remainder of th;6 discussion will be directed toward~
color diffusion transfer assemblages of the invention.
The silver halide emulsion or emulsions can be any of the emulsions described above. The assemblages can be designed to yield single color or multicolor images.
In film units d~signed to provide multicolor images the silver hallde emulsions are arranged in units each sensitiv~ to a different one of the three primary regions of the visible spectrum and have associated therewith a dye image providLng material that provides an image dye which absorbs radiation in one of the three primary lQ regions of the vislble spectrum. Each unit can be comprised of a single emulsion layer or of multiple emulsion layers sensitive to a given region of the spectrum. The various layers, including the layers of the image-forming units, can be arranged ~n various orders as known in the art. In an alternative format, the emulsions sensitive to each of the three primary regions of the spectrum can be disposed as a single segmented layer, e.g., as by the use of microvessels as described in Whitmore U.S. Patent 4,362,806 is~ued December 7, 1982.
Depending upon the dye image providing ma~erial employed, it can be incorporated in the silver halide emulsion layer or in a separate layer associated with the emulsion layer. Similarly, the photographic reagent releasing compound and the 3-pyrazolidone developing agent can be incorporated in the s~lver halide emulsion layer, in a layer asæociated therewith, or, as indicated above, these latter components can be incorporated in the alkaline processing composition used to develop the film unit.
The dye image providing material can be any of a number known in the art. Useful materials contain a dye moiety and a monitoring moiety. The monitoring moiety, in the presence of an alkaline processing solution and as a function of silver halide development, is responsible for a change ln mobility of the dye moiety. Dye image providing materials can be initially mob~le, and rendered J~ t ~ ~ t,~
immo~ile as a function of ~ilver halide development, 86 described in U.S. Patent 2,9B3,606. Alternatively, dye image providing materials can be initially immobile and rendered mobile, in t~e presence of an alkaline processin~ solution, as a function of silver halide development. This latter class of materials are referred to as redox dye releasing compounds. In such compounds, the monitoring group is a carrier from which the dye is released as a direct functior. of silver halide development or an an inverse function of silver halide development.
Compounds which release dye as an inverse function of silver halide development are referred to as negative-working release compounds while compounds ~hich release dye as an inverse function of silver halide development are referred to as positive-working release compounds.
A preferred class of negative-working release compounds are the ortho or para sulfonamidophenol6 and naphthols described in U.S. Patents 4,054,312, 4,055,4~8 ~nd 4,076,529. In these compounds the dye moiety is attached to 8 ~ulfonamido group which i6 ortho or para to the phenolic hydroxy group and is released by hydrolysis after oxidation of the sulfonamido compound during development.
A preferred class of positive-working release compounds are the nitr~benzene and quinone compounds described in U,S. Patent 4,139,379, In these compound~
the dye moiety is attached to an electrophilic cleavage group, such as a carbamate group, ortho to the nitro group or the quinone oxygen, and is released upon reduction of the compound ~y an electron donor compound contained in the element or the processing composition, unless the electron donor is oxidized during development.
Other useful positive-working release compounds are the hydroquinones described in U.S. Patent 3,980,479 and the benzisoxazolone compounds described in U.S. Patent 4,199,354.
Further details regarding the above release compounds, the manner in which they func~ion, and the procedures by which they can be prepared are contained in the patents referred to above.
In addition to the layers referred to above, the elements and assemblages can contain additional layers conventional in photographic elements and film units, such as spacer layers 9 filter layers, antihala~ion lsyers, scavenger layers, pH lowering layers (sometimes referred to as acid layers and neutralizing layers), timing layers, opaque light-reflecting layers, opaque light-absorbing layers, and the like. Useful supports include polymeric films, paper ~including polymer-coated paper), glass and the like.
To obtain a dye image with assemblages of the present invention, an alkaline environment is provided to permit the development of developable silver halide and consequent release of photographic rea8ent and change in mobility of the dye image providing material. This results in an imagewise pattern of photographic reagent as a direct function of silver halide development and an imagewise pa~tern of diffusible dye either as a direct or an inverse function of silver halide development.
The difusible dye can be transferred to an image receiving layer and employed as a transfer image.
Alternatively, it can merely be removed from the assemblage. Whether the diffusible dye is employed to form a ~ransfer image or not, the remaining dye image providing material, from which dye has not been released, can be employed to form either a retained image or a transfer image by techniques well known to those skilled in the art.
The effect which the imagewise pattern of released photographic reagent will have on image formation will depend upon 1) the photographic reagent released, 2) ~he type of silver halide employed and 3) the type of dye image providing material employed.
The alkaline processing composition can be an aqueous alkaline solution as described above. It ean be a com~onent of the assemblage and introduced into reactive association with other components of the film unit from ruptura~le container which is adapted to be positioned during processing of the assemblage ~o that a compressive force applied to the container by pressure-applying members will rupture the container and effect fl di~charge of the containers contents within the assemblage.
Preferred rupturable containers are described in U~S.
Patents 2,543,1Bl; 2,643,886; 2,653,732; ~,723,051;
3,056,492; 3,056,491 and 3,152,515. However, other methods of introducing the alkaline processing composition can be employed.
The dye image receiving layer can be on ~
separate support which is brought into contact with the emulsion layer(s~ during or subsequent to processing.
However, it preferably forms an integral part of the assemblage.
Any material can be employed ~s the ~mage receiving layer in the assemblages of this inveneion as long as it will mordant, or otherwise fix, the dye which diEfuses to it. The particular material chosen will, of course, depend upon the dyes to be mordanted. The image receiving layer can contsin ultraviolet absorbers to protect the dye images from fading due to ultraviolet light, brighteners and ~imilar materials to protect or enhance photographic dye ima~es, and the like.
~arious formats for diffusion tran~fer assemblages are known in the art. The layer arrangement employed with them can be used in the assemblages of this invention. In one useful format, the dye image receiving layer is located on a separate ~upport adapted to be superposed on the photogr~phic element after exposure thereof. Such image receiving layers are generally disclosed, ~or example, in U.S~ Patene 3,362,819.
~$~ s~
-3~-In another useful format, the dye image receiving layer is located integral with the pho~ographic elPmen~
and is positioned between ~he ~upport and the lowermost silver halide emulsion layer. One such format i~
disclosed in Belgian Paten~ 757,460. In such 8 format, the support for the photographic element i8 transparent and bears in order, an image receiving layer, a substantially opaque light-reflective layer, and then t~e photosensitive layer or layers. After imagewise exposure, a rupturable container containing the alkaline processing composition and an opaque process sheet are brought into superposed position position. Pressure-applying member~
in the camera rupture the container and spread processing composition over the photographic element 8S the assemblage is withdrawn from the camera. The processing composition develops each exposed silver halide emulsion layer and dye images, formed as a function of development, diffuse to the image receiving layer to provide right-reading image which is viewed through the ~0 transparent support on the opaque reflecting l~yer backgrounds. For other details co~cerning the format of this pareicular integral film unit, reference i~ made to the above-mentioned Belgian Paten~ 757,960.
Another format is disclos~sd in Belgian Patent 757,959. In this embodiment, the ~upport for the photographic element is transparent and bears, in order, the image reeeiving layer, ~ substantially opaque, light-reflective layer and the photosensitive layer or layers. A rupturable cont~iner, containing an alkaline processing composition and an opacifier, i~ positioned between the uppermost emulsion layer and a transparent top sheet which has t~ereon a neutralizing layer and a timing layer. The assemblage is placed in a camera, exposed through the transparent top sheet and ehen passed through ~ pair of pressure-applying members in the camera as it i~
being removed therefrom. The pressure-applying ~embers rupture ~he container and ~pread processin~ composition and opacifier over the pho~o~raphic layers to commence development and protect the photosensitive layer~ from further light exposure. The processing composition develops each silver halide layer and dye images, formed as a result of development, diffuse to the image receiving layer to provide a right-reading image which is viewed thro~gh the transparent support vn the opaque reflecting layer background. For further details concerning the format of this particular i~tegral assemblage, reference is made to the above-mentioned Belgian ~atent 757,95g.
Still other useful formats in which ~his invention can be employed are described in U.S. Patents 3,415,644; 3,415,645; 3,415,646; 3,647,437; 3,635,707; and 3,993,48~.
The term "nondiffusible" used herein has the meaning commonly applied to the term in photograpby and denotes materials that for all practical purposes do not migrate nor wander through organic colloid layers such as gelatin in an alkaline med;um, in photographic elements and preferably when processed in a medium having ~ pH ~f 11 or greater~ The same meansing is to be attached to the term l'immobile." The term "diffusible" has the converse meaning and denotes the materials having the property of diffusi~g effectively thro~gh the colloid layers of photographic elements in an alkaline medium.
"Mobile" has the same meaning.
The term "associated therewith" ~s us~d herein i~ intended to mean that the materials can be in either the same or different layers ~o long as the materials are accesssible to one another during processing.
The following examples illustrate the release of development inhibitor as a direct unction of cilver halide development with a 3-pyrazolidone developing 2gent, The photographic elements employed are image transfer materials designed to provide a retained image.
They contain negative working ~ilver halide and a redox dye releaser which releases a diffusible dye as a direct function of silver halide development. During processing released dye diffuses out of the element into the process;ng solution leaving in the element an imagewise distribution of redox dye releaser whi~h is either initially colored or converted to its colored form during processing. Thus, there i6 retained in the element, as ~n inverse function of silver halide developmentJ colored redox dye releaser which provide~ the final image.
The specific control elements employed in the exa~ples have a relatively high contrast and consequently a relatively short exposure latitude. By providing imagewise release of development inhibitor as a direct function of silver halide developmen~, development i8 inhibited to a greater extent in high exposure areas than in low exposure areas. This results in a lowering of contrast and a consequent extension of exposure latitude.
In the following examples, in which the control and inventive elements were processed to yield essentially the same minimum and maximum densities, sn extension of exposure latitude in the inventive element, compared with the control element, illustrates the imagewise release of development inhibition by oxidized 3-pyrazolidone developing agent and one of the advantageous effects obtained thereby.
Example 1 A color photographic element having the following schematic structure (A) was prepared. The ~umerical values denote quantities in (g/~ ).
Gelatin - 1.08 Red-sensitive silver halide, as silver -1.08 / redox dye releaser (see below) -1.13 in diethyllauramide - 0.57 /
gelatin - 2.16 .
Poly(ethylene terephthalate3 Film Support __ _ A second color photographic element ~B) was prepared which differed only in that it also contained 0.09 g/m2 of PRR compound No. 1 dispersed in 0.05 g/~
of diethyllauramide.
The redox dye releaser in these elements had the structure:
OH
~ /CN(Cl2H2s)2 i1 .~ \o !l ~-/ /SO2NHC(CH3 )3 N=N~ OH
CH3 S02 NH~
A sample of each element was ~ensitometrically exposed for 0.1 0econd through a 0-6 graduated neutral density test object, developed for 60 seconds in 8 developer ~olution having the following composition:
28 g Potassium Hydroxide 2.0 g Potassium Sulfite 7.5 ~ Potassium Bromide 0.1 g 5-Methylbenzotriazole 1.0 g 4-Hydroxymethyl-4-Me~hyl-l-Phenyl-3-Pyrazolidone .O g ll-Aminoundecanoic Acid Water to 1 liter, pH 13.46 then ~ixed, washed, buffered to pH 10 and dried. There was obtained in each element a negative silver image and a positive dye image of the test object. The coverage o~
silver, as a function of exposure, ~as measured by X-ray fluorescence analysis and 6ilver v~. log exposure curves were generated for the negative silver images. The results are reported in Table I below.
A second sample of each element was exposed and processed as described above, except that the element6 were bleach-fixed to remove all silver. Positive dye images of the test object were ob~ained from which density vs. log exposure curves were generated. The results ~re reported in Table I below.
TABLE I
Silver Image Dye Image Agmin Agmax Exposure Exposure2 Element (~/m2 ) (~/m2 ) Lati~ude_ min Dmax Latit~de A(control) 0 0.26 0.38 0.1 3.2 0.49 B(invention) Q 0.26 0.62 0.1 3.3 0.72 ~ Reported as the difference in log E between the poin~s on the curves which correspond to lO percent and 90 percent of A~max 2 Reported as the difference in log E between the points on the curves which correspond to 0.2 density unit6 above Dmin and 0~2 density units below D~,ax.
This data shows a 6ignificant extension of exposure latitude as a result of imagewise release of development inhibitor by oxidized 3-pyrazolidone developing agent.
Example 2 Four photographic elements were prepared having the following common schematic structure. The numerical values denote quantitie~ in gl~ .
b~ C'Si~ ~
Didodecylhydroq~inone (oxidized develop-ing agent scavenger) ~ 0.43 / Gelstin -1.03 _ 5 Fast green-sensitive ~ilver bromo-iodide, as ~ilver - 0.65 / Gelatin -1.36 / Redox dye releaser (6ee below) - 0.76 / PRR Compound (see below) -7.35 millimole~
_ ______________________ Slow green-sensitive silver bromo-iodide, as silver - 0.65 / Gelatin -1.36 / Redox dye releaser (see below) 0.76 / PRR Compound (see below) -7 35 millimoles_ _ _ Gelatin - 1 03 ~idodecylhydroquinone (oxidized develop-ing agent scavenger) - 0.43 / ~elatin -1.03 _ Gray silver ~ntihalat:ion layer - 0.27 /
Gelatin -_1.03 //////////// ~ilm Support ///////////
.
The redox dye releaser in each of the elements has the structure:
OH
CON(~l ~3 ~3 7 )2 il i hH C~ SO2NH-~
SO2_~ N--N~ Qcoc(cH3)3 \SO2NH(CH2) 2 NHS02CH3 A sample of each element was exposed for l/50 Eecond through a 0-3 neutrsl graduated-density test object and a Wratten 99 filter.
The exposed elements were developed for the time indicated in Table II, below, with a developer solution having the following composition:
38.8 g Trisodium phosphate 2.5 g Potassium bromide 1.0 g Sodium sulfite 2.0 g ll-Aminoundecanoic acid 0.5 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone Water to 1 liter pH adjusted to 13.0 with 50% sodium hydroxide.
The elements were then washed, bleach-fixed, washed, stabilized and dried. A positive dye image wa~
obtained in each element from which density vs. log exposure curves were generated. The results are reported in Table II, below.
TABLE II
_ _ Element PRR Compound No. Dlmin Dmax Exposure C(control) None 0.2 3.0 1.05 D 1 0.2 3.2 1.30 E S 0.2 3.2 1.1~
F 6 002 3.3 1.59 -2 Reported as the difference in log E between the points on the curves which correspond to 0.2 density units above Dmin and 0.2 density unit~ below DmaX.
This data shows that each of the compounds tested provides ~n extension of exposure latitude as a result of imagewise release of development inhibitor by oxidized 3-pyrazolidone developin~ agent.
This invention has been described in detail with particular reference to eertain preferred embodiment6 thereof but it will be understood that variations and modifications can be effected within the ~pirit and ~cope 5 of the invention.
Claims (21)
1. A photographic assemblage for producing a dye image wherein an imagewise pattern of diffusible dye and an imagewise pattern of photographic reagent are formed by means of oxidized 3-pyrazolidone developing agent, the assemblage comprising a) a support bearing at least one silver halide emulsion layer having associated therewith a dye image-providing material which is capable of providing an imagewise pattern of diffusible dye as a function of silver halide development;
b) a photographic reagent releasing compound comprising an .alpha.-substituted ketone or imine in which the photographic reagent is joined to the .alpha.-carbon atom through a hetero atom which is cleavable from the .alpha.-carbon atom under alkaline conditions;
c) a dye image receiving layer;
d) an alkaline processing composition and means for discharging same within the assemblage; and e) a 3-pyrazolidone developing agent which in its oxidized form is capable of oxidizing the photographic reagent releasing compound to cleave the hetero atom from the .alpha.-carbon atom and thereby release the photographic reagent;
the assemblage being free of color developing agent.
b) a photographic reagent releasing compound comprising an .alpha.-substituted ketone or imine in which the photographic reagent is joined to the .alpha.-carbon atom through a hetero atom which is cleavable from the .alpha.-carbon atom under alkaline conditions;
c) a dye image receiving layer;
d) an alkaline processing composition and means for discharging same within the assemblage; and e) a 3-pyrazolidone developing agent which in its oxidized form is capable of oxidizing the photographic reagent releasing compound to cleave the hetero atom from the .alpha.-carbon atom and thereby release the photographic reagent;
the assemblage being free of color developing agent.
2. An assemblage of claim 1 wherein the 3-pyra-zolidone developing agent is contained within the alkaline processing composition.
3. An assemblage of claim 1 wherein the photo-graphic reagent releasing compound has one of the follow-ing structures:
and wherein: Q is =O or =NR4 where R4 is hydroxy or amino;
Y is -S-, -0 or -N-where R5 is hydrogen, alkyl, aryl or a covalent bond in a heterocyclic ring formed by Y and Z;
Z represents the atoms which, together with Y, form a photographic reagent;
n is 0 or 1;
Nu-X-E is a timing group which, upon displacement from the carbon atom to which it is attached, undergoes an intramolecular nucleophilic displacement reaction to release Y-Z, where Nu is a nucleophilic group, E is an electrophilic group and X is a linking group for spatially relating Nu and E, upon displacement from the carbon atom, to undergo an intramolecular nucleophilic displacement reaction;
R1 is hydrogen, halogen, alkyl, aryl, hetero-cyclcyl or R6 where R6 is alkyl, aryl, heterocyclyl, -C-R7 or -SO2R7 where R7 is alkyl, aryl or heterocyclyl;
R2 is alkyl, aryl, heterocyclyl, cyano, - N (R8)2, -S02 R8, -S02 OR8, -SO2 N(R8 )2, - N+(R8 )3 or OR8 where R8 is hydrogen, alkyl, aryl or heterocyclyl, or two R8 groups combined with a nitrogen atom to which they are attached form a heterocyclic nitrogen ring; and R3 represents the atoms to complete a saturated or unsaturated, carbocyclic or heterocyclic ring or ring system containing at least one 5- to 7-membered ring.
and wherein: Q is =O or =NR4 where R4 is hydroxy or amino;
Y is -S-, -0 or -N-where R5 is hydrogen, alkyl, aryl or a covalent bond in a heterocyclic ring formed by Y and Z;
Z represents the atoms which, together with Y, form a photographic reagent;
n is 0 or 1;
Nu-X-E is a timing group which, upon displacement from the carbon atom to which it is attached, undergoes an intramolecular nucleophilic displacement reaction to release Y-Z, where Nu is a nucleophilic group, E is an electrophilic group and X is a linking group for spatially relating Nu and E, upon displacement from the carbon atom, to undergo an intramolecular nucleophilic displacement reaction;
R1 is hydrogen, halogen, alkyl, aryl, hetero-cyclcyl or R6 where R6 is alkyl, aryl, heterocyclyl, -C-R7 or -SO2R7 where R7 is alkyl, aryl or heterocyclyl;
R2 is alkyl, aryl, heterocyclyl, cyano, - N (R8)2, -S02 R8, -S02 OR8, -SO2 N(R8 )2, - N+(R8 )3 or OR8 where R8 is hydrogen, alkyl, aryl or heterocyclyl, or two R8 groups combined with a nitrogen atom to which they are attached form a heterocyclic nitrogen ring; and R3 represents the atoms to complete a saturated or unsaturated, carbocyclic or heterocyclic ring or ring system containing at least one 5- to 7-membered ring.
4. An assemblage of claim 1 wherein the photo-graphic reagent releasing compound has one of the follow-ing structures:
and wherein:
Y is -S-, -O- or -N-where R5 is hydrogen, alkyl, aryl or a covalent bond in a heterocyclic ring formed by Y and Z;
Z represents the atoms which, together with Y, form a photographic reagent;
n is 0 or l;
Nu-X-E is a timing group, which upon displacement from the carbon atom to which it is attached, undergoes an intramolecular nucleophilic displacement reaction to release Y-Z, where Nu is a nucleophilic group, E is an electrophilic group and X is a linking group for spatially relating Nu and E, upon displacement from the carbon atom, to undergo an intramolecular nucleophilic displacement reaction;
Rl is hydrogen, halogen, alkyl, aryl, hetero-cyclyl, -(Nu-X-E) n Y-Z or OR6 where R6 is alkyl, aryl 9 heterocyclyl, where R7 is alkyl, aryl or heterocyclyl;
R9 is alkyl, aryl or heterocyclyl and R10 is R9, (R11)2NSO2-, R11SO2NRll-, (R1l)2NCO, or R11CONR11-where R11 is hydrogen, alkyl, aryl or heterocyclyl.
and wherein:
Y is -S-, -O- or -N-where R5 is hydrogen, alkyl, aryl or a covalent bond in a heterocyclic ring formed by Y and Z;
Z represents the atoms which, together with Y, form a photographic reagent;
n is 0 or l;
Nu-X-E is a timing group, which upon displacement from the carbon atom to which it is attached, undergoes an intramolecular nucleophilic displacement reaction to release Y-Z, where Nu is a nucleophilic group, E is an electrophilic group and X is a linking group for spatially relating Nu and E, upon displacement from the carbon atom, to undergo an intramolecular nucleophilic displacement reaction;
Rl is hydrogen, halogen, alkyl, aryl, hetero-cyclyl, -(Nu-X-E) n Y-Z or OR6 where R6 is alkyl, aryl 9 heterocyclyl, where R7 is alkyl, aryl or heterocyclyl;
R9 is alkyl, aryl or heterocyclyl and R10 is R9, (R11)2NSO2-, R11SO2NRll-, (R1l)2NCO, or R11CONR11-where R11 is hydrogen, alkyl, aryl or heterocyclyl.
5. An assemblage of claim 3 wherein the group Y-Z forms a development inhibitor.
6. An assemblage of claim 4 wherein:
n is 0;
Y-Z is a development inhibitor;
Rl is hydrogen;
R9 is aryl; and R10 is (R11)2NSO 2-, R11 S02NR11-, (Rll)2NCO- or RllCONR11-.
n is 0;
Y-Z is a development inhibitor;
Rl is hydrogen;
R9 is aryl; and R10 is (R11)2NSO 2-, R11 S02NR11-, (Rll)2NCO- or RllCONR11-.
7. An assemblage of any one of claims 3, 4 or 5 wherein the 3-pyrazolidone developing agent is selected from the group consisting of 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone, 4-hydroxymethyl-4-methyl-l-(3,4-di-methylphenyl)-3-pyrazolidone, and 4-hydroxy-methyl-4-methyl-1-p-tolyl-3-pyrazolidone.
8. An assemblage of claim 1 wherein the silver halide emulsion is a direct positive emulsion and the dye image providing material releases a diffusible dye as a direct function of silver halide development.
9. An assemblage of claim 8 wherein the dye-image providing material is a sulfonamido dye releaser.
10. An assemblage of claim 1 wherein the silver halide emulsion is a negative-working emulsion and the dye image providing material releases a mobile dye as an inverse function of silver halide development.
11. An assemblage of claim 10 wherein the dye image providing material is a quinone dye releaser or nitro dye releaser and the film unit further contains an electron donor associated with the dye releaser.
12. A process of releasing a photographic re-agent from a photographic reagent releasing compound comprising an .alpha.-substituted ketone or imine in which a photographic reagent is joined to the .alpha.- atom through a hetero atom which is cleavable from the .alpha.-carbon atom, the process comprising the step of causing the photographic reagent releasing compound to react, under alkaline conditions 9 with oxidized 3- pyra-zolidone developing agent to cleave the hetero atom from the .alpha.-carbon atom and thereby release the photographic reagent.
13. A process of claim 12 wherein the photo-graphic reagent releasing compound has one of the follow-ing structures:
and wherein: Q is =0 or R4 where R4 is hydroxy or amino;
Y is -S-, -O- or -N-where R5 is hydrogen, alkyl, aryl or a covalent bond in a heterocyclic ring formed by Y and Z;
Z represents the atoms which, together with Y, form a photographic reagent;
n is 0 or 1;
Nu-X-E is a timing group which, upon displacement from the carbon atom to which it is attached, undergoes an intramolecular nucleophilic displacement reaction to release Y-Z, where Nu is a nucleophilic group, E is an electrophilic group and X is a linking group for spatially relating Nu and E, upon displacement from the carbon atom, to undergo an intramolecular nucleophilic displacement reaction;
R1 is hydrogen, halogen, alkyl, aryl, hetero-cyclyl, where R6 is alkyl, aryl, heterocyclyl, where R7 is alkyl, aryl or heterocyclyl;
R2 is alkyl, aryl, heterocyclyl, cyano, -N(R82, -SO2R8, -SO2OR8, -SO2N(R8 )2, - N+(R8 )3 or OR8 where Ra is hydrogen, alkyl, aryl or heterocyclyl, or two R8 groups can combine with a nitrogen atom to which they are attached to form a heterocyclic nitrogen ring; and R3 represents the atoms to complete a saturated or unsaturated, carbocyclic or heterocyclic ring Or ring system containing at least one 5- to 7-membered ring.
and wherein: Q is =0 or R4 where R4 is hydroxy or amino;
Y is -S-, -O- or -N-where R5 is hydrogen, alkyl, aryl or a covalent bond in a heterocyclic ring formed by Y and Z;
Z represents the atoms which, together with Y, form a photographic reagent;
n is 0 or 1;
Nu-X-E is a timing group which, upon displacement from the carbon atom to which it is attached, undergoes an intramolecular nucleophilic displacement reaction to release Y-Z, where Nu is a nucleophilic group, E is an electrophilic group and X is a linking group for spatially relating Nu and E, upon displacement from the carbon atom, to undergo an intramolecular nucleophilic displacement reaction;
R1 is hydrogen, halogen, alkyl, aryl, hetero-cyclyl, where R6 is alkyl, aryl, heterocyclyl, where R7 is alkyl, aryl or heterocyclyl;
R2 is alkyl, aryl, heterocyclyl, cyano, -N(R82, -SO2R8, -SO2OR8, -SO2N(R8 )2, - N+(R8 )3 or OR8 where Ra is hydrogen, alkyl, aryl or heterocyclyl, or two R8 groups can combine with a nitrogen atom to which they are attached to form a heterocyclic nitrogen ring; and R3 represents the atoms to complete a saturated or unsaturated, carbocyclic or heterocyclic ring Or ring system containing at least one 5- to 7-membered ring.
14. A process of claim 12 wherein the photo-graphic reagent releasing compound has one of tbe fol-lowing structures:
and wherein:
where R5 is hydrogen, alkyl, aryl or a covalent bond in a heterocyclic ring formed by Y and Z;
Z represents the atoms which, together with Y, form a photographic reagent;
n is 0 or 1;
Nu-X-E is a timing group which, upon displacement from the carbon atom to which it is attached, undergoes an intramolecular nucleophilic displacement reaction to release Y-Z, where Nu is a nucleophilic group, E is an electrophilic group and X is a linking group for spatially relating Nu and E, upon displacement from the carbon atom, to undergo an intramolecular nucleophilic displacement reaction;
R1 is hydrogen, halogen, alkyl, aryl, hetero-cyclyl, -(Nu-X-E)n Y-Z or O-R6 where R6 is alkyl, aryl, heterocyclyl, where R7 is alkyl, aryl or heterocyclyl;
R9 is alkyl, aryl or heterocyclyl and R10 is R9, (R11)2NS02-, R11SO2NR11-, (Rll)2 NCO-, or RllCONR1l-where Rll is hydrogen, alkyl, aryl or heterocyclyl.
and wherein:
where R5 is hydrogen, alkyl, aryl or a covalent bond in a heterocyclic ring formed by Y and Z;
Z represents the atoms which, together with Y, form a photographic reagent;
n is 0 or 1;
Nu-X-E is a timing group which, upon displacement from the carbon atom to which it is attached, undergoes an intramolecular nucleophilic displacement reaction to release Y-Z, where Nu is a nucleophilic group, E is an electrophilic group and X is a linking group for spatially relating Nu and E, upon displacement from the carbon atom, to undergo an intramolecular nucleophilic displacement reaction;
R1 is hydrogen, halogen, alkyl, aryl, hetero-cyclyl, -(Nu-X-E)n Y-Z or O-R6 where R6 is alkyl, aryl, heterocyclyl, where R7 is alkyl, aryl or heterocyclyl;
R9 is alkyl, aryl or heterocyclyl and R10 is R9, (R11)2NS02-, R11SO2NR11-, (Rll)2 NCO-, or RllCONR1l-where Rll is hydrogen, alkyl, aryl or heterocyclyl.
15. A process of claim 13 wherein the group Y-Z
forms a development inhibitor.
forms a development inhibitor.
16. A process of claim 14 wherein:
n is 0;
Y-Z is a development inhibitor;
R1 is hydrogen;
R9 is aryl; and R10 is (R11)2NSO2-, RllSO2NRll-, (R11)2NCO-.
n is 0;
Y-Z is a development inhibitor;
R1 is hydrogen;
R9 is aryl; and R10 is (R11)2NSO2-, RllSO2NRll-, (R11)2NCO-.
17. A process of claim 12 wherein oxidized 3-pyrazolidone developing agent is generated by silver halide development.
18. A process of claim 12 wherein the 3-pyra-zolidone developing agent is selected from the group con-sisting of 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazoli-done, 4-hydroxymethyl-4-methyl-1-(3,4-dimethylphenyl)-3-pyrazolidone, and 4-hydroxymethyl-4-methyl-1-p-tolyl-3-pyrazolidone.
19. A process of claim 17 further comprising, concurrent with the release of photographic reagent, forming an imagewise pattern of diffusible dye as a func-tion of silver halide development.
20. A process of claim 19 wherein the imagewise pattern of diffusible dye is formed as a direct function of silver halide development.
21. A process of claim 19 wherein the imagewise pattern of diffusible dye is formed in an inverse function of silver halide development.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US20781280A | 1980-11-17 | 1980-11-17 | |
| US207,812 | 1980-11-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1160881A true CA1160881A (en) | 1984-01-24 |
Family
ID=22772093
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000386830A Expired CA1160881A (en) | 1980-11-17 | 1981-09-28 | Release of photographic reagents with oxidized 3-pyrazolidone developing agents |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS57112752A (en) |
| CA (1) | CA1160881A (en) |
| DE (1) | DE3145640A1 (en) |
| FR (1) | FR2494459B1 (en) |
| GB (1) | GB2087581B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59131934A (en) * | 1983-01-19 | 1984-07-28 | Fuji Photo Film Co Ltd | Color photosensitive silver halide material |
| JPH0677143B2 (en) * | 1984-09-20 | 1994-09-28 | コニカ株式会社 | Photosensitive element for color diffusion transfer method |
| JPS61129643A (en) * | 1984-11-28 | 1986-06-17 | Konishiroku Photo Ind Co Ltd | Direct positive photosensitive silver halide material |
| JPS63153548A (en) * | 1986-12-17 | 1988-06-25 | Konica Corp | Silver halide color photographic sensitive material |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4199354A (en) * | 1973-01-26 | 1980-04-22 | Eastman Kodak Company | Positive-working immobile photographic compounds and photographic elements containing same |
| US3980479A (en) * | 1974-10-02 | 1976-09-14 | Eastman Kodak Company | Positive-working immobile photographic compounds which cleave by intramolecular nucleophilic displacement in alkali unless oxidized |
| DE2502892A1 (en) * | 1975-01-24 | 1976-07-29 | Agfa Gevaert Ag | LIGHT SENSITIVE COLOR PHOTOGRAPHIC MATERIAL |
| CA1134818A (en) * | 1977-12-23 | 1982-11-02 | Philip T.S. Lau | Release compounds and photographic emulsions, elements and processes utilizing them |
-
1981
- 1981-09-28 CA CA000386830A patent/CA1160881A/en not_active Expired
- 1981-11-12 FR FR8121127A patent/FR2494459B1/en not_active Expired
- 1981-11-17 DE DE19813145640 patent/DE3145640A1/en not_active Withdrawn
- 1981-11-17 GB GB8134565A patent/GB2087581B/en not_active Expired
- 1981-11-17 JP JP18319381A patent/JPS57112752A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| GB2087581B (en) | 1984-06-27 |
| JPS57112752A (en) | 1982-07-13 |
| FR2494459B1 (en) | 1987-02-27 |
| DE3145640A1 (en) | 1982-06-24 |
| GB2087581A (en) | 1982-05-26 |
| FR2494459A1 (en) | 1982-05-21 |
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