CA1178837A - Diffusion transfer photographic system using substituted phenylmercaptoazoles - Google Patents
Diffusion transfer photographic system using substituted phenylmercaptoazolesInfo
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- CA1178837A CA1178837A CA000393496A CA393496A CA1178837A CA 1178837 A CA1178837 A CA 1178837A CA 000393496 A CA000393496 A CA 000393496A CA 393496 A CA393496 A CA 393496A CA 1178837 A CA1178837 A CA 1178837A
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Abstract
ABSTRACT OF THE DISCLOSURE
There is disclosed a diffusion transfer photo-graphic system wherein development of an exposed photosensitive element with an aqueous alkaline processing composition is effected in the presence of a compound represented by the formula
There is disclosed a diffusion transfer photo-graphic system wherein development of an exposed photosensitive element with an aqueous alkaline processing composition is effected in the presence of a compound represented by the formula
Description
63~)5 11'78837 BACKGROUND OE' THE INVENTION
-This application relates generally to photography and, more specifically, to diffusion transfer photographic systems including products and processes.
Diffusion transfer photographic systems wherein images are formed in color by the use of image dye-providing materials such as dye developers are well known in the art.
Generally, multicolor transfer images are formed by processing an exposed multicolor photosensitive silver halide element with an aqueous alkaline processing composition distributed between two sheet-like elements, one of these elements including an image receiving layer. The processing composition is so applied and confined within and between the two sheet-like elements as not to contact or wet outer surfaces of the two superposed elements, thus providing a film unit whose external surfaces are dry. 'rhe proccssing composi~ion preferably is distributed in viscous form from a pressure rupturable container.
It is known in the art to carry out development in the presence of development restrainers whereby development of exposed silver halide is continued for a period of time sufficient to form an imagewise distribution of diffusible unoxidized dye developers in undeveloped areas of the silver halide emulsion layer(s) with the unoxidized dye developers being transferred by diffusion to a superposed image receiving element and, after the predeterminad development period, restraining further development of exposed silver halide by means of the development restrainer. See, for example, U.S.
Patent 3,~65,498. Various development restrainers which are useful for such purposes are known including mercaptoazoles J~:
1 ~'7~33'~
f such as l-phenyl-5-mercaptotetrazole. ~owever, the use of such development restrainers is subject to certain limitations.
For example, U.S. Patent 3,260,597 discloses that mercapto-azole development restrainers or 'larrestors", such as l-phenyl-5-mercaptotetrazole, can not be used in the aqueous alkaline processing composition in any appreciable amount because development of exposed silver halide will be stopped pre-maturely particularly in the outer blue alld green sensitive emulsion layers of a multicolor system.
It is also known in the art to use blocked develop-ment restrainers which are designed to provide a timod release of a development restrainer during the development process.
See, for example, U.S. Patent 3,698,898 which discloses the use of quinone- or naphtho~uinone-methide precursors which release a photoyraphic rcagent such as 1-~hcnyl-5-ln~rc~to-tetrazole in the presence of alkali; U.S. Patent 4,009,029 which discloses a class of cyanoethyl-containing blocked development restrainers; German Offenlegungsschrift 2,427,183 which discloses various blocked development restrainers, and U.S.
Patents 3,260,597 and 3,265,49~8, referred to above, which disclose hydrolyzable blocked restrainers.
The use of phenylmercaptetrazole compounds which are substituted on the phenyl ring as de~elopment inhibitors in certain conventional photographic systems is also known. See, for example, Research Disc]osure, July 1974, page 12, and U.S.
Patent 3,295,976.
SUMMARY OF - THE INVENTION
The present application relates to a diffusion transfer photographic system wherein the development process is carried out in the presence of phenylmercaptoazoles which are substituted on thc phenyl riny.
li'7B~37 Thus this invention seeks to provide a diffusion transfer photo-graphic system wherein development of an exposed photosensitive element is carried out in the presence of pheny~lmercaptoazole compounds which are substituted on the phenyl ring~
In the diffusion transfer photographic system of this invention the compounds utilized include a blocking group designed to provide a timed release of the substituted phenylmercaptoazoles durin~ the development process~
Further, in the diffus~ion transfer ~hotographic process of this invention the pH of the processing composition initially is substantially equal to or greater than the pKa of the substituent on the phenyl ring of the phenylmercaptoazole compound and subsequently, during development, the pH is lowered below the pKa.
Additionally, this invention provides a diffusion transfer photo-graphic system wherein the substituted phenylmercaptoazole compounds may be incorporated in the aqueous alkaline processing composition, or alter-natively a system wherein the substituted phenylmercaptotetrazole compounds may be incorporated in the photosensitive element~
This invention also seeks to provide a diffusion trans photo-graphic system wherein the photographic speed of one or more silver halide emulsions may be increased~
Further, this invention seeks to provide a diffusion transfer photographic system wherein fog development may be decreased~
This invention seeks to improve color diffusion transfer photo-graphic products and processes.
Hence in a first embodiment this invention provides a photographic product for use in forming a diffusion transfer photographic image comprising a photosensitive element comprising a support carrying at least one silver halide emulsion layer having associated therewith an image dye-providing material, a second sheet-like element positioned in superposed or super-posable relationship with said photosensitive element, an image receiving . 3---~ ` ~.1'7~ 37 layer positioned in one of said elements, means for lowering the pH of an aqueous alkaline processing composition positioned in one of said ele-ments, a rupturable container releasably holding an aqueous alkaline pro-cessing composition adapted, when distributed between a pair of predetermined layers carried by said photosensitive element and said second element, to develop said silver halide emulsion and provide a diffusion transfer image on said image receiving layer, said product including at least one compound represented by the formula ,-N
X~' 11 ~ ~ SR
Rl wherein X represents the nonmetallic atoms necessary to form a nucleus which completes a 5- or 6-membered heterocyclic moiety on said structure, R is H, an alkali metal or a group which is cleavable in said aqueous alkaline processing composition and Rl is either a group which has a pKa of from about 7 to about 14 which is ionizable to an anion and wherein the silver salt of the mercaptan resulting from cleavage or ionization of -SR
is more soluble in said aqueous alkaline processing composition in the pH
range within which Rl is ionized to an anion than said silver salt is below that pH range, or a precursor, wherein said processing composition initially has a pH substantially equal to or above the pKa of Rl and said means for . 20 lowering the p~ of an aqueous alkaline processing composition is adapted to .~ lower the pH of said aqueous alkaline processing composition below the pKa ., 1 In a second embodiment this invention provides a diffusion trans-fer photographic process comprising exposing a photosensitive element comprising a support carrying at least one silver halide emulsion layer having associated therewith an image dye-providing material, applying an ~ :, .. ~ -4-~ ~i7~33~
aqueous alkaline processing composition to said exposed photosensitive element to effect development and to form an imagewise distribution of image dye-providing material as a function of development and transferring at least a portion of said imagewise distribution of image dye-providing material to an image receiving layer in superposed or superposable relation-ship therewith to thereby provide a diffusion transfer image, said develop-ment being effected in the presence of at least one compound represented by the formula X~ ~
~-C - SR
~Rl wherein X represents the nonmetallic atoms necessary to form a nucleus which completes a 5- or 6-membered heterocyclic moiety on said structure, R is H, an alkali metal or a group which is cleavable in said photographic aqueous alkaline processing composition; and Rl is a group which has a pKa of from about 7 to about 14 which is ionizable to an anion and wherein the silver salt of the mercaptan resulting from cleavage or ionization of -SR
is more soluble in said aqueous alkaline processing composition in the pH
range within whlch Rl is ionized to an anion than said silver salt is below that pH range, or a precursor, wherein said processing composition has a pH
substantially equal to or above the pKa of Rl when said composition initially contacts said compound, and subsequently lowering the pH of said aqueous alkaline processing composition below the pKa of Rl.
The compounds which are useful according to the invention are gen-erally pheny3mercaptoazoles wherein the substituted phenyl moiety is attached to either a nitrogen atom or a carbon atom of the azole moiety. Accordingly, the compounds may be represented by either of the following formulas which are both within generic Formula A.
~4a-11'71~33'7 ... ~ .
"~N "-N
X~ ~ _ SR ~N~
~ Rl ¢~ Rl FORMULA B FORMULA C
The heterocyclic moieties formed by X preferably include those wherein the heterocyclic atoms (i.e., atoms other than carbon) are members of a single heterocyclic ring as contrasted with compounds containing fused or condensed heterocyclic rings in which the heterocyclic atoms are members of more than one heterocyclic ring. Typical suitable com-~ounds includ~ monoazolcs such as ben~oxazoles, bcnzothia~oles, etc.; diazoles such as benzimidazoles; triazoles such as 1,2,4-triazoles, etc.; tetrazoles and pyrimidines. In a preferred embodiment of the invention the compounds include a tetrazole nucleus.
The substituent (Rl) on the phenyl moiety may be either any suitable substituent which has a pKa of from about 7 io about 14 which is ionizable to an anion whereby the silver salt of the mercaptan (resulting from eleavage or ionization of -SR) i8 rendered more soluble in the pH range within which Rl is ionized to an anion than it is below that pH range, or a precursor of such a substituent. Typical suitable substit-O O
: ~ Il 11 e: -OH; -C-CH3; -O-C-CH3; SO2 2 2 3 -SO2NHC8H17; 52 ~ ; -NHso2cH3; NH~02 ~ CH3; and N-OH
-C-Z where Z is H, alkyl having from 1 to 10 carbon atoms, aralkyl such as benzyl or phenethyl, phenyl or substituted phenyl.
' .
117l3~37 The compounds within generic formula A wherein Rl is N-OH
-C-Z are novel compounds.
As stated previously, the compounds may include a mercaptan group attached to a carbon atom of the azole nucleus or may include a blocking group attached to the sulfur atom with the blocking group designed to cleave from the molecule in an aqueous alkaline medium to provide a timed release of the desired phenylmercaptoazole compound. Where R is a blocking group it may be any suitable blocking~group such as, for example, those which cleave by hydrolysis; those which cleave by quinone methide elimination (e.g., R is -CH2 ~ OH) such as disclosed in United States Patent 3,698,898; those which cleave by hydrolysis followed by quinone methide elimination (e.g., R is -CH2 ~ 0-C-CH3), and those which cleave O O
Il 11 by ~--elimination (e.g., R is -CH2_GH2_CN, -CH2-CH2-C-R2, -CH2-CH2-C-OR2, il /
where R2 is alkyl, and -CH2-CH2-C-N \ where R3 and R4 are H or alkyl).
Typical suitable blocking groups include, for example, -CH2-CH2-C NH2, O O o O
-C-Cl3H27~ -CH2-CH2 ~ , -CH2-C112-C ~ O-C8Hl7, -CH2-C~12-c-c18 37' O O
-CH2-CH2-C-OH, -C112-CI-12-C-O-CH3, and succinimido groups which are sub-stituted on the nitrogen atom with alkyl or aryl as disclosed in United States Patent 3,88~,677.
In a preferred embodiment of the invention, R is -CH2-CH2S02R5 where R5 is alkyl, aryl or substituted aryl. Novel sulfone compounds within Formula A wherein R is -CH2-CH2S02R5 and their use in photographic applications are disclosed and , ~ .
il7~3837 , ~
claimed in copending Canadian patent application No. 393,516 of James R. Bartels-Keith and Alan L. Borror, filed January 4, 1982.
Cleavage of the blocking group in aqueous alkaline medium releases, in a timed fashion during development, the substituted phenylmercaptoazole moiety. Cleavage of the blocking group occurs according to the following reaction sequence:
X ¦¦ o~ ~ X~
Rl Rl where R' is R minus a proton. The rate of release of the substi-tuted phenylmercaptoazole moiety is temperature dependent, that is, more is released as the temperature at which processing of the film unit is effected rises. Thus, more of the substituted phenylmercaptoazole moiety is made available at elevated tempera-tures, i.e D ~ above room temperature, where more is typically desired, less is released at room temperature and even less below room temperature where lesser amounts are needed. Thus, these blocked compounds which are utilized according to the invention provide more uniform sensitometry for the film units of the invention over a wide temperature range of processing. In other words, the sensitometry of the film units which include such blocked compounds according to the invention is less temperature dependent than would otherwise be the case.
The compounds which are useful according to the invention have been found to modify and/or control the sensito-metry when present during diffusion transfer processing of an exposed photosensitive element, particularly when such processing is carried out at elevated temperatures, e.g., at ~ 1~
ahout 95F. Such modification and/or control include a speed increase f~r one or more of the silver halide emulsions in a multicolor diffusion transfer photographic system and/or an increase in the Dmax of one or more of the individual colors due to control of fog development, as will be illustrated in detail below herein. The advantageous results obtained through the use of the mercaptoazole compounds according to the inven-tion are not completely understood. However, to further aid those skilled in the art to understand and practice the inven-tion, the proposed theoretical mechanism by which the advan-tageous results are thought to be effected will be discussed here. It should be understood, however, that the diffusion transfer photographic system has been proved to be operative and highly effective through extensive experimentation and the proposed theoretical mechanism is not to be construed as being limiting of the invention. It is theorized that the results obtained according to the invention are due to the compounds performing different functions at differ~nt stages of the development process, that is, as weak silver solvents and promoters of development at one stage of the development process and as development inhibitors, or restrainers, at another stage of the development process, and that the dual functions of these compounds within the diffusion transfer photographic system are pH dependent.
It is well known that in the diffusion transfer ~ photographic development proc~ss the pH of any particular ;~ location within the film unit varies with time. 'l'ypically, ; the processing composition employed in the process has a very high pH, e.g., from about 13-14, and during the development process each layer of the multilayer film unit goes thro~lgh a ,, ~ .
3;37 broad pH range which includes very high pH levels and relatively low pH levels. When the pH is substantially equal to or above the pKa of the substitutent Rl on the phenyl rin~, the dianion is formed, for example, N - N
N\ ~ S~
N
R1~3 and acts ~s a weak silver solvent to form relatively soluble silver salts, thus promoting development. When thc pll falls below the pKa of the substituent Rl~ the monoanion is formed, for example, N - N
N
~Rl and the silver salt of the monoanion of the compound is very low in solubility resulting in a development restrainer action.
In the instances whère certain substituted phenyl-mercaptotetrazole compounds were taught for use in specified photographic applications, i.e., the Research Disclosure ar-ticle and U.S. Patent 3,295,976, previously cited, the processes do not involve different pH at different st~ges of the development process. Thus, the pH-dependent d~al functions of these com-pounds were not known or utilized in the processes disclosed in these references.
The compounds used according to the invention may be incorporated in various loca~ions within the diffusion transfer film unit such as, for example, in the processing composition, in one or more layers within the photosensitive element or in one or more layers in the image-receiving element such as the image-receiving layer. In view of the foregoing discussion, it will be understood that, according to the invention, develop-ment of the exposed photosensitive element is carried out with a processing composition having an initial p}l substantially equal to or above the pka of Rl, at least for some period of time after the processing composition comes into contact with the mercapto-azole compound so as to enable the substituent to ioni~e to form the dianion. In addition, at some point during the development process the pH or the environment where the compound is located is reduced below the pka of Rl so as to form the monoanion.
BRIEP DESCRIPTION OF TIIE DRAWINGS
For a better understanding of the invention as well as other objects and further features thereof, reference is made to the following detailed description of various preferred embodiments thereof taken in conjunction with the accompanying drawings wherein:
Figure 1 is a graphical illustration of the relative amount of silver developed with respect to time in exposed and unexposed areas for a control film unit and a film unit according to the invention, both processed at room temperature; and ; Figure 2 is a similar graphical illustration for the same film units processed at 95F.
DESCRIPTION OF TIIE PREFERRED EMBODIMENTS
The preferred compounds which are employed in accordance with the invention are represented by the formulas --- - ` li 7~837 SH
N~ OH ( I ) Sll N - OH
N~ N _~--C - CH
N -N~ 3 (II) SH OH
N ~3 ( I I I ) N_N/
SH
IN~ N~SO NH
N=N/ 2 2 ( IV) SH
I ~ N ~ SO 2NE~CH 3 (V ) fH
¦ ~ N--~ SO2NH~ (VI ) N= N~
SH
N~I~
N8N~ ~NHSO2CH3 (VII) . .
~ ` 11'7~33~
j~N~ (VIII~
N_N/
S~
N=N/ ~NHS02~CH3 ~ IX) si~
N=N/ ~S02NHC8H17 (X) Sll N _--N / ~ CH 3 ( X I ) S (CH2) 2 2 3 N~ OEI (XII) N _N~
S (CH2) 2S02CH3 ~ (~ SO 2N H2 ( X I I I ) N`_-N
S (CH2) 2CCH3 (XIV~
¦ ~N~OH
N--N~
-This application relates generally to photography and, more specifically, to diffusion transfer photographic systems including products and processes.
Diffusion transfer photographic systems wherein images are formed in color by the use of image dye-providing materials such as dye developers are well known in the art.
Generally, multicolor transfer images are formed by processing an exposed multicolor photosensitive silver halide element with an aqueous alkaline processing composition distributed between two sheet-like elements, one of these elements including an image receiving layer. The processing composition is so applied and confined within and between the two sheet-like elements as not to contact or wet outer surfaces of the two superposed elements, thus providing a film unit whose external surfaces are dry. 'rhe proccssing composi~ion preferably is distributed in viscous form from a pressure rupturable container.
It is known in the art to carry out development in the presence of development restrainers whereby development of exposed silver halide is continued for a period of time sufficient to form an imagewise distribution of diffusible unoxidized dye developers in undeveloped areas of the silver halide emulsion layer(s) with the unoxidized dye developers being transferred by diffusion to a superposed image receiving element and, after the predeterminad development period, restraining further development of exposed silver halide by means of the development restrainer. See, for example, U.S.
Patent 3,~65,498. Various development restrainers which are useful for such purposes are known including mercaptoazoles J~:
1 ~'7~33'~
f such as l-phenyl-5-mercaptotetrazole. ~owever, the use of such development restrainers is subject to certain limitations.
For example, U.S. Patent 3,260,597 discloses that mercapto-azole development restrainers or 'larrestors", such as l-phenyl-5-mercaptotetrazole, can not be used in the aqueous alkaline processing composition in any appreciable amount because development of exposed silver halide will be stopped pre-maturely particularly in the outer blue alld green sensitive emulsion layers of a multicolor system.
It is also known in the art to use blocked develop-ment restrainers which are designed to provide a timod release of a development restrainer during the development process.
See, for example, U.S. Patent 3,698,898 which discloses the use of quinone- or naphtho~uinone-methide precursors which release a photoyraphic rcagent such as 1-~hcnyl-5-ln~rc~to-tetrazole in the presence of alkali; U.S. Patent 4,009,029 which discloses a class of cyanoethyl-containing blocked development restrainers; German Offenlegungsschrift 2,427,183 which discloses various blocked development restrainers, and U.S.
Patents 3,260,597 and 3,265,49~8, referred to above, which disclose hydrolyzable blocked restrainers.
The use of phenylmercaptetrazole compounds which are substituted on the phenyl ring as de~elopment inhibitors in certain conventional photographic systems is also known. See, for example, Research Disc]osure, July 1974, page 12, and U.S.
Patent 3,295,976.
SUMMARY OF - THE INVENTION
The present application relates to a diffusion transfer photographic system wherein the development process is carried out in the presence of phenylmercaptoazoles which are substituted on thc phenyl riny.
li'7B~37 Thus this invention seeks to provide a diffusion transfer photo-graphic system wherein development of an exposed photosensitive element is carried out in the presence of pheny~lmercaptoazole compounds which are substituted on the phenyl ring~
In the diffusion transfer photographic system of this invention the compounds utilized include a blocking group designed to provide a timed release of the substituted phenylmercaptoazoles durin~ the development process~
Further, in the diffus~ion transfer ~hotographic process of this invention the pH of the processing composition initially is substantially equal to or greater than the pKa of the substituent on the phenyl ring of the phenylmercaptoazole compound and subsequently, during development, the pH is lowered below the pKa.
Additionally, this invention provides a diffusion transfer photo-graphic system wherein the substituted phenylmercaptoazole compounds may be incorporated in the aqueous alkaline processing composition, or alter-natively a system wherein the substituted phenylmercaptotetrazole compounds may be incorporated in the photosensitive element~
This invention also seeks to provide a diffusion trans photo-graphic system wherein the photographic speed of one or more silver halide emulsions may be increased~
Further, this invention seeks to provide a diffusion transfer photographic system wherein fog development may be decreased~
This invention seeks to improve color diffusion transfer photo-graphic products and processes.
Hence in a first embodiment this invention provides a photographic product for use in forming a diffusion transfer photographic image comprising a photosensitive element comprising a support carrying at least one silver halide emulsion layer having associated therewith an image dye-providing material, a second sheet-like element positioned in superposed or super-posable relationship with said photosensitive element, an image receiving . 3---~ ` ~.1'7~ 37 layer positioned in one of said elements, means for lowering the pH of an aqueous alkaline processing composition positioned in one of said ele-ments, a rupturable container releasably holding an aqueous alkaline pro-cessing composition adapted, when distributed between a pair of predetermined layers carried by said photosensitive element and said second element, to develop said silver halide emulsion and provide a diffusion transfer image on said image receiving layer, said product including at least one compound represented by the formula ,-N
X~' 11 ~ ~ SR
Rl wherein X represents the nonmetallic atoms necessary to form a nucleus which completes a 5- or 6-membered heterocyclic moiety on said structure, R is H, an alkali metal or a group which is cleavable in said aqueous alkaline processing composition and Rl is either a group which has a pKa of from about 7 to about 14 which is ionizable to an anion and wherein the silver salt of the mercaptan resulting from cleavage or ionization of -SR
is more soluble in said aqueous alkaline processing composition in the pH
range within which Rl is ionized to an anion than said silver salt is below that pH range, or a precursor, wherein said processing composition initially has a pH substantially equal to or above the pKa of Rl and said means for . 20 lowering the p~ of an aqueous alkaline processing composition is adapted to .~ lower the pH of said aqueous alkaline processing composition below the pKa ., 1 In a second embodiment this invention provides a diffusion trans-fer photographic process comprising exposing a photosensitive element comprising a support carrying at least one silver halide emulsion layer having associated therewith an image dye-providing material, applying an ~ :, .. ~ -4-~ ~i7~33~
aqueous alkaline processing composition to said exposed photosensitive element to effect development and to form an imagewise distribution of image dye-providing material as a function of development and transferring at least a portion of said imagewise distribution of image dye-providing material to an image receiving layer in superposed or superposable relation-ship therewith to thereby provide a diffusion transfer image, said develop-ment being effected in the presence of at least one compound represented by the formula X~ ~
~-C - SR
~Rl wherein X represents the nonmetallic atoms necessary to form a nucleus which completes a 5- or 6-membered heterocyclic moiety on said structure, R is H, an alkali metal or a group which is cleavable in said photographic aqueous alkaline processing composition; and Rl is a group which has a pKa of from about 7 to about 14 which is ionizable to an anion and wherein the silver salt of the mercaptan resulting from cleavage or ionization of -SR
is more soluble in said aqueous alkaline processing composition in the pH
range within whlch Rl is ionized to an anion than said silver salt is below that pH range, or a precursor, wherein said processing composition has a pH
substantially equal to or above the pKa of Rl when said composition initially contacts said compound, and subsequently lowering the pH of said aqueous alkaline processing composition below the pKa of Rl.
The compounds which are useful according to the invention are gen-erally pheny3mercaptoazoles wherein the substituted phenyl moiety is attached to either a nitrogen atom or a carbon atom of the azole moiety. Accordingly, the compounds may be represented by either of the following formulas which are both within generic Formula A.
~4a-11'71~33'7 ... ~ .
"~N "-N
X~ ~ _ SR ~N~
~ Rl ¢~ Rl FORMULA B FORMULA C
The heterocyclic moieties formed by X preferably include those wherein the heterocyclic atoms (i.e., atoms other than carbon) are members of a single heterocyclic ring as contrasted with compounds containing fused or condensed heterocyclic rings in which the heterocyclic atoms are members of more than one heterocyclic ring. Typical suitable com-~ounds includ~ monoazolcs such as ben~oxazoles, bcnzothia~oles, etc.; diazoles such as benzimidazoles; triazoles such as 1,2,4-triazoles, etc.; tetrazoles and pyrimidines. In a preferred embodiment of the invention the compounds include a tetrazole nucleus.
The substituent (Rl) on the phenyl moiety may be either any suitable substituent which has a pKa of from about 7 io about 14 which is ionizable to an anion whereby the silver salt of the mercaptan (resulting from eleavage or ionization of -SR) i8 rendered more soluble in the pH range within which Rl is ionized to an anion than it is below that pH range, or a precursor of such a substituent. Typical suitable substit-O O
: ~ Il 11 e: -OH; -C-CH3; -O-C-CH3; SO2 2 2 3 -SO2NHC8H17; 52 ~ ; -NHso2cH3; NH~02 ~ CH3; and N-OH
-C-Z where Z is H, alkyl having from 1 to 10 carbon atoms, aralkyl such as benzyl or phenethyl, phenyl or substituted phenyl.
' .
117l3~37 The compounds within generic formula A wherein Rl is N-OH
-C-Z are novel compounds.
As stated previously, the compounds may include a mercaptan group attached to a carbon atom of the azole nucleus or may include a blocking group attached to the sulfur atom with the blocking group designed to cleave from the molecule in an aqueous alkaline medium to provide a timed release of the desired phenylmercaptoazole compound. Where R is a blocking group it may be any suitable blocking~group such as, for example, those which cleave by hydrolysis; those which cleave by quinone methide elimination (e.g., R is -CH2 ~ OH) such as disclosed in United States Patent 3,698,898; those which cleave by hydrolysis followed by quinone methide elimination (e.g., R is -CH2 ~ 0-C-CH3), and those which cleave O O
Il 11 by ~--elimination (e.g., R is -CH2_GH2_CN, -CH2-CH2-C-R2, -CH2-CH2-C-OR2, il /
where R2 is alkyl, and -CH2-CH2-C-N \ where R3 and R4 are H or alkyl).
Typical suitable blocking groups include, for example, -CH2-CH2-C NH2, O O o O
-C-Cl3H27~ -CH2-CH2 ~ , -CH2-C112-C ~ O-C8Hl7, -CH2-C~12-c-c18 37' O O
-CH2-CH2-C-OH, -C112-CI-12-C-O-CH3, and succinimido groups which are sub-stituted on the nitrogen atom with alkyl or aryl as disclosed in United States Patent 3,88~,677.
In a preferred embodiment of the invention, R is -CH2-CH2S02R5 where R5 is alkyl, aryl or substituted aryl. Novel sulfone compounds within Formula A wherein R is -CH2-CH2S02R5 and their use in photographic applications are disclosed and , ~ .
il7~3837 , ~
claimed in copending Canadian patent application No. 393,516 of James R. Bartels-Keith and Alan L. Borror, filed January 4, 1982.
Cleavage of the blocking group in aqueous alkaline medium releases, in a timed fashion during development, the substituted phenylmercaptoazole moiety. Cleavage of the blocking group occurs according to the following reaction sequence:
X ¦¦ o~ ~ X~
Rl Rl where R' is R minus a proton. The rate of release of the substi-tuted phenylmercaptoazole moiety is temperature dependent, that is, more is released as the temperature at which processing of the film unit is effected rises. Thus, more of the substituted phenylmercaptoazole moiety is made available at elevated tempera-tures, i.e D ~ above room temperature, where more is typically desired, less is released at room temperature and even less below room temperature where lesser amounts are needed. Thus, these blocked compounds which are utilized according to the invention provide more uniform sensitometry for the film units of the invention over a wide temperature range of processing. In other words, the sensitometry of the film units which include such blocked compounds according to the invention is less temperature dependent than would otherwise be the case.
The compounds which are useful according to the invention have been found to modify and/or control the sensito-metry when present during diffusion transfer processing of an exposed photosensitive element, particularly when such processing is carried out at elevated temperatures, e.g., at ~ 1~
ahout 95F. Such modification and/or control include a speed increase f~r one or more of the silver halide emulsions in a multicolor diffusion transfer photographic system and/or an increase in the Dmax of one or more of the individual colors due to control of fog development, as will be illustrated in detail below herein. The advantageous results obtained through the use of the mercaptoazole compounds according to the inven-tion are not completely understood. However, to further aid those skilled in the art to understand and practice the inven-tion, the proposed theoretical mechanism by which the advan-tageous results are thought to be effected will be discussed here. It should be understood, however, that the diffusion transfer photographic system has been proved to be operative and highly effective through extensive experimentation and the proposed theoretical mechanism is not to be construed as being limiting of the invention. It is theorized that the results obtained according to the invention are due to the compounds performing different functions at differ~nt stages of the development process, that is, as weak silver solvents and promoters of development at one stage of the development process and as development inhibitors, or restrainers, at another stage of the development process, and that the dual functions of these compounds within the diffusion transfer photographic system are pH dependent.
It is well known that in the diffusion transfer ~ photographic development proc~ss the pH of any particular ;~ location within the film unit varies with time. 'l'ypically, ; the processing composition employed in the process has a very high pH, e.g., from about 13-14, and during the development process each layer of the multilayer film unit goes thro~lgh a ,, ~ .
3;37 broad pH range which includes very high pH levels and relatively low pH levels. When the pH is substantially equal to or above the pKa of the substitutent Rl on the phenyl rin~, the dianion is formed, for example, N - N
N\ ~ S~
N
R1~3 and acts ~s a weak silver solvent to form relatively soluble silver salts, thus promoting development. When thc pll falls below the pKa of the substituent Rl~ the monoanion is formed, for example, N - N
N
~Rl and the silver salt of the monoanion of the compound is very low in solubility resulting in a development restrainer action.
In the instances whère certain substituted phenyl-mercaptotetrazole compounds were taught for use in specified photographic applications, i.e., the Research Disclosure ar-ticle and U.S. Patent 3,295,976, previously cited, the processes do not involve different pH at different st~ges of the development process. Thus, the pH-dependent d~al functions of these com-pounds were not known or utilized in the processes disclosed in these references.
The compounds used according to the invention may be incorporated in various loca~ions within the diffusion transfer film unit such as, for example, in the processing composition, in one or more layers within the photosensitive element or in one or more layers in the image-receiving element such as the image-receiving layer. In view of the foregoing discussion, it will be understood that, according to the invention, develop-ment of the exposed photosensitive element is carried out with a processing composition having an initial p}l substantially equal to or above the pka of Rl, at least for some period of time after the processing composition comes into contact with the mercapto-azole compound so as to enable the substituent to ioni~e to form the dianion. In addition, at some point during the development process the pH or the environment where the compound is located is reduced below the pka of Rl so as to form the monoanion.
BRIEP DESCRIPTION OF TIIE DRAWINGS
For a better understanding of the invention as well as other objects and further features thereof, reference is made to the following detailed description of various preferred embodiments thereof taken in conjunction with the accompanying drawings wherein:
Figure 1 is a graphical illustration of the relative amount of silver developed with respect to time in exposed and unexposed areas for a control film unit and a film unit according to the invention, both processed at room temperature; and ; Figure 2 is a similar graphical illustration for the same film units processed at 95F.
DESCRIPTION OF TIIE PREFERRED EMBODIMENTS
The preferred compounds which are employed in accordance with the invention are represented by the formulas --- - ` li 7~837 SH
N~ OH ( I ) Sll N - OH
N~ N _~--C - CH
N -N~ 3 (II) SH OH
N ~3 ( I I I ) N_N/
SH
IN~ N~SO NH
N=N/ 2 2 ( IV) SH
I ~ N ~ SO 2NE~CH 3 (V ) fH
¦ ~ N--~ SO2NH~ (VI ) N= N~
SH
N~I~
N8N~ ~NHSO2CH3 (VII) . .
~ ` 11'7~33~
j~N~ (VIII~
N_N/
S~
N=N/ ~NHS02~CH3 ~ IX) si~
N=N/ ~S02NHC8H17 (X) Sll N _--N / ~ CH 3 ( X I ) S (CH2) 2 2 3 N~ OEI (XII) N _N~
S (CH2) 2S02CH3 ~ (~ SO 2N H2 ( X I I I ) N`_-N
S (CH2) 2CCH3 (XIV~
¦ ~N~OH
N--N~
2 ) 2 3 tXV) N~
N~N~ ~ S2NH2 li7~83~
2 ) 2 N=~ ~
N~ OH (XVI) N=N/ \~,/
S(CH2)2 N - OH
N~ ~ 1l N~ C -- CH3 (X~III) N=N~ \ ~J
SCH2~o_C_cH3 N~ OH (XVIII) N--N/
SCH2~o_C_cH3 r 1 ~ ~ C - CH3 (XIX) N ~/
The mercaptoazole compounds which are useful according to the invention may be prepared by reactions which are well known in ~hc art. For cxample, 2-mercaptoimidazoles can be pre-pared by the reactions disclosed in The Chemistry of Hetero-cyclic Compounds Vol. 6: Imidazole and Its Derivatives, Part I, ~ 10 llofmann, Interscience Publishers, Inc., New York, 1953, pages : 77-85; Mercaptothiazoles and mercaptobenzothiazoles can be pre-pared according to the methods disclosed in The Chemistry of Heterocyclic Compounds Vol. 34: Thiazole and Its Derivatives, : Part I, Metzger, John Wiley and Sons, 1979, pages 260-269; Part 15 2, pages 370-377; benzoxazolethiones can be prepared according to the methods disclosed in l~eterocyclic Compounds, Vol. S, Elderfield, john Wiley and Sons, 1957, pages 439-444; 5-mercapto-1,3,4-oxadiazoles can be prepared according to the methods dis-closed in Heterocyclic Compounds, Vol. 7, Elderfield, John Wiley and Sons, 1961, page 352; mercapto-1,3,4-thiadiazoles, ibid, pages 587-612; and tetrazoles by the techniques disclosed in Heterocyclic CompoundR, Vol. 8, Elderfield, John Wiley and 33~
, _, .
Sons, 1967, pages 1-107. Mercapto-1,2,4-triazoles can be prepared by known literature techniques as described, for example, in Jour. Chem. Soc. E. Haggarth 1163 (1949). The compounds within Pormulas A, 8 and C where R is a blocking group can be prepared also by known reactions such as by pre-forming the monosodium salt of the appropriate mercaptoazole derivative and carrying out a condensation reaction with the appropriate blocking group in a solvent such as acetone, ethanol, acetonitrile, etc., or by reacting the mercaptoazole derivative with the appropriate blocking group in a suitable solvent in the presence of one equivalent of sodium bicarbonate.
Alternatively, the appropriate mercaptoazole derivative can be formed and the blocking group attached by means of a Michael addition with an appropriate olefin such as CH2=CH-Y where Y is an electron withdrawing group such as cyano, etc., according to known teachings in the art.
The preparation of compound I is described in Pharmazie, 29(2), (1974), pp 95-99. The preparation of compound IV is described in Khim. Geterotsikl. Soedin., Sb.l:
Azotsoderzhashchie Geterotsikl, 1967, pp 199-201. Compounds VI and VII can be prepared in accordance with the disclosure of United States Patent 3~295,976.
Compound II and compounds XII-XIX are per se novel compounds.
As stated previously, Rl may also be a precursor of a substituent which has the requisite properties and the desired substituent may be formed in situ. For example, where it is desired to develop the exposed photosensitive element in ~14~
7~8~'~
the presence of a compound within Formula A which has a hydroxy group on the phenyl ring, it is possible to incorporate in the film unit as a precursor a compound within Formula A which has a hydrolyzable ester group on the phenyl ring and generate the desired hydroxy group in situ during photographic processing.
It should be noted here that the acetyl group which is substituted on the phenyl ring in compound XI does not ionize to any appreciable extent to form an anion in an aqueous alkaline photographic processing composition. However, it has been shown by experimentation that incorporating compound XI in a film unit according to the invention will provide advantageous results. Thus, it would appear that compound XI undergoes a change in aqueous alkaline processing composition and that the acetyl substituent is a precursor of a group which has the requisite properties described above which provide the desired results. It has also been found that when incorporated in the processing composition for a period of time, for example, about a week or more, prior to processing of the exposed photosensi-tive element, the compound does not provide the desired results, thus indicating that it has long te~m instability characteris-tics in the aqueous alkaline processing composition. It is ther~-fore preferred to incorporate the compound elsewhere in the film unit, for example, in the photosensitive element.
Table I lists the pka of various substituents in certain of the compounds illustrated above.
TABLE I
COMPOUND pka I 10.10 + 0.1 II 11.4 III 9.5Q + 0.1 IV 9.95 + Q.l ~15;
~1 ~ 8B37 .
T~BLE I cont'd C~MPOUND ~
V 11.55 + 0.1 VI 9.55 + 0.1 VII 8.65 + 0.1 IX 8.80 ~ 0.1 Solubility product measurements were made for the silver salt of phenylmercaptotetrazole (PMT) at pll 13.5 and or the silver salt of compound II at pH 7 and pH 13.5 (above and helow the pka of the oxime substituent). The results are listed in Table II.
TABLE II
COMPOUND pH ~
PM~ 7 4 x lo 16 II 13.5 2 x 10 15 * Z.C.H. Tan, Photogr.Sci.~ng. 19, 17 ~1975) It is seen that while phenylmercaptotetrazole was relatively unaffected by pH the ionization of the oxime substituent increased the solubility of the silver salt of compound II by an order of magnitude.
The solubilities of the silver salts of PMT and compound II in the presence of excess amounts of their anions were measured at pH 7.0 and 13.5. Each solution was 4 x 10 3 molar in silver. The results are shown in Table III wherein the solubility data is expressed in ~moles/liter of total silver.
~ ~16~
TAB.LE III
COMPOUND II PMT
Molar Ratio pH pH
Compound/Ag7.0 13.5 7.0 13.5 1.25/1 ~1 19 <1 1.75/1 <1 44 <1 2 2.13/1 <1 93 1 4 2.5/1 2 140 3 8 4.5/1 2 320 15 18 7.5/1 5 1400 58 63 ~16a-~ ~ 11788~7 It can be seen that compound II is a weak to moderate silver solvent at high pH while PMT is not. Further, it is evident that when the oxime substituent is protonated it reverts to behavior which is similar to that of PMT. In fact, compound II forms an even less soluble salt in neutral solution than does PMT, thus giving it greater differentiation on the availability of silver in soluble form as the pH drops in the diffusion transfer development process.
As stated previously, the compounds which are employed according to the invention may be incorporated in any location in the film uni-t with the preferred location in any particular instance being dependent upon various factors such as the compound itself, the type of film unit and the results desired. The compounds generally may be incorporated in the film unit in any useful amount. Routine scoping tests may be used to ascertain the concentration appropriate for any given film unit and location. When the compounds are incor-porated in the processiny composition they are present prefer-ably in an amount of from about 0.02 to about 0.07% by weight.
When incorporated in a layer in the photosensitive element the compounds are typically present in a ratio of from about 1 mg/m2 to about 3 mg/m to about 3800 mg/m2 of silver. It has been o~served that, typically, where the compounds are incorporated in the photosensitive element, the total amoun-t required per film unit to give a desired result is less th~n that required when the compound is incorporated in the processing composition.
It has also been observed that too great an amount of the compounds can lead to reduced control of on`e or more of the imaye dye-providing materials which results in high Dmin values in the photographic reproduction or can lead to a loss in D
for one or more colors as will be apparent from the Examples.
33~7 , ~ ~.
In a preferred emb~iment of the invention com-pounds aeeording to the invention ean be ineorporated in more than one location in the diffusion transfer film unit. For example, part of the total quanti-y of the substituted phenyl-mercaptoazole eompound ean be ineorporated in the processingeomposition and the remainder in the photosensitive element.
Thus, during the initial stages of development, the quantity available ean be appropriate to provide a speed increase for one or more silver halide emulsions (silver solvent effect) without providing any undesired premature development restraint ; and the additional quantity dissolved during ~roccssing could give a total concentration desired to prevent further develop-ment. This embodiment is partieularly useful where R is H or an alkali metal for the compound incorporated in the pro-cessin~ composition and R is a cleavable group for the compound incorporated in the photosensitive element.
The compounds used in accordance with the invention may be used generally in assoeiation with any silver halide emulsion. It is preferred to use the compounds in a diffusion transfer photograp~ic system which ineludes a negative - silver halide emulsion, i.e., one whieh develops in the areas of exposure. The diffusion transfer photographie system of the invention may inelude any image dye-providing material in assoeiation with the silver halide emulsion(s).
The image dye-providing materials whieh can be utilized generally may be eharacterized as either (l) initially soluble or diffusible in the proeessing eomposition but which a~ sel~ctivcly renderod nondiffusible imayewisc as a Eunction of development; or (2) initially insoluble or nondiffusible in the proeessing eomposition but whieh seleetively provide a diffusible product imagewise as a function of development.
The image dye-providing materials may be complete dyes or dye intermediates, e.g., color couplers. The requisite differential in mobility or solubility may be obtained, for example, by a chemical reaction such as a redox reaction, a coupling reaction or a cleavage reaction. In a particularly preferred embodiment of the invention the image dye-providing materials are dye developers which are initially diffusible materials. The dye developers contain, in the same molecule, both the chromophoric system of a dye and a silver halide developing function as is described in U.S. Patent 2,983,606.
Other image dye-providing materials which may be used include, for example, initially diffusible coupling dyes such as are useful in the diffusion transfer process described in U. S.
Patent 3,087,817 and which are rendered nondiffusible by coupling with the oxidation product of a color developer;
initially nondiffusible dyes which release a diffusible dye Eollowiny oxida~ion, som~times refcrred to as "redox ~yc releaser" dyes, such as described in U.S. Patents 3,725,062 and 4,076,529; initially nondiffusible image dye-providing materials which release a diffusible dye following oxidation and intramolecular ring closure as are described in U.S. Patent
N~N~ ~ S2NH2 li7~83~
2 ) 2 N=~ ~
N~ OH (XVI) N=N/ \~,/
S(CH2)2 N - OH
N~ ~ 1l N~ C -- CH3 (X~III) N=N~ \ ~J
SCH2~o_C_cH3 N~ OH (XVIII) N--N/
SCH2~o_C_cH3 r 1 ~ ~ C - CH3 (XIX) N ~/
The mercaptoazole compounds which are useful according to the invention may be prepared by reactions which are well known in ~hc art. For cxample, 2-mercaptoimidazoles can be pre-pared by the reactions disclosed in The Chemistry of Hetero-cyclic Compounds Vol. 6: Imidazole and Its Derivatives, Part I, ~ 10 llofmann, Interscience Publishers, Inc., New York, 1953, pages : 77-85; Mercaptothiazoles and mercaptobenzothiazoles can be pre-pared according to the methods disclosed in The Chemistry of Heterocyclic Compounds Vol. 34: Thiazole and Its Derivatives, : Part I, Metzger, John Wiley and Sons, 1979, pages 260-269; Part 15 2, pages 370-377; benzoxazolethiones can be prepared according to the methods disclosed in l~eterocyclic Compounds, Vol. S, Elderfield, john Wiley and Sons, 1957, pages 439-444; 5-mercapto-1,3,4-oxadiazoles can be prepared according to the methods dis-closed in Heterocyclic Compounds, Vol. 7, Elderfield, John Wiley and Sons, 1961, page 352; mercapto-1,3,4-thiadiazoles, ibid, pages 587-612; and tetrazoles by the techniques disclosed in Heterocyclic CompoundR, Vol. 8, Elderfield, John Wiley and 33~
, _, .
Sons, 1967, pages 1-107. Mercapto-1,2,4-triazoles can be prepared by known literature techniques as described, for example, in Jour. Chem. Soc. E. Haggarth 1163 (1949). The compounds within Pormulas A, 8 and C where R is a blocking group can be prepared also by known reactions such as by pre-forming the monosodium salt of the appropriate mercaptoazole derivative and carrying out a condensation reaction with the appropriate blocking group in a solvent such as acetone, ethanol, acetonitrile, etc., or by reacting the mercaptoazole derivative with the appropriate blocking group in a suitable solvent in the presence of one equivalent of sodium bicarbonate.
Alternatively, the appropriate mercaptoazole derivative can be formed and the blocking group attached by means of a Michael addition with an appropriate olefin such as CH2=CH-Y where Y is an electron withdrawing group such as cyano, etc., according to known teachings in the art.
The preparation of compound I is described in Pharmazie, 29(2), (1974), pp 95-99. The preparation of compound IV is described in Khim. Geterotsikl. Soedin., Sb.l:
Azotsoderzhashchie Geterotsikl, 1967, pp 199-201. Compounds VI and VII can be prepared in accordance with the disclosure of United States Patent 3~295,976.
Compound II and compounds XII-XIX are per se novel compounds.
As stated previously, Rl may also be a precursor of a substituent which has the requisite properties and the desired substituent may be formed in situ. For example, where it is desired to develop the exposed photosensitive element in ~14~
7~8~'~
the presence of a compound within Formula A which has a hydroxy group on the phenyl ring, it is possible to incorporate in the film unit as a precursor a compound within Formula A which has a hydrolyzable ester group on the phenyl ring and generate the desired hydroxy group in situ during photographic processing.
It should be noted here that the acetyl group which is substituted on the phenyl ring in compound XI does not ionize to any appreciable extent to form an anion in an aqueous alkaline photographic processing composition. However, it has been shown by experimentation that incorporating compound XI in a film unit according to the invention will provide advantageous results. Thus, it would appear that compound XI undergoes a change in aqueous alkaline processing composition and that the acetyl substituent is a precursor of a group which has the requisite properties described above which provide the desired results. It has also been found that when incorporated in the processing composition for a period of time, for example, about a week or more, prior to processing of the exposed photosensi-tive element, the compound does not provide the desired results, thus indicating that it has long te~m instability characteris-tics in the aqueous alkaline processing composition. It is ther~-fore preferred to incorporate the compound elsewhere in the film unit, for example, in the photosensitive element.
Table I lists the pka of various substituents in certain of the compounds illustrated above.
TABLE I
COMPOUND pka I 10.10 + 0.1 II 11.4 III 9.5Q + 0.1 IV 9.95 + Q.l ~15;
~1 ~ 8B37 .
T~BLE I cont'd C~MPOUND ~
V 11.55 + 0.1 VI 9.55 + 0.1 VII 8.65 + 0.1 IX 8.80 ~ 0.1 Solubility product measurements were made for the silver salt of phenylmercaptotetrazole (PMT) at pll 13.5 and or the silver salt of compound II at pH 7 and pH 13.5 (above and helow the pka of the oxime substituent). The results are listed in Table II.
TABLE II
COMPOUND pH ~
PM~ 7 4 x lo 16 II 13.5 2 x 10 15 * Z.C.H. Tan, Photogr.Sci.~ng. 19, 17 ~1975) It is seen that while phenylmercaptotetrazole was relatively unaffected by pH the ionization of the oxime substituent increased the solubility of the silver salt of compound II by an order of magnitude.
The solubilities of the silver salts of PMT and compound II in the presence of excess amounts of their anions were measured at pH 7.0 and 13.5. Each solution was 4 x 10 3 molar in silver. The results are shown in Table III wherein the solubility data is expressed in ~moles/liter of total silver.
~ ~16~
TAB.LE III
COMPOUND II PMT
Molar Ratio pH pH
Compound/Ag7.0 13.5 7.0 13.5 1.25/1 ~1 19 <1 1.75/1 <1 44 <1 2 2.13/1 <1 93 1 4 2.5/1 2 140 3 8 4.5/1 2 320 15 18 7.5/1 5 1400 58 63 ~16a-~ ~ 11788~7 It can be seen that compound II is a weak to moderate silver solvent at high pH while PMT is not. Further, it is evident that when the oxime substituent is protonated it reverts to behavior which is similar to that of PMT. In fact, compound II forms an even less soluble salt in neutral solution than does PMT, thus giving it greater differentiation on the availability of silver in soluble form as the pH drops in the diffusion transfer development process.
As stated previously, the compounds which are employed according to the invention may be incorporated in any location in the film uni-t with the preferred location in any particular instance being dependent upon various factors such as the compound itself, the type of film unit and the results desired. The compounds generally may be incorporated in the film unit in any useful amount. Routine scoping tests may be used to ascertain the concentration appropriate for any given film unit and location. When the compounds are incor-porated in the processiny composition they are present prefer-ably in an amount of from about 0.02 to about 0.07% by weight.
When incorporated in a layer in the photosensitive element the compounds are typically present in a ratio of from about 1 mg/m2 to about 3 mg/m to about 3800 mg/m2 of silver. It has been o~served that, typically, where the compounds are incorporated in the photosensitive element, the total amoun-t required per film unit to give a desired result is less th~n that required when the compound is incorporated in the processing composition.
It has also been observed that too great an amount of the compounds can lead to reduced control of on`e or more of the imaye dye-providing materials which results in high Dmin values in the photographic reproduction or can lead to a loss in D
for one or more colors as will be apparent from the Examples.
33~7 , ~ ~.
In a preferred emb~iment of the invention com-pounds aeeording to the invention ean be ineorporated in more than one location in the diffusion transfer film unit. For example, part of the total quanti-y of the substituted phenyl-mercaptoazole eompound ean be ineorporated in the processingeomposition and the remainder in the photosensitive element.
Thus, during the initial stages of development, the quantity available ean be appropriate to provide a speed increase for one or more silver halide emulsions (silver solvent effect) without providing any undesired premature development restraint ; and the additional quantity dissolved during ~roccssing could give a total concentration desired to prevent further develop-ment. This embodiment is partieularly useful where R is H or an alkali metal for the compound incorporated in the pro-cessin~ composition and R is a cleavable group for the compound incorporated in the photosensitive element.
The compounds used in accordance with the invention may be used generally in assoeiation with any silver halide emulsion. It is preferred to use the compounds in a diffusion transfer photograp~ic system which ineludes a negative - silver halide emulsion, i.e., one whieh develops in the areas of exposure. The diffusion transfer photographie system of the invention may inelude any image dye-providing material in assoeiation with the silver halide emulsion(s).
The image dye-providing materials whieh can be utilized generally may be eharacterized as either (l) initially soluble or diffusible in the proeessing eomposition but which a~ sel~ctivcly renderod nondiffusible imayewisc as a Eunction of development; or (2) initially insoluble or nondiffusible in the proeessing eomposition but whieh seleetively provide a diffusible product imagewise as a function of development.
The image dye-providing materials may be complete dyes or dye intermediates, e.g., color couplers. The requisite differential in mobility or solubility may be obtained, for example, by a chemical reaction such as a redox reaction, a coupling reaction or a cleavage reaction. In a particularly preferred embodiment of the invention the image dye-providing materials are dye developers which are initially diffusible materials. The dye developers contain, in the same molecule, both the chromophoric system of a dye and a silver halide developing function as is described in U.S. Patent 2,983,606.
Other image dye-providing materials which may be used include, for example, initially diffusible coupling dyes such as are useful in the diffusion transfer process described in U. S.
Patent 3,087,817 and which are rendered nondiffusible by coupling with the oxidation product of a color developer;
initially nondiffusible dyes which release a diffusible dye Eollowiny oxida~ion, som~times refcrred to as "redox ~yc releaser" dyes, such as described in U.S. Patents 3,725,062 and 4,076,529; initially nondiffusible image dye-providing materials which release a diffusible dye following oxidation and intramolecular ring closure as are described in U.S. Patent
3,433,939 or undergo silver assisted cleavage to release a diffusible dye in accordance with the disclosure of U.S. Patent 3,719,489; and initially nondiffusible image dye-providing materials which release a diffusible dye following coupling with an oxidized color developer as described in U.S. Patent 3,227,550-The compounds may be incorporated into the photo-graphic elements by any suitable technique. In embodiments 1~'7~3837 ~ , where the compounds are incorporated in a separate discrete layer or in a silver halide emulsion layer they are typically coated from a water dispersion and the layer includes a binder material such as gelatin or the like-The diffusion transfer film units of the invention include those wherein the image receiving element is designed to be separated from the photosensitive element after processing and integral positive-negative diffusion transfer film units which are retained intact after processing. In a preferred em-bodiment the diffusion transfer film units of the invention utilize initially diffusible dye developers as the image dye-providing materials. As described in U.S. Patent 2,983,606, a photosensitive element containing a dye developer and a silver halide emulsion is photoexposed and a processing composition applied thereto, for example, by immersion, coating, spraying, flowing, etc., in the dark. The exposed photosensitive element is supexposed prior to, during, or after the processing composi-tion is applied, on a sheet-like support element which may be utilized as an image-receiving element. In a preferred embodi-ment, the processing composition is applied to the exposed photo-sensitive element in a substàntially uniform layer as the photo-sensitive element is brought into superposed relationship with the image-receiving layer. The processing composition, posi-tioned intermediate the photosensitive element and the image-receiving layex, permeates the emulsion to initiate development of the latent image contained therein. The dye developer is i~nobilized or precipitated in exposed areas as a consequence of the development of the latent lmage. This immobilization is apparently, at least in part, due to a change in the solubility characteristics of the dye developer upon oxidation and especi-1~ 33~7 ~ .
ally as regards its solubility in alkaline solutions. It may also be due in part to a tanning effect on the emulsion by oxidized developing agent, and in part to a localized exhaustion of alkali as a result of development. In unexposed and partially exposed areas of the emulsion, the dye developer is unreacted and diffusible and thus provides an imagewise distribution of unoxidized dye developer, diffusible in the processing composi-tion, as a function of the point-to-point degree of exposure of the silver halide emulsion. At least part of this imagewise distribution of unoxidized dye developer is transferred, by imbibition, to a superposed image-receiving layer or element, said transfer substantially excluding oxidized dye developer.
The image-receiving layer receives a depthwise diEfusion, from the developed emulsion, of unoxidized dye developer without appreciably disturbing the imagewise distribution thereof to provide a reversed or positive color image of the developed image. The image-receiving element may contain agents adapted to mordant or otherwise fix the diffused, unoxidized dye developer. In a preferred embodiment of said U.S. Patent No.
2,983,606 and in certain commercial applications thereof, the desired positive image is revealed by separating the image-receiving layer from the ~hotosensitive element at the end of a sui~able imbibition period. ~lternatively, as also disclose~d in said U.S. Patent No. 2,983,606, the image-receiving layer need not be separated from its superposed contact with the photosensi-tive element, subse~uent to transfer image formation, if the support for the image-receiving layer, as well as any other layers ~ntermediate said support and image-receiving layer, is transparent and a processing composition containing a substance, e.g., a white pigment, effective to mask the developed silver -~ ` 117~837 halide emulsion or emulsions is applied between the image-receiving layer and said silver halide emulsion or emulsions.
Dye developers, as noted in said U.S. Patent No.
2,983,606, are compounds which contain, in the same molecule, S both the chromophoric system of a dye and also a silver halide developing function. By "a silver halide developing function"
is meant a grouping adapted to develop exposed silver halide.
A preferred silver halide development function is a hydro-quinonyl group. In general, the development function includes a benzonoid developing function, that is, an aromatic developing group which forms quinonoid or quinone substances when oxidized.
Multicolor images may be obtained using dye developers in diffusion transfer processes by several techniques. One such technique contemplates obtaining multicolor transfer images utili~ing dye developers by employment of an inteyral mul~ilayer pho~osensitive elemen~, such as is discloscd in the aforementioned U.S. Patent No. 2,983,606 and in U.S. Patent No.
3,345,163, wherein at least two selectively sensiti~ed photo-sensitive strata, superposed on a single support, ~re processed, simultaneously and without separation, with a single con~on image-receiving layer. A suitable arrange~ent of this type comprises a support carrying a red-sensitive silvex halide emulsion stratum, a gre~l-sensitive silver halide emulsion stratum and a blue-sensitive silver halide emulsion stratum, said emulsions having associated therewith, respectively, for example, a cyan dye developer, a magenta dye developer and a yellow dye developer. The dye developer may be utilized in the silver halide emulsion stratum, for example in the form o~ par~icles, or it may be disposed in a stratum behind the appropriate silver halide emulsion st.rata. Each set of silver 1178~37 halide emulsion and associated dye developer state may be separated from other sets by suitable interlayers, for example, by a layer or stratum of gelatin or polyvinyl alcohol. In cer-tain instances, it may be desirable to incorporate a yellow filter in front of the green-sensitive emulsion and such yellow filter may be incorporated in an interlayer. However, where desirable, a yellow dye developer of the appropriate spectral characteristics and present in a state capable of functioning as a yellow filter may be so employed and a separate yellow filter omitted.
Particularly useful products for obtaining multi-cqlor dye developer images are disclosed in United States Patent No. 3,415,644. This patent discloses photographic products wherein a photosensitive element and an image-receiving element are maintained in fixed relationship prior to exposure, and this relationship is maintained as a laminate after processing and image formation. In these products, the final image is viewed through a transparent ~support) element against a light-reflecting, i.e., white background. Photoexposure is made through said transparent element and application of the processing composition provides a layer of light-reflecting material to provide a white background. The light-reflecting material (referred to in said patent as an "opacifying agent"~
is preferahly titanium dioxide, and it also performs an opacifying function, i.e., it is effective to mask the developed silver halide emulsions so that the transfer image may be viewed without interference therefrom, and it also acts to protect the photoexposed silver halide emulsions from post-expos.ure fogging by light passing thro~gh said transparent layer if the photQexposed film unit is. removed from the camera beore image~formation:is completed.
X ~23_ ' ~178837 United States Patent No. 3,647,437 is concerned with improvements in products and processes disclosed in said United States Patent No 3,415,644, and discloses the provision of light-absorbing materials to permit such processes to be performed, out-side of the camera in which photoexposure is effected, under much more intense ambient light conditions. A light-absorbing material or reagent, preferably a pH-sensitive phthalein dye, is provided so positioned and/or constituted as not to interfere with photo-exposure but so positioned between the photoexposed silver halide emulsions and the transparent support during processing after photoexposure as to absorb light which otherwise might fog the photoexposed emulsions. Furthermore, the light-absorbing material is so positioned and/or constituted after processing as not to interfere with viewing the desired image shortly after said image has been formed. In the preferred embodiments, the light-absorbing material, also sometimes referred to as an optical filter agent, is initially contained in the processing composition together with a light-reflecting material, e.g., titanium dioxide. The concentration of the light-absorbing dye is selected to provide the light transmission opacity required to perform the particular process under the selected light conditions.
In a particularly useful embodiment, the light-absorbing dye is lighly colored at the pH of the processing composition, e.g., 13-14, but is substantially non-absorbing of visible light at a lower pH, e.g., less than 10-12. This pH reduction may be effected by an acid-reacting reagent appropriately positioned in the film unit, e.g., in a layer between the transparent support and the image-receiving layer.
The dye developers are preferably selected for 3Q th~ir ability to provide colors that are useful in carrying X -24_ 3'7 out substractive color photography, that is, the previously mentioned cyan, magenta and yellow. ~he dye developers employed may be incorporated in the respective silver halide emulsion or, in the preferred embodiment, in a separate layer behind the respective silver halide emulsion, and such a layer of dye developer may be applied by use of a coating solution containing the respective dye developer distributed, in a concentration calculated to give the desired coverage of dye developer per unit area, in a film-forming natural, or synthetic, polymer, for example, gelatin, polyvinyl alcohol, and the like, adapted to be permeated by the processing composition.
Other diffusion transfer products and processes according to the invention are the types described in United States Patents 3,573,043 and 3,594,165.
A particularly useful film unit according to the invention is one wherein the photosensitive element includes a light-reflecting layer between the silver halide layer and the image dye-providing layer (as described in Canadian Patent 668,952), the substrate of the photosensitive element carries the polymeric acid neutralizing layer which in turn carries the timing layer (as described in United States Patent 3,573,043) and the processing composition includes an oximated polydiacetone acrylamide thickening agent (as described in United States Patent
ally as regards its solubility in alkaline solutions. It may also be due in part to a tanning effect on the emulsion by oxidized developing agent, and in part to a localized exhaustion of alkali as a result of development. In unexposed and partially exposed areas of the emulsion, the dye developer is unreacted and diffusible and thus provides an imagewise distribution of unoxidized dye developer, diffusible in the processing composi-tion, as a function of the point-to-point degree of exposure of the silver halide emulsion. At least part of this imagewise distribution of unoxidized dye developer is transferred, by imbibition, to a superposed image-receiving layer or element, said transfer substantially excluding oxidized dye developer.
The image-receiving layer receives a depthwise diEfusion, from the developed emulsion, of unoxidized dye developer without appreciably disturbing the imagewise distribution thereof to provide a reversed or positive color image of the developed image. The image-receiving element may contain agents adapted to mordant or otherwise fix the diffused, unoxidized dye developer. In a preferred embodiment of said U.S. Patent No.
2,983,606 and in certain commercial applications thereof, the desired positive image is revealed by separating the image-receiving layer from the ~hotosensitive element at the end of a sui~able imbibition period. ~lternatively, as also disclose~d in said U.S. Patent No. 2,983,606, the image-receiving layer need not be separated from its superposed contact with the photosensi-tive element, subse~uent to transfer image formation, if the support for the image-receiving layer, as well as any other layers ~ntermediate said support and image-receiving layer, is transparent and a processing composition containing a substance, e.g., a white pigment, effective to mask the developed silver -~ ` 117~837 halide emulsion or emulsions is applied between the image-receiving layer and said silver halide emulsion or emulsions.
Dye developers, as noted in said U.S. Patent No.
2,983,606, are compounds which contain, in the same molecule, S both the chromophoric system of a dye and also a silver halide developing function. By "a silver halide developing function"
is meant a grouping adapted to develop exposed silver halide.
A preferred silver halide development function is a hydro-quinonyl group. In general, the development function includes a benzonoid developing function, that is, an aromatic developing group which forms quinonoid or quinone substances when oxidized.
Multicolor images may be obtained using dye developers in diffusion transfer processes by several techniques. One such technique contemplates obtaining multicolor transfer images utili~ing dye developers by employment of an inteyral mul~ilayer pho~osensitive elemen~, such as is discloscd in the aforementioned U.S. Patent No. 2,983,606 and in U.S. Patent No.
3,345,163, wherein at least two selectively sensiti~ed photo-sensitive strata, superposed on a single support, ~re processed, simultaneously and without separation, with a single con~on image-receiving layer. A suitable arrange~ent of this type comprises a support carrying a red-sensitive silvex halide emulsion stratum, a gre~l-sensitive silver halide emulsion stratum and a blue-sensitive silver halide emulsion stratum, said emulsions having associated therewith, respectively, for example, a cyan dye developer, a magenta dye developer and a yellow dye developer. The dye developer may be utilized in the silver halide emulsion stratum, for example in the form o~ par~icles, or it may be disposed in a stratum behind the appropriate silver halide emulsion st.rata. Each set of silver 1178~37 halide emulsion and associated dye developer state may be separated from other sets by suitable interlayers, for example, by a layer or stratum of gelatin or polyvinyl alcohol. In cer-tain instances, it may be desirable to incorporate a yellow filter in front of the green-sensitive emulsion and such yellow filter may be incorporated in an interlayer. However, where desirable, a yellow dye developer of the appropriate spectral characteristics and present in a state capable of functioning as a yellow filter may be so employed and a separate yellow filter omitted.
Particularly useful products for obtaining multi-cqlor dye developer images are disclosed in United States Patent No. 3,415,644. This patent discloses photographic products wherein a photosensitive element and an image-receiving element are maintained in fixed relationship prior to exposure, and this relationship is maintained as a laminate after processing and image formation. In these products, the final image is viewed through a transparent ~support) element against a light-reflecting, i.e., white background. Photoexposure is made through said transparent element and application of the processing composition provides a layer of light-reflecting material to provide a white background. The light-reflecting material (referred to in said patent as an "opacifying agent"~
is preferahly titanium dioxide, and it also performs an opacifying function, i.e., it is effective to mask the developed silver halide emulsions so that the transfer image may be viewed without interference therefrom, and it also acts to protect the photoexposed silver halide emulsions from post-expos.ure fogging by light passing thro~gh said transparent layer if the photQexposed film unit is. removed from the camera beore image~formation:is completed.
X ~23_ ' ~178837 United States Patent No. 3,647,437 is concerned with improvements in products and processes disclosed in said United States Patent No 3,415,644, and discloses the provision of light-absorbing materials to permit such processes to be performed, out-side of the camera in which photoexposure is effected, under much more intense ambient light conditions. A light-absorbing material or reagent, preferably a pH-sensitive phthalein dye, is provided so positioned and/or constituted as not to interfere with photo-exposure but so positioned between the photoexposed silver halide emulsions and the transparent support during processing after photoexposure as to absorb light which otherwise might fog the photoexposed emulsions. Furthermore, the light-absorbing material is so positioned and/or constituted after processing as not to interfere with viewing the desired image shortly after said image has been formed. In the preferred embodiments, the light-absorbing material, also sometimes referred to as an optical filter agent, is initially contained in the processing composition together with a light-reflecting material, e.g., titanium dioxide. The concentration of the light-absorbing dye is selected to provide the light transmission opacity required to perform the particular process under the selected light conditions.
In a particularly useful embodiment, the light-absorbing dye is lighly colored at the pH of the processing composition, e.g., 13-14, but is substantially non-absorbing of visible light at a lower pH, e.g., less than 10-12. This pH reduction may be effected by an acid-reacting reagent appropriately positioned in the film unit, e.g., in a layer between the transparent support and the image-receiving layer.
The dye developers are preferably selected for 3Q th~ir ability to provide colors that are useful in carrying X -24_ 3'7 out substractive color photography, that is, the previously mentioned cyan, magenta and yellow. ~he dye developers employed may be incorporated in the respective silver halide emulsion or, in the preferred embodiment, in a separate layer behind the respective silver halide emulsion, and such a layer of dye developer may be applied by use of a coating solution containing the respective dye developer distributed, in a concentration calculated to give the desired coverage of dye developer per unit area, in a film-forming natural, or synthetic, polymer, for example, gelatin, polyvinyl alcohol, and the like, adapted to be permeated by the processing composition.
Other diffusion transfer products and processes according to the invention are the types described in United States Patents 3,573,043 and 3,594,165.
A particularly useful film unit according to the invention is one wherein the photosensitive element includes a light-reflecting layer between the silver halide layer and the image dye-providing layer (as described in Canadian Patent 668,952), the substrate of the photosensitive element carries the polymeric acid neutralizing layer which in turn carries the timing layer (as described in United States Patent 3,573,043) and the processing composition includes an oximated polydiacetone acrylamide thickening agent (as described in United States Patent
4,202,694.
The invention will now be described further in detail ; with respect to specific preferred embodiments by way of examples, it being understood that these are illustrative only and the invention is not intended to be limited to the materials, condi-.j.
., .
tions, process parameters, etc. which are recited therein. All parts and percentages are by weight unless otherwise indicated.
EXAMPLE I
As a control a film unit was prepared as follows:
The photosensitive element comprised a subcoated transp~rent polyethylene terephthalate photographic film base having coated thereon the following layers in succession:
1. a layer of sodium cellulose sulfate coated at a coverage of about 27.6 mgs/m2;
2. a layer of a cyan dye developcr represcnted hy the formula CH
H4 - NH- O2S ~
2 ~ lH3 _ C~ 5~C ~ NH-CH
CH3 ~ C/ ~ C ~ OH
1 2 ~ fH ~
S2 N~-CH
l-lo ~ 112 ~ ~ OH
HO ~
dispersed in gelatin and coated at a coverage of about 747 mgs/m2 of the dye developer and about 1554 mgs/m2 of gelatin and including about S8 mgs/m2 of 4'-methylphenyl~
hydroquinone and about 270 mgs/m~ of 2-phenylbenzimidazole;
3. a red-sensitive silver iodobromide emulsion layer ; coated at a coverage of about 1280 mgs/m2 of silver and about ! 768 mgs/m' of gelatin;
3'7 4. an interlayer comprising about 2505 mgs/m of a 60-29~6-4-0.4 pentapolymer of butylacrylate, diacetone acryl-amide, methacrylic acid, styrene and acrylic acid and about 78 mgs/m2 of polyacrylamide;
The invention will now be described further in detail ; with respect to specific preferred embodiments by way of examples, it being understood that these are illustrative only and the invention is not intended to be limited to the materials, condi-.j.
., .
tions, process parameters, etc. which are recited therein. All parts and percentages are by weight unless otherwise indicated.
EXAMPLE I
As a control a film unit was prepared as follows:
The photosensitive element comprised a subcoated transp~rent polyethylene terephthalate photographic film base having coated thereon the following layers in succession:
1. a layer of sodium cellulose sulfate coated at a coverage of about 27.6 mgs/m2;
2. a layer of a cyan dye developcr represcnted hy the formula CH
H4 - NH- O2S ~
2 ~ lH3 _ C~ 5~C ~ NH-CH
CH3 ~ C/ ~ C ~ OH
1 2 ~ fH ~
S2 N~-CH
l-lo ~ 112 ~ ~ OH
HO ~
dispersed in gelatin and coated at a coverage of about 747 mgs/m2 of the dye developer and about 1554 mgs/m2 of gelatin and including about S8 mgs/m2 of 4'-methylphenyl~
hydroquinone and about 270 mgs/m~ of 2-phenylbenzimidazole;
3. a red-sensitive silver iodobromide emulsion layer ; coated at a coverage of about 1280 mgs/m2 of silver and about ! 768 mgs/m' of gelatin;
3'7 4. an interlayer comprising about 2505 mgs/m of a 60-29~6-4-0.4 pentapolymer of butylacrylate, diacetone acryl-amide, methacrylic acid, styrene and acrylic acid and about 78 mgs/m2 of polyacrylamide;
5. A layer of a magenta dye developer represented by the formula 110--CH2--CHZ~
N -SO ~ N - N ~ CH3 lQ 1l ~CH2 - CH2~ 2 ~ Q \ ~/ o ~ N
O OH
OH
dispersed in gelatin and coated at a coverage of about 646 mgs/m of the dye developer, about 448 mgs/m of gelatin and including about 229 mgs/m2 of 2-phenylbenzimidazole;
N -SO ~ N - N ~ CH3 lQ 1l ~CH2 - CH2~ 2 ~ Q \ ~/ o ~ N
O OH
OH
dispersed in gelatin and coated at a coverage of about 646 mgs/m of the dye developer, about 448 mgs/m of gelatin and including about 229 mgs/m2 of 2-phenylbenzimidazole;
6. a green-sensitive silver iodobromide layer coated at a coverage of about 1050 mgs/m of silver and about 504 mgs/m2 of gelatin;
7. a layer comprising about 215 mgs/m2 of dodecyl-amino-reductone and about 215 mgs/m of gelatin;
8. an interlayer comprising about 1366 mgs/m2 of the pentapolymer described in layer 4, about 87 mgs/m , about 78 mgs/m of polyacrylamide and about 71 mgs/m2 of succindialdehyde;
9. a layer of a yellow dye developer represented by the formula X ~27 ~ `-. `` 1~78837 3 7 ~ CH N ~
0~ ~
/ Cr H20 O O OH
OH
lQ dispersed in gelatin and coated at a coverage of about 968 mgs/m of dye developer and about 451 mgs/m of gelatin and including about 208 mgs/m2 of 2-phenylbenzimidazole;
0~ ~
/ Cr H20 O O OH
OH
lQ dispersed in gelatin and coated at a coverage of about 968 mgs/m of dye developer and about 451 mgs/m of gelatin and including about 208 mgs/m2 of 2-phenylbenzimidazole;
10. a blue-sensitive silver iodobromide emulsion layer coated at a coverage of about 1280 mgs/m2 of silver, ahout 775 mgs/m of gelatin and about 306 mgs/m2 of 4-methyl phenyl hydroquinone;
. 11. an overcoat layer coated at a coverage of about ; 461 mgs/m of gelatin and about 21 mgs/m2 of carbon black.
The image~receiving element comprised a transparent polyethylene terephthalate film base coated with the following layers in succession:
1. as a polymeric acid layer approximately 9 parts of a 1/2 butyl ester of polyethylene/maleic anhydride copolymer ~ and 1 part of polyvinyl butyral coated at a coverage of about "' 2450 mgs/ft (26,372 mgs/m2);
2. a timing layer containing about 425 mgs/ft2 (4575 mgs/m ) of a 60-30-4-6 tetrapolymer of butylacrylate, ~; diacetone acrylamide, styrene and methacrylic acid and . including 9~ polyvinyl alcohol; and :, ::
~ X ~28-33~7 ~ ` ~
3. a polymeric image receiving layer of: (a) 3 parts of a mlxture of 2 parts polyvinyl alcohol and l part poly-4-vinyl pyridine and (b) l part of a graft copolymer comprised of 4-vinylpyridine (4VP) and vinylbenzyl trimethyl 5 ammonium chloride (TMQ) grafted onto hydroxyethyl cellulose (HEC) at a ratio of HEC/4VP/~MQ of 2.2/2.2/1 coated at a coverage of about 300 mgs/ft2 (3229 mgs/m2).
The film unit was processed with an aqueous alkaline processing composition as follows:
Titanium dioxide 38.05 g.
Carboxymethyl hydroxyethyl cellulose2.00 g.
Potassium hydroxide (45~ aqueous solution) ll.ll g.
Benzotriazole 0.28 g.
6-methyl uracil 0.30 g.
N-hydroxyethyl-N,N',N'-tris-carboxymethyl ethylene diamine0.75 g.
Polyethylene glycol (MW 4000) 0.45 g.
Bis(2-aminoethyl)sulfide 0.02 g.
Colloidal silica (30~ aqueous dispersion) 1.85 g.
N-phenethyl-~-picolinium bromide (50~ aqueous solution) ~ 2.55 g.
4-aminopyrazolo(3,4-d)pyrimidine0.25 g.
IlOO~ H H ~ S2-c16~l J l~ ~
0.30 cJ.
-` ` li'7~837 ~ OH
~ COOH HOOC
C18H37~ ~
~ 1.36 g.
Water to make a total of 100. g.
A film unit according to the invention was prepared identical to the control with the èxception that th~ proccssing composition further included 0.05~ of compound II.
The film units were processed at room temperature as follows: one half of each film unit was exposed through the transparent base of the image-receiving element to light from a Xenon source (100 meter car.dle seconds) which was passed in ! 10 turn through an ultraviolet filter, neutral density filters to reduce the film plane light flux to 0.5 m c s, and a Wratten 47B blue filter; the other half of each film unit was not exposed. The film units were then processed by passing them through a pair of rollers at a gap spacing of 0.0030" and the relative amount of silver developed ~a function of the infra-red light absorbed) was measured as a function of time for both the exposed and unexposed areas. The relative amount of developed silver vs time curves are shown in Fig. 1. It is seen that the presence of compound II reduced fog development (relative amount of developed silver in unexposed areas) in comparison to the --~ 11'7E~837 control. It is also apparent that the difference between the relative amount of silver developed in exposed and unexposed regions in the presence of compound II is significantly greater than the corresponding difference for the control.
The experiment was repeated with processing being carried out at 95F. The relative amount of developed silver vs time curves are shown in Fig. 2. It is seen that fog development in the control increased significantly at the higher processing temperature, whereas the increase was only slight with compound II present. Further, at the higher processirlg tempera-ture the presence of compound II greatly reduced fog development in comparison to the control without any appreciable change in the rate at which e~posed silver halide was developed.
EXAMPLE II
As a control a film unit was prepared as follows:
The photosensitive element comprised a subcoated opaque polyethylene terephthalate photographic film base having coated thereon the following layers in succession:
1. a cyan dye developer layer coated at a coverage of about 742 mgs/m2 of the cyan dye developer described in xample I, about 1485 mgs/m of gelatin, about 68 mgs/m of 4'-methylphenylhydroquinone and about 270 mgs/m2 of 2-phenyl-benximidazole;
2. a red-sensitive silver iodobromide emulsion layer coated at a coverage of about 1290 mgs/m2 of silver and about 775 mgs/m2 of gelatin;
3. an interlayer of a 60-30-4-6 tetrapolymer of butyl acrylate, diacetone acrylamide, styrene and methacrylic acid coated at a coverage of about 2582 mgs/m2 of the tetra-polymer and about 68 mgs/m2 of polyacrylamide;
~178837 , ~
4. a magneta dye developer layer coated at a coverage of about 646 mgs~m2 of the magenta dye developer de.scribed in Example I, about 452 mgs/m2 of gelatin, about
. 11. an overcoat layer coated at a coverage of about ; 461 mgs/m of gelatin and about 21 mgs/m2 of carbon black.
The image~receiving element comprised a transparent polyethylene terephthalate film base coated with the following layers in succession:
1. as a polymeric acid layer approximately 9 parts of a 1/2 butyl ester of polyethylene/maleic anhydride copolymer ~ and 1 part of polyvinyl butyral coated at a coverage of about "' 2450 mgs/ft (26,372 mgs/m2);
2. a timing layer containing about 425 mgs/ft2 (4575 mgs/m ) of a 60-30-4-6 tetrapolymer of butylacrylate, ~; diacetone acrylamide, styrene and methacrylic acid and . including 9~ polyvinyl alcohol; and :, ::
~ X ~28-33~7 ~ ` ~
3. a polymeric image receiving layer of: (a) 3 parts of a mlxture of 2 parts polyvinyl alcohol and l part poly-4-vinyl pyridine and (b) l part of a graft copolymer comprised of 4-vinylpyridine (4VP) and vinylbenzyl trimethyl 5 ammonium chloride (TMQ) grafted onto hydroxyethyl cellulose (HEC) at a ratio of HEC/4VP/~MQ of 2.2/2.2/1 coated at a coverage of about 300 mgs/ft2 (3229 mgs/m2).
The film unit was processed with an aqueous alkaline processing composition as follows:
Titanium dioxide 38.05 g.
Carboxymethyl hydroxyethyl cellulose2.00 g.
Potassium hydroxide (45~ aqueous solution) ll.ll g.
Benzotriazole 0.28 g.
6-methyl uracil 0.30 g.
N-hydroxyethyl-N,N',N'-tris-carboxymethyl ethylene diamine0.75 g.
Polyethylene glycol (MW 4000) 0.45 g.
Bis(2-aminoethyl)sulfide 0.02 g.
Colloidal silica (30~ aqueous dispersion) 1.85 g.
N-phenethyl-~-picolinium bromide (50~ aqueous solution) ~ 2.55 g.
4-aminopyrazolo(3,4-d)pyrimidine0.25 g.
IlOO~ H H ~ S2-c16~l J l~ ~
0.30 cJ.
-` ` li'7~837 ~ OH
~ COOH HOOC
C18H37~ ~
~ 1.36 g.
Water to make a total of 100. g.
A film unit according to the invention was prepared identical to the control with the èxception that th~ proccssing composition further included 0.05~ of compound II.
The film units were processed at room temperature as follows: one half of each film unit was exposed through the transparent base of the image-receiving element to light from a Xenon source (100 meter car.dle seconds) which was passed in ! 10 turn through an ultraviolet filter, neutral density filters to reduce the film plane light flux to 0.5 m c s, and a Wratten 47B blue filter; the other half of each film unit was not exposed. The film units were then processed by passing them through a pair of rollers at a gap spacing of 0.0030" and the relative amount of silver developed ~a function of the infra-red light absorbed) was measured as a function of time for both the exposed and unexposed areas. The relative amount of developed silver vs time curves are shown in Fig. 1. It is seen that the presence of compound II reduced fog development (relative amount of developed silver in unexposed areas) in comparison to the --~ 11'7E~837 control. It is also apparent that the difference between the relative amount of silver developed in exposed and unexposed regions in the presence of compound II is significantly greater than the corresponding difference for the control.
The experiment was repeated with processing being carried out at 95F. The relative amount of developed silver vs time curves are shown in Fig. 2. It is seen that fog development in the control increased significantly at the higher processing temperature, whereas the increase was only slight with compound II present. Further, at the higher processirlg tempera-ture the presence of compound II greatly reduced fog development in comparison to the control without any appreciable change in the rate at which e~posed silver halide was developed.
EXAMPLE II
As a control a film unit was prepared as follows:
The photosensitive element comprised a subcoated opaque polyethylene terephthalate photographic film base having coated thereon the following layers in succession:
1. a cyan dye developer layer coated at a coverage of about 742 mgs/m2 of the cyan dye developer described in xample I, about 1485 mgs/m of gelatin, about 68 mgs/m of 4'-methylphenylhydroquinone and about 270 mgs/m2 of 2-phenyl-benximidazole;
2. a red-sensitive silver iodobromide emulsion layer coated at a coverage of about 1290 mgs/m2 of silver and about 775 mgs/m2 of gelatin;
3. an interlayer of a 60-30-4-6 tetrapolymer of butyl acrylate, diacetone acrylamide, styrene and methacrylic acid coated at a coverage of about 2582 mgs/m2 of the tetra-polymer and about 68 mgs/m2 of polyacrylamide;
~178837 , ~
4. a magneta dye developer layer coated at a coverage of about 646 mgs~m2 of the magenta dye developer de.scribed in Example I, about 452 mgs/m2 of gelatin, about
11 mgs/m2 of carbon black and about 226 mgs/m2 of 2-phenyl-benzimidazole, 5. a green~sensitive silver iodobromide layer coated at a coverage of about 795 mgs/m of silver and about 525 mgs/m2 of gelatin;
6. an interlayer including about 1452 mgs/m of lQ the tetrapolymer described in layer 3, about 75 mgs/m of polyacrylamide and about 71 mgs/m2 of succindialdehyde;
7. a yellow dye developer layer coated at a coverage of about 968 mgs/m of the yellow dye developer described in Example I, about 452 mgs/m of gelatin, about 27 mgs/m2 of carbon black and about 204 mgs/m2 of 2-phenyl : henzimidazole;
8. a blue-sensitive silver iodobromide emulsion layer coated at a coverage of about 1280 mgs/m of silver, ahout 563 mg5/m of gelatin and about 204 mgs/m of 4'-methyl 2Q phenyl hydroquinone;
9. an overcoat layer coated at a coverage of about 484 mgs/m2 of gelatin and about 43 mgs/m of carbon black.
The image-receiving element was identical to that described in ~xample I.
The film unit was processed with a control aqueous alkaline processing composition which was the same as the con-trol described in ~xample I with the exception that it included 0.55 g of benzotriazole and did not include any 4-aminopyrazolo (3~4 d~pyrimidine.
~32 li7B837 The film unit was exposed (0.5 meter-candle-seconds) on a sensitometer to a photographic test exposure scale, or ~tep wedge, through the transparent support of the image-receiving element and processed at 75F with the processing co~position by passing the film unit through a pair of pressure rollers set at a gap spacing of about 0.0030 inch. The film unit was retained intact and viewed through the transparent base. There was obtained a well developed image.
The neutral density column of the image was read on lQ the densitometer to obtain the DmaX values for red, green and blue c~rves, respectively. In addition, the speed of the red~
green and blue curves, respectively (defined as the negative log of the relative exposure required to give red, green and blue absorption in the neutral column a reflection density of 0.75~ was measured. The values obtained are shown in Table IV.
The experiment was repeated with five additional film units (IIA_IIE) with the exception that the processing composition further included compound XI in the amounts shown in Table IV.
TABLE IV
Film % Comp'd Dmax Rel. Speed Unit XI R G B R G B
Control --- 2.31 2.20 2.22 1.41 1.29 1.23 IIA 0.013 2.36 2.23 2.31 1.45 1.42 1.45 IIB 0.025 2.36 2.21 2.25 1.45 1.45 1.53 IIC 0.05 2.37 2.17 2.18 1.45 1.49 1.50 IID 0.075 2.36 2.18 2.24 1.43 1.45 1.27 IIL 0.1 2.34 2.16 2.23 1.40 1.33 0.44 It can be seen that the presence of compound XI pro-3Q vided a sli~ht inCrRa~e in the D of the individual colors ~33~
at certain concentrations and also provided an appreciable increase in the green and blue speeds at certain concentrations.
Thus it is apparent that in this case about 0.025~ of compound XI gave the optimum combination of speed increase and DmaX
increase. The data also show that in a given film unit excessive concentrations of the compound for that film unit can lead to undesirable results; thus in Film Unit IIE the blue speed dropped considerably indicating premature inhibition of develop-ment of the blue-sensitive silver halide layer.
EXAMPLE III
The experiment described in Example II was repeated with six film units (IIIA-IIIF) which included compound II in the amounts shown in Table V. In addition, certain of the film units were also processed at 95F. The room temperature data for the control film unit of Example II were used for comparison. In addition, a control film unit was processed at 95F.
TABLE V
Film %Comp'd Dmax Rel. Speed Unit II R G B R G B
-20 Contr~ 2.312.20 2.22 1.41 1.29 1.23 IIIA 0.05 2.392.24 2.36 1.36 1.35 1.38 IIIB 0.06 2.432.28 2.38 1.39 1.40 1.44 IIIC 0-07 2.422.25 2.35 1.38 1.40 1.46 IIID 0.08 2.361.97 2.13 1.35 1.41 1.48 IIIE 0.09 2.351.91 2.04 1.40 1.48 1.55 IIIF 0.10 2.321.81 1.88~1.40 1.52 1.60 Film ~ Dmax ~ Rel. Speed Unit R G B R G B
Control -0.45 -0.28 -0.45 +0.10 ~0.16 +0.08 - 30 IIIA 0.05- - - - - _ IIIB 0.06-0.20 -0.05 -0.12 +0.05+0.01 -0.08 IIIC 0.07-0.17 -0.02 -0.10 +0.04+0.01 -0.08 IlI~ 0.08-0.13 +0.26 +0.12 +0.07+0.02 -0.06 IIIE 0.09-0.07 +0.33 +0.23 +0.02-0.04 -0.10 IIIF 0.10 .ll~ 7 The results show that at room temperature processing (75F) the presence of compound II provided an increase in the D of the individual colors at concentrations up to 0.07% and max an increase in the green and blue speeds in each film unit. When the film units were processed at 95F the presence of compound II
provided a significant impro~ement over the control in DmaX
since the DmaX of the individual colors went down considerably less, in comparison to the values obtained at 75F, in most instances, and actually increased in others.
EXAMPLE IV
Two sets of film units, identical to thos~ dcscribcd in Example II except that the processing composition of one (IVA) contained 0.025% of compound XI and that of the other, ~IVB) contained 0.05% of compound II were processed at 75F and 95F. The data are shown in Table VI. The data for the control film unit of Example II were used for comparison.
TABLE VI
Film Dmax Rel. Speed Unit R G B R G B
Control 2.31 2.20 2.22 1.41 1.29 1.23 IVA 2.36 2.21 2.25 1.45 1.45 1.53 IVB 2.27 2.22 2.26 1.39 1.39 1.42 ~ Dmax ~ Rel.Speed Control -0.45 -0.28 -0.45+0.10 +0.16 +0.08 IVA -0.25 +0.01 -0.01 +0.04 -0.03 -0.12 IVB -0.15 -0.01 +0.02 +0.08 +0.05 -0.04 It can be seen that again the presence of compounds XI and II provided significant increases in the green and blue relative speeds at 75F and provided significant improvement in the red, green and blue D~x at 95F, with the relative speeds of these colors being desirably closer than in the control.
~lt7~83''~
EXAMPLE V
A control film unit was prepared as follows: The photosensitive element comprised a subcoated opaque poly-- ethylene terephthalate photographic film base having coated thereon in succession:
l. a layer of sodium cellulose sulfate coate~ at a coverage of about 14 mgs/m2;
2. a cyan dye developer layer comprising about 747 mgs/m2 of the cyan dye developer illustrated in Example I, about 1554 mgs/m2 of gelatin, about 207 mgs/m2 of 2-phenyl-benzimidazole and about 68 mgs/m2 of 4'-methyl phenyl hydro-. .
quinone;
3. a red-sensitive silver iodobromide emulsion layer coated at a coverage of about 1280 mgs/m2 of silver and about 768 mgs/m2 of gelatin; 2 4. an interlayer comprising about 1882 mgs/m of thc pentapolymer described in Example I and about 58 mgs/m2 of polyacrylamide;
5. a magenta dye developer layer comprising about 545 mgs/m2 of the magenta dye developer illustrated in Example I, about 382 mgs/m2 of gelatin and about 23~ mgs/m2 of 2-phenylbenzimidaæole;
6. a green-sensitive silver iodobromide emulsion layer coated at a coverage of about 560 mgs/m2 of silver and about 246 mgs/m2 of gelatin;
117~337 7. a green-sensitive silvex iodobromide emulsion layer coated at a coverage of about 1050 mgs/m2 of silver and about 504 mgs/m of gelatin;
8. an interlayer comprising about 1598 mgs/m2 of the pentapolymer described in Example I, about 102 mgs/m2 of polyacrylamide and about 82.5 mgs/m2 of succindialdehyde;
9. a yellow dye developer layer comprising about 820 mgs/m2 of the yellow dye developer illustrated in Example I, about 385 mgs/m2 of gelatin and about 207 mgs/m2 of 2-phenylbenzimidazole;
10. a blue-sensitive silver iodobromide emulsion layer coated at a coverage of about 1280 mgs/m2 of silver, about 775 mgs/m2 of gelatin and about 306 mgs/m2 of 4'-methyl-phenyl hydroquinone; and 11. a topcoat layer of about 484 mgs/m2 of gelatin.
The image-receiving element comprised a transparent subcoated polyethylene terephthalate film base on which the ~ollowing laycrs wcre coated in succession:
1. as a polymeric acid layer approximatcly 9 parts of a 1/2 butyl ester of polyethylene/maleic anhydride copolymer and 1 part of polyvinyl butyral coated at a coverage of about 26,372 mgs/m2;
2. a timing layer coated at a coveraye of about 10,000 mgs/m2 of a graft tetrapolymer of diacetone acrylamide, acrylamide, ~-cyanoethylacrylate and 2-acrylamido-2-methane sulfonic acid on polyvinylalcohol;
3. a polymeric image receiving layex coated at a coverage of about 2200 mgs/m2 of: ta) 3 parts of a mixture of 2 parts polyvinyl alcohol and 1 part poly-4-vinylpyridine and (b) 1 part of a graft copolymer comprised of 4-vinylpyridine ~i7883'7 (4VP) and vinyl benzyltrimethyl a nium chloride (TMQ) grafted onto hydroxyethyl cellulose (HEC) at a ratio HEC/4VP/TMQ of 2.2/2.2/1; and about 74 mgs/m2 of 1,4-butanediol diglycidyl ether;
4. a top coat layer comprising about 320 mgs/m2 of polyvinyl alcohol.
The film unit was processed with the processing composition described in Example 1 as a control with the excep-tion that it included 0.55 g of benzotriazole and 0.93 g of the aqueous colloidal silica dispersion.
Also four additional film units (VA-VD) were prepared and processed in the same manner with the exception that the processing composition further included compound I
in the amounts shown in Table VII. An identical set of film . . .
units was also processed at 95F.
TABLE VII
Film~Comp'd Dmax Rel. Speed Unit I R G B R G B
Control - 1.63 1.87 2.04 1.61 1.49 1.40 VA 0.025 1.61 1.92 2.01 1.59 1.45 1.35 VB 0.05 1.58 1.95 2.15 1.57 1.45 1.37 VC 0.1 1.56 l.9B 2.11 1.62 1.55 1.48 VD 0.2 1.40 1.82 1.89 1.64 1.58 1.43 ~Dmax ~Rel. Speed R G BR G B
Control - -0.58 -0.41 -0.45 0.00 -0.02 -0.06 VA 0.02~ -0.39 -0.33 -0.27-0.06 -0.03 -0.05 VB 0.05 -0.21 -0.19 -0.19-0.05 -0.04 -0.07 VC 0.1 -0.09 -0.21 -0.09-0.10 -0.10 -0.03 VD 0.2 -0.02 -0.08 +0.05 -0.05 +0.06 +0.13 It can be seen that at room temperature processing the presence of compound I provided an increase in the green 3`7 and blue DmaX at concentrations up to 0.1% without any appre-ciable loss in relative speed. At 95F processing the presence of compound I gave a much smaller loss in ~max for red, green and blue in comparison to the control, again without any significant change in the relative speeds.
EXAMPLE VI
This experiment represents a comparison of compounds I and II and phenylmercaptotetrazole (PMT) with a control at room temperature.
The control film unit comprised a subcoated opaque film base having the following layers coated thereon in succession:
1. a layer of sodium cellulose sulfate coated at a coverage of about 100 mgs/m2;
2. a cyan dye developer layer coated at a coverage of about 635 mgs/m of the cyan dye developer described in Example I, about 430 mgs/m of gelatin, about 237 mgs/m of N-dodecylaminopurine and about 128 mgs/m of 4'-methyl phenyl hydroquinone;
3. a red sensitive; silver iodobromide emulsion layer coated at a coverage of about 1500 mgs/m of silver and about 900 mgs/m2 of gelatin;
4. an interlayer comprising about 1264 mgs/m2 of the pentapolymer described in Example I and about 67 mgs/m2 of polyacrylamide;
5. a magenta dye developer layer coated at a coverage of about 646 mgs/m of a magenta dye developer repre-sented by the formula (CH2) OH ~ ~ \ H3 oH
2!3 ~-so~3 ~ OH
H2) 3 CH
and about 323 mgs/m of gelatin;
6. a green-sensitive silver iodobromide emulsion layer coated at a coverage of about 1300 mgs/m2 of silver and about 596 mgs/m of gelatin;
7. an interlayer comprising about 950 mgs/m2 of the pentapolymer described in Example I and about 50 mgs/m2 of polyacrylamide;
8. a yellow dye developer layer coated at a coverage of about 820 mgs/m2 of thé yellow dye developer described in ~xample I, and about 328 mgs/m2 of gelatin;
9. a spacer layer comprising about 150 mgs/m2 of N-dodecylaminopurine and about 150 mgs/m2 of gelatin;
10. a blue sensitive silver iodobromide emulsion layer coated at a coverage of about 1200 mgs/m2 of silver, about 421 mgs/m2 of gelatin and about 320 mgs/m2 of 4' methyl phenyl hydroquinone; and 11. a topcoat layer comprising about 484 mgs/m2 of gelatin.
The image-receiving element comprised a transparent base having coated thereon in succession:
17883~
1. a polymeric acid layer as described in Example V;
2. a timing layer comprising about 2570 mgs/m2 of the pentapolymer described in Example I and about 206 mgs/m of polyacrylamide;
3. a polymeric image receiving layer as described in Example V with the exception that the coverages of the ether and the mixture of graft copolymer (PVA-P-4-VP) were 103 mgs/m' and 2990 mgs/m2 respectively;
4. a topcoat layer comprising about 721 mgs/m2 o~ a polyoxyethylene-polyoxypropylene block copolymer (Pluronic*
F-127, commercially available from BASF Wyandotte Co.) and about 309 mgs/m2 o~ polyvinylalcohol.
The control film unit was processed with a processing composition as described in Example V.
Three additional film units (VIA- VIC) were prepared and processed in the same manner with the exception that the processing composition further included 0.05% of PMT, compound I
and compound II respectively. The results are shown in Table VIII.
TABLE VIII
Film Dmax Dmin Rel. Speed Unit R G B R G B R G B
Control 1.80 2.24 1.65 0.21 0.21 0.18 1.41 1.37 1.64 VI A 1.75 2.23 2.20 0.23 0.25 o.76 1.29 1~03 *
VI B 1.75 2.24 1.98 0.22 0.20 0.18 1.39 1.38 1.44 VI C 1.81 2.27 2.06 0.23 0.22 0.19 1.34 1.33 1.27 * blue relative speed too slow to measure It is seen that the presence of PMT causes a large increase in the blue Dmin and a very lar~e decrease in the blue speed, thus indicating that the PMT restrained development of the blue sensitive silver halide emulsion prematurely. The *Trade Mark . ~
- 117883~
presence of compounds I and II provided an increase in the blue DmaX without any increase in the blue Dmin.
EXAMPLE VII
As a control a film unit was prepared as follows:
the photosensitive element comprised a subcoated transparent polyethylene terephthalate photographic film base having coated thereon the following layers in succession:
1. a layer of sodium cellulose sulfate coated at a coverage of about 14.4 mgs/m2;
2. a cyan dye developer layer comprising about 747 mgs/m2 of the cyan dye developer illustrated in Example I, about 1554 mgs/m2 of gelatin, about 270 mgs/m2 of 2-phenylbenæ-imidazole and about 68 mgs/m of 4'-methylphenylhydroquinone;
3. a red-sensitive silver iodobromide emulsion layer coated at a coverage of about 1280 mgs/m2 of silver and about 768 mgs/m2 of gelatin; 2 4. an interlayer comprising about 2505 mgs/m of the pentapolymer described in Example I and about 78 mgs/m2 of polyacrylamide;
5. a magenta dye d,eveloper layer comprsing about 646 mgs/m2 of the magenta dye developer described in Example I, about 452 mgs/m2 of gelatin and about 229 mgs/m of 2-phenyl-benzimidazole;
6. a green-sensitive ~ilver iodobromide emulsion layer coated at a coverage of about 510 mgs/m2 of silver and about 224 mgs/m2 of gelatin;
7. a spacer layer comprising about 1045 mgs/m2 of polymethylmethacrylate and about 55 mgs/m of polyacrylamide;
~17~837 8. a green-sensitive silver iodobromide emulsion layer coated at a coverage of about 700 mgs/m of silver and about 336 mgs/m2 of gelatin;
9. an interlayer comprising about 1366 mgs/m2 of the pentapolymer described in Example I and about 87 mgs/m2 of polyacrylamide;
10. a yellow dye developer layer com2rising about 820 mgs/m2 of the yellow dye developer illustrated in Example I, about 384 mgs/m2 of gelatin and about 208 mgs/m2 of 2-phenyl-benzimidazole;
11. a blue-sensitive silver iodobromide emulsion layer coated at a coverage of about 1280 mgs/m2 of silver, about 775 mgs/m2 of gelatin and about 306 mgs/m2 of 4'-methyl-phenylhydroquinone;
6. an interlayer including about 1452 mgs/m of lQ the tetrapolymer described in layer 3, about 75 mgs/m of polyacrylamide and about 71 mgs/m2 of succindialdehyde;
7. a yellow dye developer layer coated at a coverage of about 968 mgs/m of the yellow dye developer described in Example I, about 452 mgs/m of gelatin, about 27 mgs/m2 of carbon black and about 204 mgs/m2 of 2-phenyl : henzimidazole;
8. a blue-sensitive silver iodobromide emulsion layer coated at a coverage of about 1280 mgs/m of silver, ahout 563 mg5/m of gelatin and about 204 mgs/m of 4'-methyl 2Q phenyl hydroquinone;
9. an overcoat layer coated at a coverage of about 484 mgs/m2 of gelatin and about 43 mgs/m of carbon black.
The image-receiving element was identical to that described in ~xample I.
The film unit was processed with a control aqueous alkaline processing composition which was the same as the con-trol described in ~xample I with the exception that it included 0.55 g of benzotriazole and did not include any 4-aminopyrazolo (3~4 d~pyrimidine.
~32 li7B837 The film unit was exposed (0.5 meter-candle-seconds) on a sensitometer to a photographic test exposure scale, or ~tep wedge, through the transparent support of the image-receiving element and processed at 75F with the processing co~position by passing the film unit through a pair of pressure rollers set at a gap spacing of about 0.0030 inch. The film unit was retained intact and viewed through the transparent base. There was obtained a well developed image.
The neutral density column of the image was read on lQ the densitometer to obtain the DmaX values for red, green and blue c~rves, respectively. In addition, the speed of the red~
green and blue curves, respectively (defined as the negative log of the relative exposure required to give red, green and blue absorption in the neutral column a reflection density of 0.75~ was measured. The values obtained are shown in Table IV.
The experiment was repeated with five additional film units (IIA_IIE) with the exception that the processing composition further included compound XI in the amounts shown in Table IV.
TABLE IV
Film % Comp'd Dmax Rel. Speed Unit XI R G B R G B
Control --- 2.31 2.20 2.22 1.41 1.29 1.23 IIA 0.013 2.36 2.23 2.31 1.45 1.42 1.45 IIB 0.025 2.36 2.21 2.25 1.45 1.45 1.53 IIC 0.05 2.37 2.17 2.18 1.45 1.49 1.50 IID 0.075 2.36 2.18 2.24 1.43 1.45 1.27 IIL 0.1 2.34 2.16 2.23 1.40 1.33 0.44 It can be seen that the presence of compound XI pro-3Q vided a sli~ht inCrRa~e in the D of the individual colors ~33~
at certain concentrations and also provided an appreciable increase in the green and blue speeds at certain concentrations.
Thus it is apparent that in this case about 0.025~ of compound XI gave the optimum combination of speed increase and DmaX
increase. The data also show that in a given film unit excessive concentrations of the compound for that film unit can lead to undesirable results; thus in Film Unit IIE the blue speed dropped considerably indicating premature inhibition of develop-ment of the blue-sensitive silver halide layer.
EXAMPLE III
The experiment described in Example II was repeated with six film units (IIIA-IIIF) which included compound II in the amounts shown in Table V. In addition, certain of the film units were also processed at 95F. The room temperature data for the control film unit of Example II were used for comparison. In addition, a control film unit was processed at 95F.
TABLE V
Film %Comp'd Dmax Rel. Speed Unit II R G B R G B
-20 Contr~ 2.312.20 2.22 1.41 1.29 1.23 IIIA 0.05 2.392.24 2.36 1.36 1.35 1.38 IIIB 0.06 2.432.28 2.38 1.39 1.40 1.44 IIIC 0-07 2.422.25 2.35 1.38 1.40 1.46 IIID 0.08 2.361.97 2.13 1.35 1.41 1.48 IIIE 0.09 2.351.91 2.04 1.40 1.48 1.55 IIIF 0.10 2.321.81 1.88~1.40 1.52 1.60 Film ~ Dmax ~ Rel. Speed Unit R G B R G B
Control -0.45 -0.28 -0.45 +0.10 ~0.16 +0.08 - 30 IIIA 0.05- - - - - _ IIIB 0.06-0.20 -0.05 -0.12 +0.05+0.01 -0.08 IIIC 0.07-0.17 -0.02 -0.10 +0.04+0.01 -0.08 IlI~ 0.08-0.13 +0.26 +0.12 +0.07+0.02 -0.06 IIIE 0.09-0.07 +0.33 +0.23 +0.02-0.04 -0.10 IIIF 0.10 .ll~ 7 The results show that at room temperature processing (75F) the presence of compound II provided an increase in the D of the individual colors at concentrations up to 0.07% and max an increase in the green and blue speeds in each film unit. When the film units were processed at 95F the presence of compound II
provided a significant impro~ement over the control in DmaX
since the DmaX of the individual colors went down considerably less, in comparison to the values obtained at 75F, in most instances, and actually increased in others.
EXAMPLE IV
Two sets of film units, identical to thos~ dcscribcd in Example II except that the processing composition of one (IVA) contained 0.025% of compound XI and that of the other, ~IVB) contained 0.05% of compound II were processed at 75F and 95F. The data are shown in Table VI. The data for the control film unit of Example II were used for comparison.
TABLE VI
Film Dmax Rel. Speed Unit R G B R G B
Control 2.31 2.20 2.22 1.41 1.29 1.23 IVA 2.36 2.21 2.25 1.45 1.45 1.53 IVB 2.27 2.22 2.26 1.39 1.39 1.42 ~ Dmax ~ Rel.Speed Control -0.45 -0.28 -0.45+0.10 +0.16 +0.08 IVA -0.25 +0.01 -0.01 +0.04 -0.03 -0.12 IVB -0.15 -0.01 +0.02 +0.08 +0.05 -0.04 It can be seen that again the presence of compounds XI and II provided significant increases in the green and blue relative speeds at 75F and provided significant improvement in the red, green and blue D~x at 95F, with the relative speeds of these colors being desirably closer than in the control.
~lt7~83''~
EXAMPLE V
A control film unit was prepared as follows: The photosensitive element comprised a subcoated opaque poly-- ethylene terephthalate photographic film base having coated thereon in succession:
l. a layer of sodium cellulose sulfate coate~ at a coverage of about 14 mgs/m2;
2. a cyan dye developer layer comprising about 747 mgs/m2 of the cyan dye developer illustrated in Example I, about 1554 mgs/m2 of gelatin, about 207 mgs/m2 of 2-phenyl-benzimidazole and about 68 mgs/m2 of 4'-methyl phenyl hydro-. .
quinone;
3. a red-sensitive silver iodobromide emulsion layer coated at a coverage of about 1280 mgs/m2 of silver and about 768 mgs/m2 of gelatin; 2 4. an interlayer comprising about 1882 mgs/m of thc pentapolymer described in Example I and about 58 mgs/m2 of polyacrylamide;
5. a magenta dye developer layer comprising about 545 mgs/m2 of the magenta dye developer illustrated in Example I, about 382 mgs/m2 of gelatin and about 23~ mgs/m2 of 2-phenylbenzimidaæole;
6. a green-sensitive silver iodobromide emulsion layer coated at a coverage of about 560 mgs/m2 of silver and about 246 mgs/m2 of gelatin;
117~337 7. a green-sensitive silvex iodobromide emulsion layer coated at a coverage of about 1050 mgs/m2 of silver and about 504 mgs/m of gelatin;
8. an interlayer comprising about 1598 mgs/m2 of the pentapolymer described in Example I, about 102 mgs/m2 of polyacrylamide and about 82.5 mgs/m2 of succindialdehyde;
9. a yellow dye developer layer comprising about 820 mgs/m2 of the yellow dye developer illustrated in Example I, about 385 mgs/m2 of gelatin and about 207 mgs/m2 of 2-phenylbenzimidazole;
10. a blue-sensitive silver iodobromide emulsion layer coated at a coverage of about 1280 mgs/m2 of silver, about 775 mgs/m2 of gelatin and about 306 mgs/m2 of 4'-methyl-phenyl hydroquinone; and 11. a topcoat layer of about 484 mgs/m2 of gelatin.
The image-receiving element comprised a transparent subcoated polyethylene terephthalate film base on which the ~ollowing laycrs wcre coated in succession:
1. as a polymeric acid layer approximatcly 9 parts of a 1/2 butyl ester of polyethylene/maleic anhydride copolymer and 1 part of polyvinyl butyral coated at a coverage of about 26,372 mgs/m2;
2. a timing layer coated at a coveraye of about 10,000 mgs/m2 of a graft tetrapolymer of diacetone acrylamide, acrylamide, ~-cyanoethylacrylate and 2-acrylamido-2-methane sulfonic acid on polyvinylalcohol;
3. a polymeric image receiving layex coated at a coverage of about 2200 mgs/m2 of: ta) 3 parts of a mixture of 2 parts polyvinyl alcohol and 1 part poly-4-vinylpyridine and (b) 1 part of a graft copolymer comprised of 4-vinylpyridine ~i7883'7 (4VP) and vinyl benzyltrimethyl a nium chloride (TMQ) grafted onto hydroxyethyl cellulose (HEC) at a ratio HEC/4VP/TMQ of 2.2/2.2/1; and about 74 mgs/m2 of 1,4-butanediol diglycidyl ether;
4. a top coat layer comprising about 320 mgs/m2 of polyvinyl alcohol.
The film unit was processed with the processing composition described in Example 1 as a control with the excep-tion that it included 0.55 g of benzotriazole and 0.93 g of the aqueous colloidal silica dispersion.
Also four additional film units (VA-VD) were prepared and processed in the same manner with the exception that the processing composition further included compound I
in the amounts shown in Table VII. An identical set of film . . .
units was also processed at 95F.
TABLE VII
Film~Comp'd Dmax Rel. Speed Unit I R G B R G B
Control - 1.63 1.87 2.04 1.61 1.49 1.40 VA 0.025 1.61 1.92 2.01 1.59 1.45 1.35 VB 0.05 1.58 1.95 2.15 1.57 1.45 1.37 VC 0.1 1.56 l.9B 2.11 1.62 1.55 1.48 VD 0.2 1.40 1.82 1.89 1.64 1.58 1.43 ~Dmax ~Rel. Speed R G BR G B
Control - -0.58 -0.41 -0.45 0.00 -0.02 -0.06 VA 0.02~ -0.39 -0.33 -0.27-0.06 -0.03 -0.05 VB 0.05 -0.21 -0.19 -0.19-0.05 -0.04 -0.07 VC 0.1 -0.09 -0.21 -0.09-0.10 -0.10 -0.03 VD 0.2 -0.02 -0.08 +0.05 -0.05 +0.06 +0.13 It can be seen that at room temperature processing the presence of compound I provided an increase in the green 3`7 and blue DmaX at concentrations up to 0.1% without any appre-ciable loss in relative speed. At 95F processing the presence of compound I gave a much smaller loss in ~max for red, green and blue in comparison to the control, again without any significant change in the relative speeds.
EXAMPLE VI
This experiment represents a comparison of compounds I and II and phenylmercaptotetrazole (PMT) with a control at room temperature.
The control film unit comprised a subcoated opaque film base having the following layers coated thereon in succession:
1. a layer of sodium cellulose sulfate coated at a coverage of about 100 mgs/m2;
2. a cyan dye developer layer coated at a coverage of about 635 mgs/m of the cyan dye developer described in Example I, about 430 mgs/m of gelatin, about 237 mgs/m of N-dodecylaminopurine and about 128 mgs/m of 4'-methyl phenyl hydroquinone;
3. a red sensitive; silver iodobromide emulsion layer coated at a coverage of about 1500 mgs/m of silver and about 900 mgs/m2 of gelatin;
4. an interlayer comprising about 1264 mgs/m2 of the pentapolymer described in Example I and about 67 mgs/m2 of polyacrylamide;
5. a magenta dye developer layer coated at a coverage of about 646 mgs/m of a magenta dye developer repre-sented by the formula (CH2) OH ~ ~ \ H3 oH
2!3 ~-so~3 ~ OH
H2) 3 CH
and about 323 mgs/m of gelatin;
6. a green-sensitive silver iodobromide emulsion layer coated at a coverage of about 1300 mgs/m2 of silver and about 596 mgs/m of gelatin;
7. an interlayer comprising about 950 mgs/m2 of the pentapolymer described in Example I and about 50 mgs/m2 of polyacrylamide;
8. a yellow dye developer layer coated at a coverage of about 820 mgs/m2 of thé yellow dye developer described in ~xample I, and about 328 mgs/m2 of gelatin;
9. a spacer layer comprising about 150 mgs/m2 of N-dodecylaminopurine and about 150 mgs/m2 of gelatin;
10. a blue sensitive silver iodobromide emulsion layer coated at a coverage of about 1200 mgs/m2 of silver, about 421 mgs/m2 of gelatin and about 320 mgs/m2 of 4' methyl phenyl hydroquinone; and 11. a topcoat layer comprising about 484 mgs/m2 of gelatin.
The image-receiving element comprised a transparent base having coated thereon in succession:
17883~
1. a polymeric acid layer as described in Example V;
2. a timing layer comprising about 2570 mgs/m2 of the pentapolymer described in Example I and about 206 mgs/m of polyacrylamide;
3. a polymeric image receiving layer as described in Example V with the exception that the coverages of the ether and the mixture of graft copolymer (PVA-P-4-VP) were 103 mgs/m' and 2990 mgs/m2 respectively;
4. a topcoat layer comprising about 721 mgs/m2 o~ a polyoxyethylene-polyoxypropylene block copolymer (Pluronic*
F-127, commercially available from BASF Wyandotte Co.) and about 309 mgs/m2 o~ polyvinylalcohol.
The control film unit was processed with a processing composition as described in Example V.
Three additional film units (VIA- VIC) were prepared and processed in the same manner with the exception that the processing composition further included 0.05% of PMT, compound I
and compound II respectively. The results are shown in Table VIII.
TABLE VIII
Film Dmax Dmin Rel. Speed Unit R G B R G B R G B
Control 1.80 2.24 1.65 0.21 0.21 0.18 1.41 1.37 1.64 VI A 1.75 2.23 2.20 0.23 0.25 o.76 1.29 1~03 *
VI B 1.75 2.24 1.98 0.22 0.20 0.18 1.39 1.38 1.44 VI C 1.81 2.27 2.06 0.23 0.22 0.19 1.34 1.33 1.27 * blue relative speed too slow to measure It is seen that the presence of PMT causes a large increase in the blue Dmin and a very lar~e decrease in the blue speed, thus indicating that the PMT restrained development of the blue sensitive silver halide emulsion prematurely. The *Trade Mark . ~
- 117883~
presence of compounds I and II provided an increase in the blue DmaX without any increase in the blue Dmin.
EXAMPLE VII
As a control a film unit was prepared as follows:
the photosensitive element comprised a subcoated transparent polyethylene terephthalate photographic film base having coated thereon the following layers in succession:
1. a layer of sodium cellulose sulfate coated at a coverage of about 14.4 mgs/m2;
2. a cyan dye developer layer comprising about 747 mgs/m2 of the cyan dye developer illustrated in Example I, about 1554 mgs/m2 of gelatin, about 270 mgs/m2 of 2-phenylbenæ-imidazole and about 68 mgs/m of 4'-methylphenylhydroquinone;
3. a red-sensitive silver iodobromide emulsion layer coated at a coverage of about 1280 mgs/m2 of silver and about 768 mgs/m2 of gelatin; 2 4. an interlayer comprising about 2505 mgs/m of the pentapolymer described in Example I and about 78 mgs/m2 of polyacrylamide;
5. a magenta dye d,eveloper layer comprsing about 646 mgs/m2 of the magenta dye developer described in Example I, about 452 mgs/m2 of gelatin and about 229 mgs/m of 2-phenyl-benzimidazole;
6. a green-sensitive ~ilver iodobromide emulsion layer coated at a coverage of about 510 mgs/m2 of silver and about 224 mgs/m2 of gelatin;
7. a spacer layer comprising about 1045 mgs/m2 of polymethylmethacrylate and about 55 mgs/m of polyacrylamide;
~17~837 8. a green-sensitive silver iodobromide emulsion layer coated at a coverage of about 700 mgs/m of silver and about 336 mgs/m2 of gelatin;
9. an interlayer comprising about 1366 mgs/m2 of the pentapolymer described in Example I and about 87 mgs/m2 of polyacrylamide;
10. a yellow dye developer layer com2rising about 820 mgs/m2 of the yellow dye developer illustrated in Example I, about 384 mgs/m2 of gelatin and about 208 mgs/m2 of 2-phenyl-benzimidazole;
11. a blue-sensitive silver iodobromide emulsion layer coated at a coverage of about 1280 mgs/m2 of silver, about 775 mgs/m2 of gelatin and about 306 mgs/m2 of 4'-methyl-phenylhydroquinone;
12. a top coat layer of about 484 mgs/m of gelatin.
The image receiving element was identical to that described in Example V. The film unit was processed with a processing composition as described in Example V.
Six additional film units were prepared (VIIA-VIIF).
Film Units VIIA-VIIC further included 1 mg/m , 2 mgs/m and 3 mgs/m2, respectively, of compound II in layer 5 of the photo-sensitive element and Film Units VIID-VIIF furthex included 1 mg~m2, 2 mgs/m2 and 3 mgs/m2 of compound XI in layer S of the photosensitive element. An identical set of film units was also processed at 95F. The results are shown in Table IX.
- ` ` li'7883~7 TABLE IX
Film Dmax Rel. Speed Unit R G B R G B
Control1.95 1.67 2.231.50 1.49 1.32 VII A 2.03 1.75 2.251.52 1.46 1.33 VII B 2.09 1l70 2.241.47 1.46 1.33 VII C 2.14 1.78 2.281.41 1.39 1.29 VII D 2.01 1.71 2.231.56 1.48 1.35 VII E 2.04 1.73 2.251.58 1.46 1.37 VII F 2.08 1.71 2.231.57 1.43 1.39 .
~ Dmax R G B
Control -0.56 -0.20 -0.18 VII A -0.48 -0.19 -0.15 VII B -0.27 -0.09 -0.11 VII C -0.22 -0.06 -0.11 VII D -0.37 -0.12 -0.14 VII E -0.27 -0.05 -0.11 VII F -0.19 +0.06 -0.05 -It can be seen that at room temperature the presence of compounds II and XI provided an increase in red and green Dmax At 95F processing the presence of compounds II and XI
gave smaller losses (varying with the coverages) of red, blue and green DmaX
EXAMPLE VIII
PREP-ARATION OF COMPOUND XII
A cataly~t was prepared by stirring a mixture of Celite ~ (10 g.) (diatomaceous earth available from Johns Manville) and potassium fluoride dihydrate (15 g.) in 250 ml.
o-f distilled water for 30 minutes. The water was removed on a rotary evaporator and the solids dried overnight at room temperature under high vacuum. The catalyst was further dried in a vacuum oven at 58-60C for about two days.
To a stirred solution of 1-(4-hydroxyphenyl)-5-mercaptotetrazole (5g.) in dry tetrahydrofuran (50 ml.) at room temperature under nitrogen there were added methylvinyl-sulfone (2.8g.) and the potassium fluoride/Celite catalyst (lg.~. The reaction mixture was stirred slowly for 24 hours.
The solids were removed by filtration and the solvent was removed from the filtrate leaving behind a clear yellow-brown oil. The oil was dried under vacuum to give a tacky gum-like material. Recrystallization from methanol followed by drying to constant weight under vacuum gave a white, solid, compound XII, m.p. 139~-141C.
The NMR spectrum of the material was consistent ; with compound XII. 13C NMR (dmso-d6); ~159.28, 153.69, 126.28, 124.05, 116.23, 53.01, 40.59, 25;29 ppm.
EXAMPLE IX
EPAIU~TION OF COMPOUND XI IT
To a suspension of.compound IV (2.166g, 8.43 mmol) in methanol (10 ml) there were added, under nitrogen, 78% methyl vinyl sulfone (1.44g, 8.42 mmol) and 0.25 ml of 40~ benzyl trimethyl ammonium hydroxide in methanol and the reaction ! mixture refluxed for twenty-four hours. The cooled reaction mixture was filtered to collect the white crystals which had formed. Thin layer chromatography showed that some starting materials were present. The desired product, compound XIII, was separated by column chromatography followed by removal of the solvent, crystallization on standing and drying. The structure , 30 of the product was confirmed by UV and 13C NMR spectra.
' ~178837 EXAMPLE X
PREPARATION OF COMPOUND XIV
-A catalyst was prepared by stirring a mixture of lOg of Celite R (diatomaceous earth available from Johns Manville) and 15 g of potassium flùoride in 250 ml of distilled water for about 30 minutes, removing the water on a rotary evaporator at 56C and drying the solid under vacuum at 58-60C
to calculated weight, 196 g. The catalyst (lg) was added to a stirred solution of Sg of compound I and 1.8g of methyl vinyl ketone in 50 ml of dry tetrahydrofuran and the suspension was stirred under nitrogen at room temperature for three days. The solids were removed by filtering and the solvent removed from the filtrate to give about 7g of a brown-yellow oil which was stirred briefly with 70 ml of ether at room temperature. The ether solution was decanted from the brown oily solid which had deposited, and the crystalline solid which formed in the ether on standing collected by filtration, washed and dried to give 4g o~ white crystals (com~ound ~IV), m.p. 118-120C.
The structure of the product was confirmed by ~ 13C NMR spectrum.
EXAMPLE XI
PREPARATION OF COMPOUND XV
A mixture of compound IV (257 mg., 1.~0 mmol), methyl vinyl ketone ~0.081 nl, 1.0 mmol) and 200 mg of potassium fluoride on Celite catalyst (6 mmol/g) in about 2 ml of pyridine was stirred overnight. The reaction mixture was poured into 5% hydrochloric acid and the solid collected by filtration.
Thin layer chromatography showed two compounds. The desired product (compound XV) was separated by colu~n chromatography, followed by removal of the solvent, crystallization on standing and drying. The structure of the product was confirmed by a proton NMR spectrum.
` 11788~7 EXAMPLE XII
PREPARATION OF COMPOUND XVI
A stirred mixture of compound I t30.0g, 0.154 m), 3-bromopropionitrile (20.72 g, 0.154 m) and sodium bicarbonate (12.98 y, 0.154 m) in 600 ml of dry acetonitrile was heated under nitrogen at 55C for 42 hours, then cooled in an ice bath ~and vacuum filtered. The filtrate was evaporated on a rotary evaporator at 25C. The syrupy residue was taken up in 500 ml of ethyl acetate, washed with 400 ml of saturated NaHCO3 solu-tion and twice with 200 ml of water, dried over sodium sulfate and adsorptive activated carbon, and vacuum filtered throuqh diatomaceous earth. The filtrate was evaporated on a rotary evaporator at 25C and the crystalline residue was taken up in 200 ml of ethyl acetate and l00 ml of hexane added to the solu-tion. The solution was stored in a refrigerator overnight and 50 ml of hexane added. The crystalline material was collected by filtration, washed with two 50 ml volumes of hexane and dried under reduced pressure at ambient temperature to give 25 g (65.7% yield) of compound XVI.
EXAMPLE XIII
PREPARATION OF COMPOUND XVII
A mixture of compound II (11.647 g, 49.58 mmol), ~-bromopropionitrile (6.626g, 49.58 mmol) and sodium bicarbonate (4.17g, 49.58 mmol) in 200 ml of dry acetonitrile was magnet-ically stirred in a 55C bath under nitrogen overnight. The reaction mixture was vacuum filtered and the filtrate was stripped of solvent by rotar~ evaporation giving an orange oily residue. The residue was taken up in ethyl acetate (75 ml) and to the solution there were added seed crystals and 150 ml of hexane. The mixture was scratched and stored overnight in a 11'7883~7 refrigerator. The crystals which formed were collected ~y filtration, washed twice with hexane and dried to give 12.74 g of compound XVII as light yellow crystals, in p. 111-113C.
The structure of the product was confirmed by IR, UV and NMR
spectra and thin layer chromatography.
EXAMPLE XII
PREPARATION OF COMPOUND XVIII
A mixture of compound I (4.14g, 21.3 mmol), p-acetoxybenzyl chloride (3.94g, 21.3 mmol) and sodium bicarbonate (1.79g, 21.3 mmol) in 130 ml of dry acetonitrile was magnet-ically stirred under dry nitrogen at 55C overnight. The reaction mixture was cooled in an ice bath, the solids removed by vacuum filtration and the solvent stripped from the filtrate to give an oily residue. The oily residue was taken up in 100 ml. of ethyl acetate, washed with 80 ml of saturated sodium bicarbonate and twice with 80 ml of water, dried over sodium sulfate and activated charcoal and the mixture vacuum filtered through dia~omaceous earth to ~ive a li~ht yellow solution. The solvent was stripped from the solution by rotary evaporation to givc 12.5 g. of a light yellow oil. The oil was taken up in a mix-ture of 20 ml of ethyl acetat~ and 80 ml of hexane and the solution allowed to stand in a refrigerator overnight. The 501-vent was stripped by rotary evaporation to give an oily residue which was taken up in 100 ml of hexane and allowed to stand.
The crystals which formed were coliected by filtration, recrys-tallized from a mixture of 100 ml of hexane and 10 ml of ethyl ; acetate, washed with 20 ml of hexane and dried to give 6.17g of the desired product ~compound XVIII), m.p. 153-154C (84.6%
yield). The structure of the product was confirmed by $R, UV
and NMR spectra and thin layer chromatography.
'.
:;
'7883t7 EXAMPLE XV
As a control a film unit was prepared as follows:
the negative element comprised an opaque subcoated polyethylene terephthalate film base on which the following layers were coated in succession.
1. as a polymeric acid layer approximately 9 parts of a 1/2 butyl ester of polyethylene/maleic anhydride copolymer and 1 part of polyvinyl butyral coated at a coverage of about 26,460 mgs.~m. ;
2. a timing layer comprising about 97% of a 60-29-6-4-0.4 pentapolymer of butylacrylate, diacetone acrylamide, methacrylic acid, styrene and acrylic acid and about 3% poly-vinylalcohol coated at a coverage of about 3000 mgs./m.2;
3. a cyan dye developer layer comprising about 511 mgs./m.2 of the cyan dye developer described in Example I, about 70 mgs./m. of 4'methyl phenyl hydroquinone and about 317 mgs./m. of gelatin;
4. a red-sensitive silvcr iodobromide emulsion layer comprising about 1378 mgs./m.~ of silver and about 827 mgs./m.2 of gelatin;
5. an interlayer comprising about 2090 mgs./m.2 of the pentapolymer described in layer 2, about 110 mgs./m.2 of polyacrylamide and about 44 mgs./m.2 o succinaldehyde;
6. a magenta dye developer layer comprising about 460 mgs./m2 of a magenta dye developer represented by the formula CH3 CH3 (CH2)3 OH ~ ~ \ H3 ~
(CH2)3 ~ - SO~ ~ ON
0~ H2)3 ~
-49- I~J
OH
1~ 337 and about 210 mgs./m of gelatin;
7. a green-sensitive silver iodobromide emulsion layer comprising about 723 mgs./m~2 of silver and about 318 mgs./m.2 of gelatin;
8. an interlayer comprising about 1881 mgs./m.2 of the pentapolymer described in layer 2 and about 99 mgs./m.Z of polyacrylamide;
9. a yellow dye developer layer comprising about 689 mgs./m. of the yellow dye developer described in Example I
and about 276 mgs./m.2 of gelatin;
10. a blue-sensitive silver iodobromide emulsion layer comprising about 764 mgs./m. of silver, about 499 mgs./m. of gelatin, and about 265 mgs./m.2 of 4'-methyl phenyl hydroquinone;
and 11. a topcoat layer of about 400 mgs./m.2 of gelatin.
The image receiving element comprised a transparent subcoated polyethylene terephthalate film base upon which there was coated an image receiving layer coated at a coverage of about 300 mgs./ft.2 (3229 mgs./m2) of: (a) 3 parts of a mixture of 2 parts polyvinyl alcohol and 1 part poly-4-vinylpyridine and (b) 1 part of a graft copolymer comprised of 4-vinylpyridine (4VP) and vinyl benzyl trimethyl ammonium chloride (TMQ) grafted onto hydroxyethyl cellulose (HEC) at a ratio HEC/4VP/TMQ oE
2.2/2.2/1; and about 5 mgs./ft.2 (53.8 mgs./m.2 of 1,4-butane-diol diglycidyl ether.
; The film unit was processed with a processing composition made up as follows:
~' ` 1~78837 Water 1632 ml TiO~ 2312.0 grams Oximated polydiacetoneacrylamide32.0 "
Potassium hydroxide (45~ solution) 468.0 "
Benzotriazole 22.0 "
4-aminopyrazole-t3,4-d)pyrimidine 10.0 6-methyl uracil 12.0 "
N-hydroxyethyl-N,N',N'-triscarboxymethyl ethylene diamine 30.0 "
Polyethylene glycol tM.w. 4000)18.0 Bis(20aminoethyl)sulfide 0.8 "
Colloidal silica (30% solids) 37.0 "
N-phenethyl-~-picolinium bromidè
tS0~ solids) 102.0 "
Allopurinol 3 . 3 2-methyl imidazole 23.~ "
6-methyl-5-bromo azabenzimidazole 4.8 "~52-C16~33 , ~ ~ 14.0 1~ 11 ~H O~
~ OOH HOO~--C~37O \ ~
~ 62.3 "
` :ii78837 The negative element was exposed (2 meter-candle-seconds) on a sensitometer to a test exposure scale with white light, and then brought together with the image receiving ele-ment and processed at room temper~ture (24C) by passing the film unit through a pair of rollers set at a gap spacing of about 0.0026 inch. The film unit was kept intact and viewed through the base of the image receiving element.
An identical film unit was processed in the same manner at 35C. The neutral density columns of the images were read on a densitometer to obtaih the Dmax and Dmin values for red, green and blue, respectlvely. The values obtained are shown in Table IX.
Seven additional film units according to the inven-tion (VIIIA - VIIIG) were prepared. These were identical to the control with the exception that the negatives also included a top coat layer comprising about 20 mg./ft.2 (215 mgs./m.2) of a blocked compound according to the invention (as shown in Tablc IX) and about 20 mg./ft.2 of gelatin. Thc ~ilm units were processed as described above at 24C and at 35C. The results are shown in Table X~.
TABLE X
Film Com- Dmax Dmin Unit Pound R G B R G B
Control 1.81 1.60 1.310.15 0.16 0.24 VIIIA XII 1.60 1.48 1.40 0.180.17 0.24 VIIIB XIII 1.33 1.43 1.41 0.150.16 0.23 - VIIIC XIV 1.68 1.74 1.91 0.160.17 0.26 VIIID XV 1.44 1.39 1.37 0.160.13 0.16 VIIIE XVI 1.30 1.42 1.46 0.150~13 0.15 VIIIF XVII 1.58 1.65 1.64 0.160.13 0.15 VIIIG XVIII1.48 1.83 1.88 0.140.15 0.23 Table X (continued) Film Com- Dmax Dmin Unit Pound R G B R G B
Control - 1.43 1.20 0.9~0.16 0.17 0.25 VIIIA XII 1.32 1.23 1.12 0.160.17 0.24 VIIIs XIII 1.07 1.13 1.11 0.160.17 0.25 VIIIC XIV 1.65 1.67 1.62 0.160.17 0.26 VIIID XV 1.28 1.24 1.14 0.160.14 0.17 VIIIE XVI 1.24 1.27 1.24 0.170.14 0.17 VIIIF XVII 1.40 1.35 1.34 0.160.14 0.17 VIIIG XVIII1.67 1.78 1.61 0.140.15 0.25 It is seen that at both 24C and 35C the blue DmaX
of Film Units VIIIA - VIIIG is higher than that of the Control and, in some instances much higher. At 24C the green DmaX of Film Units VIIC, VIIF and VIIG is higher than that of the Control lS while at 35C the green DmaX of all the Film Units except VIIIB is higher.
EXAMPLE XVI
PREPARATION OF COMPOUND XIX
A mixture of compound II (1.175 g, 5 mmol), sodium bicarbonate (420 mg., 5 mmol) and p-acetoxybenzyl chloride (925 mg., 5 mmol) in 30 ml of acetone was heated to boiling on a steam bath for 24 ho~rs. The solution was vacuum filtered and the solvent was removed from the filtrate by rotary evapora-tion a~ 25C to givo a light ycllow oil. Thc oil was taken up in 30 ml. of methanol, the solution vacuum filtered and the filtrate allowed to stand overnight in a refrigerator. The light yellow crystals which formed were collected by filtration and dried under reduced pressure at room temperature to give 1.34g (70~ yield) of compound XIX, m.p. 126-127C.
! C18H17N5O3S requires 56.38~ C, 4.47~ H, 18.27% N and 8.36% S. Elemental analysis found 56.50% C, 4.57% H, 18.27% N
and 8.12% S.
1'78837 Although the invention has been described with respect to specific preferred embodiments, it is not intended to be l.imited thereto but rather those skilled in the art will recog-nize that variations and modifications may be made within the spirit of the invention and the scope of the appended claims.
, -5~-
The image receiving element was identical to that described in Example V. The film unit was processed with a processing composition as described in Example V.
Six additional film units were prepared (VIIA-VIIF).
Film Units VIIA-VIIC further included 1 mg/m , 2 mgs/m and 3 mgs/m2, respectively, of compound II in layer 5 of the photo-sensitive element and Film Units VIID-VIIF furthex included 1 mg~m2, 2 mgs/m2 and 3 mgs/m2 of compound XI in layer S of the photosensitive element. An identical set of film units was also processed at 95F. The results are shown in Table IX.
- ` ` li'7883~7 TABLE IX
Film Dmax Rel. Speed Unit R G B R G B
Control1.95 1.67 2.231.50 1.49 1.32 VII A 2.03 1.75 2.251.52 1.46 1.33 VII B 2.09 1l70 2.241.47 1.46 1.33 VII C 2.14 1.78 2.281.41 1.39 1.29 VII D 2.01 1.71 2.231.56 1.48 1.35 VII E 2.04 1.73 2.251.58 1.46 1.37 VII F 2.08 1.71 2.231.57 1.43 1.39 .
~ Dmax R G B
Control -0.56 -0.20 -0.18 VII A -0.48 -0.19 -0.15 VII B -0.27 -0.09 -0.11 VII C -0.22 -0.06 -0.11 VII D -0.37 -0.12 -0.14 VII E -0.27 -0.05 -0.11 VII F -0.19 +0.06 -0.05 -It can be seen that at room temperature the presence of compounds II and XI provided an increase in red and green Dmax At 95F processing the presence of compounds II and XI
gave smaller losses (varying with the coverages) of red, blue and green DmaX
EXAMPLE VIII
PREP-ARATION OF COMPOUND XII
A cataly~t was prepared by stirring a mixture of Celite ~ (10 g.) (diatomaceous earth available from Johns Manville) and potassium fluoride dihydrate (15 g.) in 250 ml.
o-f distilled water for 30 minutes. The water was removed on a rotary evaporator and the solids dried overnight at room temperature under high vacuum. The catalyst was further dried in a vacuum oven at 58-60C for about two days.
To a stirred solution of 1-(4-hydroxyphenyl)-5-mercaptotetrazole (5g.) in dry tetrahydrofuran (50 ml.) at room temperature under nitrogen there were added methylvinyl-sulfone (2.8g.) and the potassium fluoride/Celite catalyst (lg.~. The reaction mixture was stirred slowly for 24 hours.
The solids were removed by filtration and the solvent was removed from the filtrate leaving behind a clear yellow-brown oil. The oil was dried under vacuum to give a tacky gum-like material. Recrystallization from methanol followed by drying to constant weight under vacuum gave a white, solid, compound XII, m.p. 139~-141C.
The NMR spectrum of the material was consistent ; with compound XII. 13C NMR (dmso-d6); ~159.28, 153.69, 126.28, 124.05, 116.23, 53.01, 40.59, 25;29 ppm.
EXAMPLE IX
EPAIU~TION OF COMPOUND XI IT
To a suspension of.compound IV (2.166g, 8.43 mmol) in methanol (10 ml) there were added, under nitrogen, 78% methyl vinyl sulfone (1.44g, 8.42 mmol) and 0.25 ml of 40~ benzyl trimethyl ammonium hydroxide in methanol and the reaction ! mixture refluxed for twenty-four hours. The cooled reaction mixture was filtered to collect the white crystals which had formed. Thin layer chromatography showed that some starting materials were present. The desired product, compound XIII, was separated by column chromatography followed by removal of the solvent, crystallization on standing and drying. The structure , 30 of the product was confirmed by UV and 13C NMR spectra.
' ~178837 EXAMPLE X
PREPARATION OF COMPOUND XIV
-A catalyst was prepared by stirring a mixture of lOg of Celite R (diatomaceous earth available from Johns Manville) and 15 g of potassium flùoride in 250 ml of distilled water for about 30 minutes, removing the water on a rotary evaporator at 56C and drying the solid under vacuum at 58-60C
to calculated weight, 196 g. The catalyst (lg) was added to a stirred solution of Sg of compound I and 1.8g of methyl vinyl ketone in 50 ml of dry tetrahydrofuran and the suspension was stirred under nitrogen at room temperature for three days. The solids were removed by filtering and the solvent removed from the filtrate to give about 7g of a brown-yellow oil which was stirred briefly with 70 ml of ether at room temperature. The ether solution was decanted from the brown oily solid which had deposited, and the crystalline solid which formed in the ether on standing collected by filtration, washed and dried to give 4g o~ white crystals (com~ound ~IV), m.p. 118-120C.
The structure of the product was confirmed by ~ 13C NMR spectrum.
EXAMPLE XI
PREPARATION OF COMPOUND XV
A mixture of compound IV (257 mg., 1.~0 mmol), methyl vinyl ketone ~0.081 nl, 1.0 mmol) and 200 mg of potassium fluoride on Celite catalyst (6 mmol/g) in about 2 ml of pyridine was stirred overnight. The reaction mixture was poured into 5% hydrochloric acid and the solid collected by filtration.
Thin layer chromatography showed two compounds. The desired product (compound XV) was separated by colu~n chromatography, followed by removal of the solvent, crystallization on standing and drying. The structure of the product was confirmed by a proton NMR spectrum.
` 11788~7 EXAMPLE XII
PREPARATION OF COMPOUND XVI
A stirred mixture of compound I t30.0g, 0.154 m), 3-bromopropionitrile (20.72 g, 0.154 m) and sodium bicarbonate (12.98 y, 0.154 m) in 600 ml of dry acetonitrile was heated under nitrogen at 55C for 42 hours, then cooled in an ice bath ~and vacuum filtered. The filtrate was evaporated on a rotary evaporator at 25C. The syrupy residue was taken up in 500 ml of ethyl acetate, washed with 400 ml of saturated NaHCO3 solu-tion and twice with 200 ml of water, dried over sodium sulfate and adsorptive activated carbon, and vacuum filtered throuqh diatomaceous earth. The filtrate was evaporated on a rotary evaporator at 25C and the crystalline residue was taken up in 200 ml of ethyl acetate and l00 ml of hexane added to the solu-tion. The solution was stored in a refrigerator overnight and 50 ml of hexane added. The crystalline material was collected by filtration, washed with two 50 ml volumes of hexane and dried under reduced pressure at ambient temperature to give 25 g (65.7% yield) of compound XVI.
EXAMPLE XIII
PREPARATION OF COMPOUND XVII
A mixture of compound II (11.647 g, 49.58 mmol), ~-bromopropionitrile (6.626g, 49.58 mmol) and sodium bicarbonate (4.17g, 49.58 mmol) in 200 ml of dry acetonitrile was magnet-ically stirred in a 55C bath under nitrogen overnight. The reaction mixture was vacuum filtered and the filtrate was stripped of solvent by rotar~ evaporation giving an orange oily residue. The residue was taken up in ethyl acetate (75 ml) and to the solution there were added seed crystals and 150 ml of hexane. The mixture was scratched and stored overnight in a 11'7883~7 refrigerator. The crystals which formed were collected ~y filtration, washed twice with hexane and dried to give 12.74 g of compound XVII as light yellow crystals, in p. 111-113C.
The structure of the product was confirmed by IR, UV and NMR
spectra and thin layer chromatography.
EXAMPLE XII
PREPARATION OF COMPOUND XVIII
A mixture of compound I (4.14g, 21.3 mmol), p-acetoxybenzyl chloride (3.94g, 21.3 mmol) and sodium bicarbonate (1.79g, 21.3 mmol) in 130 ml of dry acetonitrile was magnet-ically stirred under dry nitrogen at 55C overnight. The reaction mixture was cooled in an ice bath, the solids removed by vacuum filtration and the solvent stripped from the filtrate to give an oily residue. The oily residue was taken up in 100 ml. of ethyl acetate, washed with 80 ml of saturated sodium bicarbonate and twice with 80 ml of water, dried over sodium sulfate and activated charcoal and the mixture vacuum filtered through dia~omaceous earth to ~ive a li~ht yellow solution. The solvent was stripped from the solution by rotary evaporation to givc 12.5 g. of a light yellow oil. The oil was taken up in a mix-ture of 20 ml of ethyl acetat~ and 80 ml of hexane and the solution allowed to stand in a refrigerator overnight. The 501-vent was stripped by rotary evaporation to give an oily residue which was taken up in 100 ml of hexane and allowed to stand.
The crystals which formed were coliected by filtration, recrys-tallized from a mixture of 100 ml of hexane and 10 ml of ethyl ; acetate, washed with 20 ml of hexane and dried to give 6.17g of the desired product ~compound XVIII), m.p. 153-154C (84.6%
yield). The structure of the product was confirmed by $R, UV
and NMR spectra and thin layer chromatography.
'.
:;
'7883t7 EXAMPLE XV
As a control a film unit was prepared as follows:
the negative element comprised an opaque subcoated polyethylene terephthalate film base on which the following layers were coated in succession.
1. as a polymeric acid layer approximately 9 parts of a 1/2 butyl ester of polyethylene/maleic anhydride copolymer and 1 part of polyvinyl butyral coated at a coverage of about 26,460 mgs.~m. ;
2. a timing layer comprising about 97% of a 60-29-6-4-0.4 pentapolymer of butylacrylate, diacetone acrylamide, methacrylic acid, styrene and acrylic acid and about 3% poly-vinylalcohol coated at a coverage of about 3000 mgs./m.2;
3. a cyan dye developer layer comprising about 511 mgs./m.2 of the cyan dye developer described in Example I, about 70 mgs./m. of 4'methyl phenyl hydroquinone and about 317 mgs./m. of gelatin;
4. a red-sensitive silvcr iodobromide emulsion layer comprising about 1378 mgs./m.~ of silver and about 827 mgs./m.2 of gelatin;
5. an interlayer comprising about 2090 mgs./m.2 of the pentapolymer described in layer 2, about 110 mgs./m.2 of polyacrylamide and about 44 mgs./m.2 o succinaldehyde;
6. a magenta dye developer layer comprising about 460 mgs./m2 of a magenta dye developer represented by the formula CH3 CH3 (CH2)3 OH ~ ~ \ H3 ~
(CH2)3 ~ - SO~ ~ ON
0~ H2)3 ~
-49- I~J
OH
1~ 337 and about 210 mgs./m of gelatin;
7. a green-sensitive silver iodobromide emulsion layer comprising about 723 mgs./m~2 of silver and about 318 mgs./m.2 of gelatin;
8. an interlayer comprising about 1881 mgs./m.2 of the pentapolymer described in layer 2 and about 99 mgs./m.Z of polyacrylamide;
9. a yellow dye developer layer comprising about 689 mgs./m. of the yellow dye developer described in Example I
and about 276 mgs./m.2 of gelatin;
10. a blue-sensitive silver iodobromide emulsion layer comprising about 764 mgs./m. of silver, about 499 mgs./m. of gelatin, and about 265 mgs./m.2 of 4'-methyl phenyl hydroquinone;
and 11. a topcoat layer of about 400 mgs./m.2 of gelatin.
The image receiving element comprised a transparent subcoated polyethylene terephthalate film base upon which there was coated an image receiving layer coated at a coverage of about 300 mgs./ft.2 (3229 mgs./m2) of: (a) 3 parts of a mixture of 2 parts polyvinyl alcohol and 1 part poly-4-vinylpyridine and (b) 1 part of a graft copolymer comprised of 4-vinylpyridine (4VP) and vinyl benzyl trimethyl ammonium chloride (TMQ) grafted onto hydroxyethyl cellulose (HEC) at a ratio HEC/4VP/TMQ oE
2.2/2.2/1; and about 5 mgs./ft.2 (53.8 mgs./m.2 of 1,4-butane-diol diglycidyl ether.
; The film unit was processed with a processing composition made up as follows:
~' ` 1~78837 Water 1632 ml TiO~ 2312.0 grams Oximated polydiacetoneacrylamide32.0 "
Potassium hydroxide (45~ solution) 468.0 "
Benzotriazole 22.0 "
4-aminopyrazole-t3,4-d)pyrimidine 10.0 6-methyl uracil 12.0 "
N-hydroxyethyl-N,N',N'-triscarboxymethyl ethylene diamine 30.0 "
Polyethylene glycol tM.w. 4000)18.0 Bis(20aminoethyl)sulfide 0.8 "
Colloidal silica (30% solids) 37.0 "
N-phenethyl-~-picolinium bromidè
tS0~ solids) 102.0 "
Allopurinol 3 . 3 2-methyl imidazole 23.~ "
6-methyl-5-bromo azabenzimidazole 4.8 "~52-C16~33 , ~ ~ 14.0 1~ 11 ~H O~
~ OOH HOO~--C~37O \ ~
~ 62.3 "
` :ii78837 The negative element was exposed (2 meter-candle-seconds) on a sensitometer to a test exposure scale with white light, and then brought together with the image receiving ele-ment and processed at room temper~ture (24C) by passing the film unit through a pair of rollers set at a gap spacing of about 0.0026 inch. The film unit was kept intact and viewed through the base of the image receiving element.
An identical film unit was processed in the same manner at 35C. The neutral density columns of the images were read on a densitometer to obtaih the Dmax and Dmin values for red, green and blue, respectlvely. The values obtained are shown in Table IX.
Seven additional film units according to the inven-tion (VIIIA - VIIIG) were prepared. These were identical to the control with the exception that the negatives also included a top coat layer comprising about 20 mg./ft.2 (215 mgs./m.2) of a blocked compound according to the invention (as shown in Tablc IX) and about 20 mg./ft.2 of gelatin. Thc ~ilm units were processed as described above at 24C and at 35C. The results are shown in Table X~.
TABLE X
Film Com- Dmax Dmin Unit Pound R G B R G B
Control 1.81 1.60 1.310.15 0.16 0.24 VIIIA XII 1.60 1.48 1.40 0.180.17 0.24 VIIIB XIII 1.33 1.43 1.41 0.150.16 0.23 - VIIIC XIV 1.68 1.74 1.91 0.160.17 0.26 VIIID XV 1.44 1.39 1.37 0.160.13 0.16 VIIIE XVI 1.30 1.42 1.46 0.150~13 0.15 VIIIF XVII 1.58 1.65 1.64 0.160.13 0.15 VIIIG XVIII1.48 1.83 1.88 0.140.15 0.23 Table X (continued) Film Com- Dmax Dmin Unit Pound R G B R G B
Control - 1.43 1.20 0.9~0.16 0.17 0.25 VIIIA XII 1.32 1.23 1.12 0.160.17 0.24 VIIIs XIII 1.07 1.13 1.11 0.160.17 0.25 VIIIC XIV 1.65 1.67 1.62 0.160.17 0.26 VIIID XV 1.28 1.24 1.14 0.160.14 0.17 VIIIE XVI 1.24 1.27 1.24 0.170.14 0.17 VIIIF XVII 1.40 1.35 1.34 0.160.14 0.17 VIIIG XVIII1.67 1.78 1.61 0.140.15 0.25 It is seen that at both 24C and 35C the blue DmaX
of Film Units VIIIA - VIIIG is higher than that of the Control and, in some instances much higher. At 24C the green DmaX of Film Units VIIC, VIIF and VIIG is higher than that of the Control lS while at 35C the green DmaX of all the Film Units except VIIIB is higher.
EXAMPLE XVI
PREPARATION OF COMPOUND XIX
A mixture of compound II (1.175 g, 5 mmol), sodium bicarbonate (420 mg., 5 mmol) and p-acetoxybenzyl chloride (925 mg., 5 mmol) in 30 ml of acetone was heated to boiling on a steam bath for 24 ho~rs. The solution was vacuum filtered and the solvent was removed from the filtrate by rotary evapora-tion a~ 25C to givo a light ycllow oil. Thc oil was taken up in 30 ml. of methanol, the solution vacuum filtered and the filtrate allowed to stand overnight in a refrigerator. The light yellow crystals which formed were collected by filtration and dried under reduced pressure at room temperature to give 1.34g (70~ yield) of compound XIX, m.p. 126-127C.
! C18H17N5O3S requires 56.38~ C, 4.47~ H, 18.27% N and 8.36% S. Elemental analysis found 56.50% C, 4.57% H, 18.27% N
and 8.12% S.
1'78837 Although the invention has been described with respect to specific preferred embodiments, it is not intended to be l.imited thereto but rather those skilled in the art will recog-nize that variations and modifications may be made within the spirit of the invention and the scope of the appended claims.
, -5~-
Claims (40)
1. A photographic product for use in forming a diffusion transfer photographic image comprising a photo-sensitive element comprising a support carrying at least one silver halide emulsion layer having associated therewith an image dye-providing material, a second sheet-like element positioned in superposed or superposable relationship with said photosensitive element, an image receiving layer posi-tioned in one of said elements, means for lowering the pH of an aqueous alkaline processing composition positioned in one of said elements, a rupturable container releasably holding an aqueous alkaline processing composition adapted, when distri-buted between a pair of predetermined layers carried by said photosensitive element and said second element, to develop said silver halide emulsion and provide a diffusion transfer image on said image receiving layer, said product including at least one compound represented by the formula wherein X represents the nonmetallic atoms necessary to form a nucleus which completes a 5- or 6-membered heterocyclic moiety on said structure, R is H, an alkali metal or an group which is cleavable in said aqueous alkaline processing compo-sition and R1 is either a group which has a pKa of from about 7 to about 14 which is ionizable to an anion and wherein the silver salt of the mercaptan resulting from cleavage or ionization of -SR is more soluble in said agueous alkaline processing composition in the pH range within which R1 is ionized to an anion than said silver salt is below that pH range, or a precursor, wherein said processing composition initially has a pH substantially equal to or above the pKa of R1 and said means for lowering the pH of an aqueous alkaline processing composition is adapted to lower the pH of said aqueous alkaline processing composition below the pKa of R1.
2. The product as defined in Claim 1 wherein the photosensitive element comprises a support carrying a blue-sensitive silver halide emulsion layer having a yellow image dye-providing material associated therewith, a green-sensitive silver halide emulsion layer having a magenta image dye-providing material associated therewith and a red-sensitive silver halide emulsion layer having a cyan image dye-providing material associated therewith.
3. The product as defined in Claim 2 wherein said yellow, magenta and cyan image dye-providing materials are initially diffusible.
4. The product as defined in Claim 3 wherein said image dye-providing materials are dye developers and said emulsions are negative working emulsions.
5. The product as defined in Claim 1 wherein said compound is incorporated in said processing composition.
6. The product as defined in Claim 5 wherein said compound is present in an amount of from about 0.02 to about 0.07 percent by weight of said processing composition.
7. The product as defined in Claim 1 wherein said second element has a transparent support and includes said means for lowering the pH of an aqueous alkaline processing composition and said image-receiving layer and wherein said processing composition in-cludes a light-reflecting pigment adapted to provide a white background against which an image formed in said image-receiving layer may be viewed through said transparent support.
8. The product as defined in Claim 7 wherein said light-reflecting pigment is titanium dioxide.
9. The product as defined in Claim l wherein R is H.
10. The product as defined in Claim 9 wherein R1 is selected from the group consisting of , -OH and -SO2NH2.
11. The product as defined in Claim 1 wherein R is a group which is cleavable in said aqueous alkaline processing composition and said compound is incorporated in said photosensitive element.
12. The product as defined in Claim 11 wherein Rl is selected from the group consisting of , -OH, and -SO2NH2.
13. The product as defined in Claim 1 wherein Rl is a group having a pKa of from about 8.5 to about 13.5.
14. The product as defined in Claim 1 wherein said compound is represented by the formula or
15. The product as defined in Claim 1 wherein said compound is represented by the formula
16. The product as defined in Claim 15 wherein R is H and R1 is selected from the group consisting of , -OH and -SO2NH2
17. The product as defined in Claim 16 wherein R1 is -OH.
18. The product as defined in Claim 1 wherein said compound is incorporated in said processing composition and in said photosensitive element.
19. The product as defined in Claim 18 wherein R is H for said compound incorporated in said processing composition and R is a group which is cleavable in said aqueous alkaline processing composition for said compound which is incorporated in said photosensitive element.
20. A diffusion transfer photographic process comprising exposing a photosensitive element comprising a support carrying at least one silver halide emulsion layer having associated therewith an image dye-providing material, applying an aqueous alkaline processing composition to said exposed photosensitive element to effect development and to form an imagewise distribution of image dye-providing material as a function of development and transferring at least a portion of said imagewise distribution of image dye-providing material to an image receiving layer in superposed or super-posable relationship therewith to thereby provide a diffusion transfer image, said development being effected in the presence of at least one compound represented by the formula wherein X represents the nonmetallic atoms necessary to form a nucleus which completes a 5- or 6-membered heterocyclic moiety on said structure, R is H, an alkali metal or a group which is cleavable in said photographic aqueous alkaline processing composition; and R1 is a group which has a pKa of from about 7 to about 14 which is ionizable to an anion and wherein the silver salt of the mercaptan resulting from cleavage or ionization of -SR is more soluble in said aqueous alkaline processing composition in the pH range within which R1 is ionized to an anion than said silver salt is below that pH range, or a precursor, wherein said processing composition has a pH
substantially equal to or above the pKa of R1 when said composition initially contacts said compound, and subsequently lowering the pH of said aqueous alkaline processing composition below the pKa of R1.
substantially equal to or above the pKa of R1 when said composition initially contacts said compound, and subsequently lowering the pH of said aqueous alkaline processing composition below the pKa of R1.
21. The process as defined in Claim 20 wherein the photosensitive element comprises a support carrying a blue-sensitive silver halide emulsion layer having a yellow image dye-providing material associated therewith, a green-sensitive silver halide emulsion layer having a magenta image dye-providing material associated therewith and a red-sensitive silver halide emulsion layer having a cyan image dye-providing material associated therewith.
22. The process as defined in Claim 20 wherein said yellow, magenta and cyan image dye-providing materials are initially diffusible.
23. The process as defined in Claim 22 wherein said image dye-providing materials are dye developers and said emulsions are negative working emulsions.
24. The process as defined in Claim 20 wherein said compound is incorporated in said processing composition.
25. The process as defined in Claim 24 wherein said compound is present in an amount of from about 0.02 to about 0.07 percent by weight of said processing composition.
26. The process as defined in Claim 20 wherein said image-receiving layer is carried by a transparent support which also carries a layer of material for lowering the pH of said processing composition and said processing composition includes a light-reflecting pigment adapted to provide a white background against which the image formed in said image-receiving layer may be viewed through said transparent support.
27. The process as defined in Claim 26 wherein said light-reflecting pigment is titanium dioxide.
28. The process as defined in Claim 20 wherein R is H.
29. The process as defined in Claim 28 wherein R1 is selected from the group consisting of , -OH and -SO2NH2.
30. The process as defined in Claim 20 wherein R is a group which is cleavable in said aqueous alkaline processing composition and said compound is incorporated in said photo-sensitive element.
31. The process as defined in Claim 30 wherein R1 is selected from the group consisting of , -OH and -SO2NH2,
32. The process as defined in Claim 20 wherein R1 is a group having a pKa of from about 8.5 to about 13.5.
33. The process as defined in Claim 20 wherein said compound is represented by the formula or
34. The process as defined in Claim 20 wherein said compound is represented by the formula
35. The process as defined in Claim 34 wherein R
is H and R1 is selected from the group consisting of -OH, and -SO2NH2.
is H and R1 is selected from the group consisting of -OH, and -SO2NH2.
36. The process as defined in Claim 35 wherein R1 is -OH.
37. The process as defined in Claim 20 wherein said compound is incorporated in said processing composition and in said photosensitive element.
38. The process as defined in Claim 37 wherein R is H for said compound incorporated in said processing composition and R is a group which is cleavable in said aqueous alkaline processing composition for said compound which is incorporated in said photosensitive element.
39. The process as defined in Claim 20 wherein said compound is incorporated in said image-receiving layer.
40. The product as defined in Claim 1 wherein said compound is incorporated in said image-receiving layer.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/222,543 US4355092A (en) | 1981-01-05 | 1981-01-05 | Novel phenylmercaptoazole compounds |
| US06/222,502 US4390613A (en) | 1981-01-05 | 1981-01-05 | Diffusion transfer photographic system utilizing substituted phenylmercaptoazoles |
| US222,502 | 1981-01-05 | ||
| US222,543 | 1981-01-05 | ||
| US222,542 | 1981-01-05 | ||
| US06/222,542 US4355101A (en) | 1981-01-05 | 1981-01-05 | Phenylmercaptoazole compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1178837A true CA1178837A (en) | 1984-12-04 |
Family
ID=27397095
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000393496A Expired CA1178837A (en) | 1981-01-05 | 1982-01-04 | Diffusion transfer photographic system using substituted phenylmercaptoazoles |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1178837A (en) |
-
1982
- 1982-01-04 CA CA000393496A patent/CA1178837A/en not_active Expired
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