CA1038864A - Azo compounds and photographic materials - Google Patents
Azo compounds and photographic materialsInfo
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- CA1038864A CA1038864A CA192,229A CA192229A CA1038864A CA 1038864 A CA1038864 A CA 1038864A CA 192229 A CA192229 A CA 192229A CA 1038864 A CA1038864 A CA 1038864A
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- carbon atoms
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- formula
- sulfamoyl
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Abstract
Magenta image dye-providing compound having formulas as follows: I. II. III. wherein: Car represents a carrier moiety which, as a function of oxidation under alkaline conditions, releases a diffusible dye from said compound; m and q each represent an integer having a value of 0 or 1; X represents a bivalent linking group; R represents hydrogen or alkyl; J represents a bivalent radical selected from sulfonyl or carbonyl; Q represents hydrogen, hydroxy or an acylamino radical; G represents hydroxy, a salt thereof, or a hydrolyzable acyloxy group; r represents an integer having a value of 1 or 2; Z represents cyano, trifluoromethyl, a carboxy, a carboxylic acid ester, nitro in the 2- or 3-position relative to the azo radical, fluorosulfonyl, sulfo, halogen, an alkylsulfonyl radical; a phenylsulfonyl radical, alkylcarbonyl, a sulfamoyl radical; n carbamoyl radical, and, in formulas I or II when r is 1, Z may represent a radical having the formula CAR-¢X-(NR-J)q!m- wherein Car, X, J, R, q and m are as described previously; R1 represents hydrogen, an alkyl radical, an alkoxy radical or a halogen atom; E is in the 5-, 6- or 7- position relative to G and represents hydrogen, carboxy, a carboxylic acid ester, sulfo, a sulfamoyl radical, a carbamoyl radical, alkylsulfonyl radical or a phenylsulfonyl radical; Z1 represents hydrogen or Z; with the proviso that there be no more than one sulfo radical and no more than one carboxy radical present in said compound.
Description
`
Field of Invention ~0~8S6~ ~
This invention relates to the art of photography and more particularly, to color diffusion transfer photography employing magenta dye-providing compounds.
Description of Prior Art Color diffusion transfer processes generally involve the use of a photographic element comprising a support, at least one silver halide emulsion layer and an image dye-provicling material which is contained in or contiguous said layer. The image dye-providing material typically can be thought o~ as having the structure Car-Col where:Ln Col is a colorant such as a dye or a dye precursor and Car is an associated carrier or monitoring group which as a function of alkaline processing effects a substantial change in the diffusivity of at least the Col portion of the compound.
After exposure, a photographic element as described above is treated with an alkaline processing solution to effe~t imagewise discrimination in the element. As mentioned previously, the imagewise discrimination is generally brought about by the monitoring or carrier group which, in the presence of the alkaline processing solution, is responsible for a substantial change in ; the diffusivity of at least the dye portion of the dye-providing material. As is known in the art, the dye-providing material can be initially immobile or initially mobile in the processing solution. Upon alkaline processing of an initially immobile dye-providing material, a mobile dye can be released imagewise or the material can be imagewise rendered soluble and thus mobile.
If the material is initially mobile, the processing solution typically renders the material insoluble (and thus immobile) in an imagewise fashion.
~ )38~316~ ~It is well known in the art to utilize image dye-providing materials in a photographic element wherein an imagewise exposed element can be contacted with an alkaline processing solution to effect an imagewise difference in mobility of at least a portion of the dye- `
providing material, i.e., to effect release of a dye or dye precursor, to render said compound insoluble or soluble. It is the particular carrier or monitoring group which determines what form the change in diffusivity (of at least the dye portion of the material~ will take. In , certain instances, an increase in solubility of a given compound can be .:, - 10 accomplished by substantially reducing the molecular weight of the 5,~ compound; see, for example, the disclosure in Gompf U. S. Patent No.
3,698,897, issued October 17, 1972. Exemplary of systems wherein the dye-providing compound splits o~f a dye are those described in Whitmore U. S. Patent No. 3,227,552, is~ued January 4, 1966 and Bloom U. S.
Patent No. 3,443,940, issued May 13, 1969 and Canadian Patent No.
~; 602,607, issued August 2, 1960. Similarly, Yutzy U. S. Patent ~o. 2,756,142, issued July 24, 1956, U. S. Patent No. 2,774,668, issued December 18, 1956 and U. S. Patent ~o. 2,983,606, issued May 9, 1961 describe photographic ~, elements wherein a dye-providing compound is rendered immobile in an imagewise fashion.
, ~3~C9~
All o~ these prior systems have utility; however, it is desired to provide new compounds which provide dyes having improved properties, such as improved hue, diffusibility, mordantability and the like.
Summary of the Invention We have found a class of magenta, azo dye-providing compounds well suited for use in color diffusion transfer color elements. The dye-providing compounds, as a function of typical processing under alkaline conditions, provide a magenta-colored substance having a mobility different than that of the compound.
Description of Preferred Embodiments The objects of the present invention are achieved through the use in color diffusion transfer elements of a new class of magenta, azo dye-providing compounds. Typically, these compounds are utilized in a photosensitive element which comprises a support having thereon at least one photosensitive silver halide emulsion, and at least one of said layers having associated therewith a magenta, azo dye-providing compound of this invention.
The compounds of this invention can be represented by the following formulas:
I ~038864 I. Car -[X~(NR~~q~
G ~ ~ - ~ 1 , .
Il ~Car _ X-J~
III Car -[X-~NR-J) j ~ N= N ~ G
... ,,,, , ~ ,m ~ zl E ~ Q
~herein: , ',~ Car represents a carrier which is a moiety that,as a function of oxidation under alkaline conditions, provides a substance having a mobility dif~erent than that of said compound;
X represents a bivalent linking group of the formula:
, -R2- ~ -R2p- where each R2 can be the same or different and - 10 each represents an alkylene radical having 1 to about 8 carbon atoms a phenylene radical or a substituted phenylene radical havlng 6 to 9 carbon atoms; L repxesents a bivalent radical such as oxy (-O-), carbonyl (-CO-), carbamoyl ~-NHCO-), sul-: fonamido ~-SO2NH-), carboxamido ~-CONH-), sulfamoyl t-NHSO-), 8ulfinyl (-SO-), sulfonyl (-SO2-) etc; n is an integer having a value of 0 or 1; p is 1 when n equals 1 and p is 1 or 0 when n equals 0 provided that when p is 1 the carbon content of the sum of both R2 radicals does not exceed 14 carbon atoms.
R represents a hydrogen atom, an alkyl radical having ; cO 1 to 6 carbon atoms;
. _5_ .
._ _ __. _. . .. ..... .
,_ _ __,__ .. _._ ._,,_.~.. __,... _ ..... . r~
`` ~0388~
J represents a bivalent radical selected from sul-fonyl (-S02-) or carbonyl t-CO-);
m and q each represent an integer having a value of O or l;
. ~ Q represents a hydrogen atom, a hydroxy radical or a radical having the formula -N~CoR3 or -NHSo2R3 wherein R3 is an alkyl radical having 1 to about 6 carbon atoms, a substi-: tuted alkyl radical having 1 to 6 carbon atoms, benzyl, phenyl, . : or a substituted phenyl radical having 6 to 9 carbon atoms;
.~: 10 G represents a hydroxy radical or salt thereof, or a hydrolyzable acyloxy group, having the formula:
O O
CR4 or -oCoR4 wherein R4 is an alkyl radical having 1 to about 18 carbon atoms, phenyl or substituted phenyl having 6 to 18 carbon . atoms;
Z represents one or more electron-withdrawing groups - . selected from a cyano radical (-CN), a trihalomethyl radical (e.g., -CF3, -CC13, etc), a carboxy radical including salts thereof, such as alkali metal salts or amine salts (e.g., -COOH, -COO-Li+~-COO-K+, -COO~Na+, -COO-NH3+, etc), a carboxylic acid ester such as alkyl or aryl esters having 1 to about 18 carbon atoms in the alkyl or aryl moiety (e.g., -CooR4 wherein R4 is as defined above)S an alkylsulfonyl radical having 1 to about 8 ca~bon atoms in the alkyl moiety (e.g., -S02CH3, -S02C2H5, etc), a sulfamoyl radical of the formula -So2NR5R6 wherein R5 is hydrogen, :
38~64 ~;
alkyl of 1 to about 8 carbon atoms or aryl of 6 to about 13 carbon - atoms (e.g., phenyl, tolyl, etc), R6 can represent the same sub-stituents as R5 or alkyl- or arylcarbonyl as well as alkyl- or arylsulfonyl having 1 to about 8 carbon atoms in the alkyl or aryl moiety (e-g-, -COCH3, -COC3H7~ -C0C6H5~ -C0cH2c6H5~ -Coc6H4cH3 -S02C6H5, -S02C~2C6H5, etc), a carbamoyl radical of the formula -CoN(R5)2 ~herein each R5`can be the same or diffe~ent and R5 is as described previously), and R5 and R6 when taken together, can represent l-(dialkylamino)alkylidene (having 1 to about 8 carbon atoms in the alkyl moiety and 1 to about 4 carbon atoms in the alkylidene moiety), a sulfo radical including salts thereof, such as alkali metal or amine salts (e.g., -S03H, -S03 Li~, -S03 K , -S03 Na , -S03 NH3 , etc), or a halogen atom (e.g., Cl, F, Br, etc), as well as a radical of the formula Car -~X-(NR-J)~]m wherein each member is as described above.
Rl represents a hydrogen atom, an alkoxy radical having from 1 to about 8 carbon atoms, a halogen atom (e.g., Cl, F, Br, etc), an alkyl radical (including substituted alkyl) having from 1 to about 8 carbon atoms (e.g., CH3, C2H5, C4Hg, C5HloCOOH, CH2C6H5, etc), or the carbon atoms necessary to form a fused ben~o ring attached at the 2- and 3-position or the 3- and 4-positions;
E, which can be in the 3-, 5-, 6- or 7-positions rela-tive to G, a carbamoyl radical, a sulfamoyl radical, a carboxy radical, a carboxylic acid ester or a sulfo radical, all as described above for Z or E can represent a hydrogen atom, zl represents a hydrogen atom or any of the electron-withdrawing substituents described for Z;
and all the compounds herein are with the proviso that there can be only one sulfo or carboxy radical present.
.
1(~3i 3864 In Formula II above, the dotted line is used to represent the fact that the carrier and associated linking group can be attached to either ring of the naphthalene nucleus; particularly, it is attached at the 3-9 5-, 6- or 7-positions relative to the moiety G.
As mentioned above, the present compounds contain a carrier moiety which, as a function (direct or inverse~ of oxidation under alkaline conditions, provides substance having a mobility different than that of the starting compound. Depending upon the carrier used, the dye-providing compounds of this invention can be of two basic types:
(1) initially immobile compounds of which at least a portion is rendered mobile or diffusible as a funct-Lon of development or (2) initlally mobile or difusible compounds which are renclered immobLle as a ~mction of development. Carriers useful in initially immobile dye-providing compounds such as those wherein the carrier, under alkaline conditions, effects a splitting off of a ballast group from the dye moiety are described further in Whitmore Canadian Patent 602,607, dated August 2, 1960 and Whitmore U. S. Patent No. 3,227,552, issued January 4, 1966.
Among the preferred initially immobile compounds are those in which the carrier, as a function of oxidation under alkaline conditions, releases a dye having a mobility diferent than that of the starting immobile compound. For example, useful carriers for compounds in which the carrier moiety undergoes intramolecular ring closure upon oxidation to split off a dye are described in U. S. Patents 3,443,939, 3,443,940 and 3,443,941, all issued May 13, 1969.
. . .
:
~)3~
Still other useful carriers are described in U. S. Paten~ No. 3,628,952, issued December 21, 1971. Additionally, carriers useful in the formation of initially mobile compounds such as those wherein the carrier functions as a developer are described in Friedman U. S. Patent 2,543,691, issued February 27, 1951, U. S. Patent 2,983,606, issued May 8, 1961 and U. S.
Patent 3,255,001, issued June 7, 1966.
Preferred compounds are those having formulas I, II and III
above wherein:
Car represents a carrier moiety which, as a function of oxidation under alkaline conditions, releases a dye having a mobility different than that of said compound;
Q represents a hydrogen atom, a hydroxy radical, or a radical having the formula -NHCoR3 or -NHSo2R3 whereln R3 preferably is alkyl of 1 to about 4 carbon atoms substituted with hydroxy, cyano, sulfamoyl, . carboxy or sulfo; benzyl, phenyl or phenyl substituted with carboxy, chloro, methyl, methoxy or sulfamoyl and when Q is hydroxy -NHCORJ or :, :. -NHSo2R3, it is located in the 5- or 8-position relative to G, ; G represents a hydroxy radical;
~- : Z represents a halogen atom, a cyano radical, a trihalomethyl radical, an alkylsulfonyl radical having 1 to 4 carbon atoms, or a sulfamoyl radical of the formula -S02NR R wherein :
:
~ _ g_ :.
~3886~L ' R5 is hydrogen, alkyl of 1 to about 4 carbon atoms or aryl of 6 to about 8 carbon atoms and R can represent the same substi-; tuents as R5 or alkyl- or arylcarbonyl as well as alk~l- or arylsulfonyl wherein th~ alkyl and ar~l mo-ieties are as described for R5, and R5 and R6, when taken together, represent a dialkyl-aminomethylene radical ha~ing 1 to about 4 carbon atoms in the alkyl moiety;
Rl represents a hydrogen atom, an alkoxy radical of 1 to about 4 carbon atoms or a halogen atom;
E represents a hydrogen atom or a sulfamoyl radical as described for Z in the preceding paragraph, and zl represents a hydrogen atom.
I Especially preferred compounds are those having j formulas I, II and III above wherein Car- represents a radical of the formula:
.
OH
IV. ,~~ ~
y ~ Ball wherein Ball represents an organic ballasting group of such size and configuration (e.g., simple organic groups or polymeric groups) as to render the compound nondiffusible during development in the alkaline processing composition and Y represents the carbon atoms necessary to complete a benzene or naphthalene nucleus including substituted benzene or naphthalene. When Y represents the atoms necessary to complete a naphthalene nucleus, Ball can be attached to either ring thereof.
~ . . . .
~ ~03~864 The nature of the ballast group (Ball) in the Formula IV for the compounds described above is not critical as long as it confers nondiffusibility to the compounds. Typical ballast groups include long chain alkyl radicals linked directly or indirectly to the compound as well as aromatic radicals of the benzene and naphthalene series indirectly attached or fused directly to the benzene nucleus, etc. Useful ballast groups generally have at least 8 carbon atoms such as a substi-tuted or unsubstituted alkyl group of 8 to 22 carbon atoms, an amide radical having 8 to 30 carbon atoms, a keto radical having 8 to 30 carbon atoms, etc, and may even comprise a polymer backbone.
Especially preferred compounds are those wherein the ballast is attached to the benzene nucleus through a carbamoyl radical (-NHCO-) or a sulfamoyl radical ~-NHS02-) in which the nitrogen ... .
is adjacent the ballast group.
In addition to the ballast, the benzene nucleus in the above formulas may have groups or atoms attached thereto such as the halogens, alkyl, aryl, alkoxy, aryloxy, nitro, amino, alkylamino, arylamino, amido, cyano, alkylmercapto, keto, carbo-alkoxy, heterocyclic groups, etc.
A suitable process for producing a photographic transfer image in color using the compounds of our invention, for example, those wherein Car is as shown in Formula IV comprises the steps of:
~ eating the above-described photosensitive element with an alkaline processing composition in the presence of a silver halide developing agent to effect development of each of the exposed silver halide emulsion layers, thereby oxidizing the developing agent and the oxidized developing agent in turn cross-oxidizing the sulfonamido compound, ~L03~i4 ~:
Field of Invention ~0~8S6~ ~
This invention relates to the art of photography and more particularly, to color diffusion transfer photography employing magenta dye-providing compounds.
Description of Prior Art Color diffusion transfer processes generally involve the use of a photographic element comprising a support, at least one silver halide emulsion layer and an image dye-provicling material which is contained in or contiguous said layer. The image dye-providing material typically can be thought o~ as having the structure Car-Col where:Ln Col is a colorant such as a dye or a dye precursor and Car is an associated carrier or monitoring group which as a function of alkaline processing effects a substantial change in the diffusivity of at least the Col portion of the compound.
After exposure, a photographic element as described above is treated with an alkaline processing solution to effe~t imagewise discrimination in the element. As mentioned previously, the imagewise discrimination is generally brought about by the monitoring or carrier group which, in the presence of the alkaline processing solution, is responsible for a substantial change in ; the diffusivity of at least the dye portion of the dye-providing material. As is known in the art, the dye-providing material can be initially immobile or initially mobile in the processing solution. Upon alkaline processing of an initially immobile dye-providing material, a mobile dye can be released imagewise or the material can be imagewise rendered soluble and thus mobile.
If the material is initially mobile, the processing solution typically renders the material insoluble (and thus immobile) in an imagewise fashion.
~ )38~316~ ~It is well known in the art to utilize image dye-providing materials in a photographic element wherein an imagewise exposed element can be contacted with an alkaline processing solution to effect an imagewise difference in mobility of at least a portion of the dye- `
providing material, i.e., to effect release of a dye or dye precursor, to render said compound insoluble or soluble. It is the particular carrier or monitoring group which determines what form the change in diffusivity (of at least the dye portion of the material~ will take. In , certain instances, an increase in solubility of a given compound can be .:, - 10 accomplished by substantially reducing the molecular weight of the 5,~ compound; see, for example, the disclosure in Gompf U. S. Patent No.
3,698,897, issued October 17, 1972. Exemplary of systems wherein the dye-providing compound splits o~f a dye are those described in Whitmore U. S. Patent No. 3,227,552, is~ued January 4, 1966 and Bloom U. S.
Patent No. 3,443,940, issued May 13, 1969 and Canadian Patent No.
~; 602,607, issued August 2, 1960. Similarly, Yutzy U. S. Patent ~o. 2,756,142, issued July 24, 1956, U. S. Patent No. 2,774,668, issued December 18, 1956 and U. S. Patent ~o. 2,983,606, issued May 9, 1961 describe photographic ~, elements wherein a dye-providing compound is rendered immobile in an imagewise fashion.
, ~3~C9~
All o~ these prior systems have utility; however, it is desired to provide new compounds which provide dyes having improved properties, such as improved hue, diffusibility, mordantability and the like.
Summary of the Invention We have found a class of magenta, azo dye-providing compounds well suited for use in color diffusion transfer color elements. The dye-providing compounds, as a function of typical processing under alkaline conditions, provide a magenta-colored substance having a mobility different than that of the compound.
Description of Preferred Embodiments The objects of the present invention are achieved through the use in color diffusion transfer elements of a new class of magenta, azo dye-providing compounds. Typically, these compounds are utilized in a photosensitive element which comprises a support having thereon at least one photosensitive silver halide emulsion, and at least one of said layers having associated therewith a magenta, azo dye-providing compound of this invention.
The compounds of this invention can be represented by the following formulas:
I ~038864 I. Car -[X~(NR~~q~
G ~ ~ - ~ 1 , .
Il ~Car _ X-J~
III Car -[X-~NR-J) j ~ N= N ~ G
... ,,,, , ~ ,m ~ zl E ~ Q
~herein: , ',~ Car represents a carrier which is a moiety that,as a function of oxidation under alkaline conditions, provides a substance having a mobility dif~erent than that of said compound;
X represents a bivalent linking group of the formula:
, -R2- ~ -R2p- where each R2 can be the same or different and - 10 each represents an alkylene radical having 1 to about 8 carbon atoms a phenylene radical or a substituted phenylene radical havlng 6 to 9 carbon atoms; L repxesents a bivalent radical such as oxy (-O-), carbonyl (-CO-), carbamoyl ~-NHCO-), sul-: fonamido ~-SO2NH-), carboxamido ~-CONH-), sulfamoyl t-NHSO-), 8ulfinyl (-SO-), sulfonyl (-SO2-) etc; n is an integer having a value of 0 or 1; p is 1 when n equals 1 and p is 1 or 0 when n equals 0 provided that when p is 1 the carbon content of the sum of both R2 radicals does not exceed 14 carbon atoms.
R represents a hydrogen atom, an alkyl radical having ; cO 1 to 6 carbon atoms;
. _5_ .
._ _ __. _. . .. ..... .
,_ _ __,__ .. _._ ._,,_.~.. __,... _ ..... . r~
`` ~0388~
J represents a bivalent radical selected from sul-fonyl (-S02-) or carbonyl t-CO-);
m and q each represent an integer having a value of O or l;
. ~ Q represents a hydrogen atom, a hydroxy radical or a radical having the formula -N~CoR3 or -NHSo2R3 wherein R3 is an alkyl radical having 1 to about 6 carbon atoms, a substi-: tuted alkyl radical having 1 to 6 carbon atoms, benzyl, phenyl, . : or a substituted phenyl radical having 6 to 9 carbon atoms;
.~: 10 G represents a hydroxy radical or salt thereof, or a hydrolyzable acyloxy group, having the formula:
O O
CR4 or -oCoR4 wherein R4 is an alkyl radical having 1 to about 18 carbon atoms, phenyl or substituted phenyl having 6 to 18 carbon . atoms;
Z represents one or more electron-withdrawing groups - . selected from a cyano radical (-CN), a trihalomethyl radical (e.g., -CF3, -CC13, etc), a carboxy radical including salts thereof, such as alkali metal salts or amine salts (e.g., -COOH, -COO-Li+~-COO-K+, -COO~Na+, -COO-NH3+, etc), a carboxylic acid ester such as alkyl or aryl esters having 1 to about 18 carbon atoms in the alkyl or aryl moiety (e.g., -CooR4 wherein R4 is as defined above)S an alkylsulfonyl radical having 1 to about 8 ca~bon atoms in the alkyl moiety (e.g., -S02CH3, -S02C2H5, etc), a sulfamoyl radical of the formula -So2NR5R6 wherein R5 is hydrogen, :
38~64 ~;
alkyl of 1 to about 8 carbon atoms or aryl of 6 to about 13 carbon - atoms (e.g., phenyl, tolyl, etc), R6 can represent the same sub-stituents as R5 or alkyl- or arylcarbonyl as well as alkyl- or arylsulfonyl having 1 to about 8 carbon atoms in the alkyl or aryl moiety (e-g-, -COCH3, -COC3H7~ -C0C6H5~ -C0cH2c6H5~ -Coc6H4cH3 -S02C6H5, -S02C~2C6H5, etc), a carbamoyl radical of the formula -CoN(R5)2 ~herein each R5`can be the same or diffe~ent and R5 is as described previously), and R5 and R6 when taken together, can represent l-(dialkylamino)alkylidene (having 1 to about 8 carbon atoms in the alkyl moiety and 1 to about 4 carbon atoms in the alkylidene moiety), a sulfo radical including salts thereof, such as alkali metal or amine salts (e.g., -S03H, -S03 Li~, -S03 K , -S03 Na , -S03 NH3 , etc), or a halogen atom (e.g., Cl, F, Br, etc), as well as a radical of the formula Car -~X-(NR-J)~]m wherein each member is as described above.
Rl represents a hydrogen atom, an alkoxy radical having from 1 to about 8 carbon atoms, a halogen atom (e.g., Cl, F, Br, etc), an alkyl radical (including substituted alkyl) having from 1 to about 8 carbon atoms (e.g., CH3, C2H5, C4Hg, C5HloCOOH, CH2C6H5, etc), or the carbon atoms necessary to form a fused ben~o ring attached at the 2- and 3-position or the 3- and 4-positions;
E, which can be in the 3-, 5-, 6- or 7-positions rela-tive to G, a carbamoyl radical, a sulfamoyl radical, a carboxy radical, a carboxylic acid ester or a sulfo radical, all as described above for Z or E can represent a hydrogen atom, zl represents a hydrogen atom or any of the electron-withdrawing substituents described for Z;
and all the compounds herein are with the proviso that there can be only one sulfo or carboxy radical present.
.
1(~3i 3864 In Formula II above, the dotted line is used to represent the fact that the carrier and associated linking group can be attached to either ring of the naphthalene nucleus; particularly, it is attached at the 3-9 5-, 6- or 7-positions relative to the moiety G.
As mentioned above, the present compounds contain a carrier moiety which, as a function (direct or inverse~ of oxidation under alkaline conditions, provides substance having a mobility different than that of the starting compound. Depending upon the carrier used, the dye-providing compounds of this invention can be of two basic types:
(1) initially immobile compounds of which at least a portion is rendered mobile or diffusible as a funct-Lon of development or (2) initlally mobile or difusible compounds which are renclered immobLle as a ~mction of development. Carriers useful in initially immobile dye-providing compounds such as those wherein the carrier, under alkaline conditions, effects a splitting off of a ballast group from the dye moiety are described further in Whitmore Canadian Patent 602,607, dated August 2, 1960 and Whitmore U. S. Patent No. 3,227,552, issued January 4, 1966.
Among the preferred initially immobile compounds are those in which the carrier, as a function of oxidation under alkaline conditions, releases a dye having a mobility diferent than that of the starting immobile compound. For example, useful carriers for compounds in which the carrier moiety undergoes intramolecular ring closure upon oxidation to split off a dye are described in U. S. Patents 3,443,939, 3,443,940 and 3,443,941, all issued May 13, 1969.
. . .
:
~)3~
Still other useful carriers are described in U. S. Paten~ No. 3,628,952, issued December 21, 1971. Additionally, carriers useful in the formation of initially mobile compounds such as those wherein the carrier functions as a developer are described in Friedman U. S. Patent 2,543,691, issued February 27, 1951, U. S. Patent 2,983,606, issued May 8, 1961 and U. S.
Patent 3,255,001, issued June 7, 1966.
Preferred compounds are those having formulas I, II and III
above wherein:
Car represents a carrier moiety which, as a function of oxidation under alkaline conditions, releases a dye having a mobility different than that of said compound;
Q represents a hydrogen atom, a hydroxy radical, or a radical having the formula -NHCoR3 or -NHSo2R3 whereln R3 preferably is alkyl of 1 to about 4 carbon atoms substituted with hydroxy, cyano, sulfamoyl, . carboxy or sulfo; benzyl, phenyl or phenyl substituted with carboxy, chloro, methyl, methoxy or sulfamoyl and when Q is hydroxy -NHCORJ or :, :. -NHSo2R3, it is located in the 5- or 8-position relative to G, ; G represents a hydroxy radical;
~- : Z represents a halogen atom, a cyano radical, a trihalomethyl radical, an alkylsulfonyl radical having 1 to 4 carbon atoms, or a sulfamoyl radical of the formula -S02NR R wherein :
:
~ _ g_ :.
~3886~L ' R5 is hydrogen, alkyl of 1 to about 4 carbon atoms or aryl of 6 to about 8 carbon atoms and R can represent the same substi-; tuents as R5 or alkyl- or arylcarbonyl as well as alk~l- or arylsulfonyl wherein th~ alkyl and ar~l mo-ieties are as described for R5, and R5 and R6, when taken together, represent a dialkyl-aminomethylene radical ha~ing 1 to about 4 carbon atoms in the alkyl moiety;
Rl represents a hydrogen atom, an alkoxy radical of 1 to about 4 carbon atoms or a halogen atom;
E represents a hydrogen atom or a sulfamoyl radical as described for Z in the preceding paragraph, and zl represents a hydrogen atom.
I Especially preferred compounds are those having j formulas I, II and III above wherein Car- represents a radical of the formula:
.
OH
IV. ,~~ ~
y ~ Ball wherein Ball represents an organic ballasting group of such size and configuration (e.g., simple organic groups or polymeric groups) as to render the compound nondiffusible during development in the alkaline processing composition and Y represents the carbon atoms necessary to complete a benzene or naphthalene nucleus including substituted benzene or naphthalene. When Y represents the atoms necessary to complete a naphthalene nucleus, Ball can be attached to either ring thereof.
~ . . . .
~ ~03~864 The nature of the ballast group (Ball) in the Formula IV for the compounds described above is not critical as long as it confers nondiffusibility to the compounds. Typical ballast groups include long chain alkyl radicals linked directly or indirectly to the compound as well as aromatic radicals of the benzene and naphthalene series indirectly attached or fused directly to the benzene nucleus, etc. Useful ballast groups generally have at least 8 carbon atoms such as a substi-tuted or unsubstituted alkyl group of 8 to 22 carbon atoms, an amide radical having 8 to 30 carbon atoms, a keto radical having 8 to 30 carbon atoms, etc, and may even comprise a polymer backbone.
Especially preferred compounds are those wherein the ballast is attached to the benzene nucleus through a carbamoyl radical (-NHCO-) or a sulfamoyl radical ~-NHS02-) in which the nitrogen ... .
is adjacent the ballast group.
In addition to the ballast, the benzene nucleus in the above formulas may have groups or atoms attached thereto such as the halogens, alkyl, aryl, alkoxy, aryloxy, nitro, amino, alkylamino, arylamino, amido, cyano, alkylmercapto, keto, carbo-alkoxy, heterocyclic groups, etc.
A suitable process for producing a photographic transfer image in color using the compounds of our invention, for example, those wherein Car is as shown in Formula IV comprises the steps of:
~ eating the above-described photosensitive element with an alkaline processing composition in the presence of a silver halide developing agent to effect development of each of the exposed silver halide emulsion layers, thereby oxidizing the developing agent and the oxidized developing agent in turn cross-oxidizing the sulfonamido compound, ~L03~i4 ~:
2) forming an imagewise distribution of diffusible dye as a function of the imagewise exposure o~ each of the silver halide emulsion layers by cleaving each cross-oxidized sulfon-amido compound; and
3) diffusing to a dye image-receiving layer at least a portion of each of the imagewise distributions of diffusible anionic dye to provide an image. ~ i ~ ne photosensitive element~in the above-described process can be treated with an alkaline processing composition to effect or initiate development in any manner. A preferred method for applying processing composition is by use of a ruptur-able container or pod which contains the composition. In general, the processing composition employed in our system contains the developing agent for development, although the composition could also just be an alkaline solution where the developer is incor-porated in the photosensitive element, in which case the alkaline solution serves to activate the incorporated developer.
A photographic fiIm unit according to our invention which is adapted to be processed by passing the unit between a pair of juxtaposed pressure-applying members, comprises:
1) a photosensitive element as described above;
2) a dye image-receiving layer; and 3) means for discharging an alkaline processing co~position within the film unit such as a ruptur-able container which is adapted to be positioned during processing of the film unit so that a compressive force applied to the container by the - pressure-applying members will effect a discharge of the contents of the container within the film unit;
the film unit containing a silver halide developing agentO
~038~6~
The dye image-receiving layer in the above-described film unit can be located on a separate support adapted to be superposed on the photosensitive element after exposure thereof.
Such image-receiving elements are generally disclosed, for .
exàmple, in U. S. Patent 3,362,819. When the means for dis-charging the processing composition is a rupturable container, ; typically it is posi-tioned in relation to the photosensitive element and the image-receiving element so that a compressive force applied to the container by pressure-applying members, such as found in a camera designed for in-camera processing, will effect a discharge of the contents of the container between the image-receiving element and the outermost layer of the photo-sensitive element. After processing, the dye image-receiving element is separated from the photosensitive element.
The dye image-receiving layer in the above-described film unit can also be located integral with the photosensitive element between the support and the lowermost photosensitive silver halide emulsion layer~ One useful format for integral receiver-negative photosensitive elements is disclosed in Belgian Patent 757,960. In such an embodiment, the support for the photosensitive element is transparent and is coated with an image-receiving layer, a substantially opaque llght reflective layer, e.g., TiO2, and then the photosensitive layer of layers described above After exposure of the photosensitive element, a rupturable container containing an alkaline processing composi-- tion and an opaque process sheet are brought into superposedposition. Pressure-applying members in the camera rupture the container and spread processing composition over the photosensi-tive element as the film unit is withdrawn from the camera. The processing composition develops each exposed silver halide emul sion layer and dye images are formed as a function o-~ development i03886~
which diffuse to the image-receiving layer to provide a right-reading image which is viewed through the transparent support on the opaque reflecting layer backg~und.
Another format for integral negative-receiver photo- ;
sensitive elemen-ts in which the present invention can be employed is disclosed in Belgian Patent 757,959. In this embodiment~ the support for the photosensitive element is transparent and is coated with the image-receiving layer, a substantially opaque, light-reflective layer and the photosensitive layer or layers 10 described above. A rupturable container containing an alkaline processing composition and an opacifier is positioned adjacent to the top layer and a transparent top sheet. The film unit is placed in a camera, exposed through the transparent top sheet and then passed through a pair of pressure-applying members in the camera as it is being removed therefrom . The pressure- ~¦
applying members rupture the container and spread processing composition and opacifier over the negative portion of the film unit to render it light insensitive. The processing composition develops each silver halide layer and dye images are formed as 20 a result of development which dlffuse -to the image-receiving layer to provide a right-reading image that is viewed thrGugh the transparent support on the opaque reflecting layer background.
Still other useful integral fo~nats in which our sulfonamido compounds can be employed are described in U. S.
Patents 3,415,644; 3,415,645; 3,415,646; 3,647,437; and 3,635,707- -The film unit or assembly of the present inventioncan be used to produce positive images in single- or multi-colors. In a three-color system, each silver halide emulsion 30 layer of the film assembly will have associated therewith an image dye-providing material possessing a predominant spectral absorption within the region of the visible spectrum to which ~03~4 `~
said silver halide emulsion is sensitive, i.e., the blue-sensitive silver halide emulsion layer will have a yellow image dye-providing material associated therewith, the green-sensitive silver halide emulsion layer will have a magenta image dye-provicling material associated therewith, and the red-sensitive silver halide emulsion layer will have a cyan image dye-providing material associated therewith. The image dye-providing material associated with each silver halide emulsion layer can be contained either in the silver halide emulsion layer itself or in a layer contiguous to the silver halide emulsion layer. The magenta image dye-providing material will, of course, be a compound of this invention, and when G i8 an ester, the compound can be contained in the silver halide emulsion.
The concentration o the compounds which preferably are alkali-cleavable upon oxidation that are employed in the present ; invention can be varied over a wide range depending upon the particular compound employed and the results which are desired. For example, the image dye-providing compounds of the present invention can be coated in layers by using coating solutions containing between about 0.5 to about 8 percent by weight of the image dye-providing compound distributed in a hydrophilic film-forming natural or synthetic polymer, such as gelatin, polyvinyl alcohol, etc., which is adapted to be permeated by aqueous alkaline processing composition. Typically, the present compounds are incorporated in a coupler solvent Ce.g., a high boiling, water immiscible organic solvent2 prior to distribution in the gelatin by techniques known in the art.
" ~
~03~
Depending upon which Car is used on the present com-pounds, a variety of silver halide developing agents can be employed in our invention. If the carrier used is that of Formula IV, any silver halide developing agent can be used as long as it cross-oxidizes with the image dye-providing compounds used herein.
The developer can be employed in the photosensitive element to be activated by the alkaline processing composition. Specific examples of developers which can be employed in our invention include: hydroquinone, N-methylaminophenol, Phenidone (l-phenyl-3-pyrazolidone), Dimezone ~l-phenyl-4,4-dimethyl-3-pyrazolidone), l-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, ascorbic acid, aminophenols, N,N-diethyl-~-phenylenediamine, 3-methyl-N,N-diethyl-~-phenylenediamine, 3-methoxy-N-ethyl-N-ethoxy- p-phenylenediamine, etc. The black-and-white developers in this list are preferred, in that they have a reduced propensity of staining the dye image-receiving layer.
In a preferred embodiment of our invention, the silver halide developer in our process becomes oxidized upon development and reduces silver halide to silver metal. The oxidized developer then cross-oxidizes the sulfonamido phenol dye-releasing compound.
The product of cross-oxidation then undergoes alkaline hydrolysis, thus releasing an imagewise distribution of diffusible anionic dye which then diffuses to the receiving layer to provide the positive dye image. The diffusible moiety is transferrable in alkaline processing composition either by virtue of its self-diffusivity or by having attached to it one or more solubilizing - groups such as COOH, S03H, So2NR5R6, OH, etc (where R5 and R6 are as described previously with at least one being hydrogen).
In using the especially preferred dye-releasing compour,ds according to our invention, the production of diffus-ible dye images is a function of the reduction of developable silver halide images which may irvolve direct or reversal ~03~3864 ~
development of the silver halide emulsions with a silverhalide developing agent. If the silver halide emulsion employed is a direct~positive silver halide emulsion, such as an internal-image emulsion or a solarizing emulsion, which is developable in unexposed areas, a positive image can be obtained on the dye image-receiving layer. After exposure of the film unit, the ,.:
alkaline processing composition pçrmeates the various layers to initiate development o* the exposed photosensitive silver halide emulsion layers. The developing agent present in the film unit develops each of the silver halide emulsion layers in the un-exposed areas (since the silver halide emulsions are direct-positive ones)~ thus causing the developing agent to become oxidized imagewise corresponding to the une~posed areas of the direct-positive silver halide emulsion layers. The oxidized ; developing agent then cross-oxidizes the dye-releasing compounds and the oxidized form of the compounds then undergoes a base-catalyzed reaction in a preferred embodiment of our invention, to release the preformed dyes imagewise as a function of the imagewise exposure of each of the silver halide emulsion layers. At least a portion of the imagewise distributions of diffusible dyes diffuse to the image-receiving layer to form a positive image of the original i subject. After being contacted by the alkaline processing com-position, a pH-lowering layer in the film unit or image-receiving unit (if such a layer is needed) lowers the pH of the film unit of image receiving to stabilize the image.
If photographic elements are used which contain com-pounds of this invention wherein Car is a silver halide developer as described, for example, in U. S. Patent No. 2,983,606, when ~03~86~ ~
the liquid processing composition is applied, it permeates the emulsion to provide a solution of the dye developer substantially uniformly distributed in the emulsion. As the exposed silver halide emulsion is developed, the oxidation product of the dye developer is immobilized or precipitated in situ with the developed sil~er, thereby providing an imagewise distribution of unoxidized dye developer dissolved in the liquid processing composition. This immobilization is apparently due, at least in part, to a change in the solubility characteristics of the dye developer upon oxidation. At least part of this imagewise distribution of unoxidized dye-developer is transferred to a superposed image-receiving layer to provide a transfer image.
Internal-image silver halide emulsions useful in those embodiments wherein a dye is released as a function of oxidation are direct-positive emulsions that form latent images predominantly ~ inside the silver halide grains, as distinguished from silver ; halide grains that form latent images predominantly on the sur-face thereof. Such inte m al-image emulsions are described by Davey et al in U. S. Patent 2,592,250, issued April 8, 1952, and elsewhere in the literature. Other useful emulsions are described in Belgian Patent No. 780,531, dated March 31, 1972. Inte m al-image silver halide emulsions can be defined in terms of the increased maximum density obtained when developed with "inte m al-type" developers over that obtained when developed with "surface-type" developers. Suitable inte m al-image emulsions are those which, ~hen measured according to normal photographic techniques ~038~64 by coating a test portion of the silver halide emulsion on a transparent support, exposing to a light-intensity scale having a fixed time between 0.01 and 1 second, and developing for 3 minutes at 20~C. in Developer A below ("internal-type'l developer), have a maximum density at least five times the maximum density obtained when an equally exposed silver halide emulsion is developed for 4 minutes at 20C. in Developer B described below ~"surface-type" developer). Preferably, the maximum density in Developer A
is at least 0.5 density unit greater than the maximum density in Developer B.
DEVELOPER A
Hydroquinone 15 g.
Monomethyl-p-aminophenol sulfate 15 g.
Sodium sulfite ~desiccated) 50 g.
Potassium bromide 10 g.
Sodium hydroxide 25 g.
Sodium thiosulfate 20 g.
Water to make one liter.
¦ P-hydroxyphenylglycine 10 g.
Sodium carbonate 100 g.
Water to make one liter The solarizing direct-positive silver halide emulsions useful in the above-described embodiment are well-known ` 20 silver halide emulsions which have been effectively fogged either chemically or by radiation to a point which corresponds approximately to the maximum density of the reversal curve as shown by Mees, The Theory of the Photographic Process, published by the Macmillan Co., New York, New York, 1942, pages 261-297. Typical methods ~or the preparation of solarizing emulsions are shown by Groves British Patent 443,245, February 25, 1936, who subjected emulsions to Roentgen rays "until an emulsion layer formed therefrom, when developed without preliminary exposure, is blackened up to the apex of its graduation curve"; Szaz British Patent 462,730, March 15, 1937, the use of ei~her light or chemicals sush as silver nitrate, organic sulfur compounds and dyes to 1C~313864 convert ordinary silver halide emulsions to solarizing direct positive emulsions; and Arens U. S. Patent 2,005,837, June 25, 1935, the use of silver nitrate and other compounds in conjunction with heat to effect solarization. Kendall and Hill U. S. Patent 2,541~472, February 13, 1951, shows useful solarized emulsions particularly susceptible to exposure with long wavelength light and initial development to produce the Herschel effect described by Mees above, produced by adding benzo-thiazoles and other compounds to the emulsions which are fogged either chemically or with white light. In using the emulsions a sufficient reversal image exposure i5 employed using minus blue light of from about 500-700 m~ wavelength preferably 520-554 m~, to substantially destroy ; the latent lmage in the silver halide grains in the region of the image exposure. Particularly useful are the fogged direct-positive emulsions of Berriman U. S. Patent 3,367,778; Illingsworth U. S. Patents 3,501,305, 3,501,306 and 3,501,307; and combinations thereof.
Internal-image silver halide emulsions which contain or which are processed in the presence of fogging or nucleating agents are particularly useful in the above-described embodiment since the use of fogging agents is a convenient way to inject electrons into the silver halide grains. Suitable fogging agents include the hydrazines disclosed in Ives U. S. Patents 2,588,982 issued March 11, 1952 and 2,563,785 issued August 7, 1951; the hydrazides and hydrazones disclosed in Whitmore U. S. Patent 3,227,552 issued January 4, 1966; or mixtures thereof. The quantity of fogging agent employed can be widely varied depending upon the results desired. Generally, the concentration of fogging agent is from about 1 to about 20 mg. per square foot of photo-sensitive layer in the photosensitive element or from about 0.1 to ~03886~
about 2 grams per liter of developer if it is located in the developer.
Other embodiments in which our imaging chemistry can be employed include the techniques described in U.S. Patents 3,227,550, 3,227,551, 3,227,552 and 3,364,022, and in British Patent 904,364, p. 19, lines }-41, wherein our dye image-providing materials are substituted for the nondiffusible dye-providing couplers described therein. For example, a film unit using development inhibitor-releasing couplers as described in U.S. Patent 3,227,551 may be employed in conjunction with the dye image-providing materials described herein. In this method, however, the developing agent employed must include one which oxidatively couples to release the inhibitor compounds. These developing agents are genera~ly selected from the class of aromatic primary amino develop-ing agents such as ~-aminophenols or ~-phenylenediamines.
Another embodiment of our invention uses the image-~ reversing technique disclosed in British Patent 904,364, page 19, ; lines 1-41. In this system our dye-providing compounds are used in combination with physical development nuclei in a nuclei layer contiguous to the photosensitive silver halide emulsion layer.
The film unit contains a silver halide solvent, preferably in a : rupturable container with the alkaline processing composition, and the photosensitive element contains an immobilizing coupler, which is capable of reacting with oxidized developer to form an immobile product. This embodiment also must include developing agents which are reactive with the immobilizing coupler. Preferred compounds include the primary aromatic amines described above.
me various silver halide emulsion layers of a color film assembly of the invention can be disposed in the usual order, i.e., the blue-sensitive silver halide emulsion layer first with respect to the exposure side, ~038~64 followed by the green-sensitive and red-sensitive silver halide emulsion layess. If desired, a yellow dye layer or a Carey Lea silver layer can be present between the blua-sensitive and green-sensitive silver halide emulsion layer for absorbing or filtering blue radiation that may be transmitted through the blue-sensitive layer. If desired, the selectively sensitized silver halide emulsion layers can be disposed in a different order, e.g., the blue-sensitive layer first with respect to the exposure side, followed by the rad-sensitive and green-sensitive layers.
The silver halide emulsions used in this invention can comprise, for example, silver chloride, silver bromide, silver ~ chlorobromide, silver bromoiodide, silver chlorobromoiodide or ; mixtures thereof. The emulsions can be coarse- or fine-grain and can be prepared by any of the well-known procedures, e.g., single-jet emulsions such as those described in Trivelli and Smith, The Photographic Journal, Vol. LXXIX, May, 1939 (pp 330-338), double-jet emulsions, such as Lippmann emulsions, ammoniacal emulsions, thiocyanate or thioether ripened emulsions such as those described in Nietz et al, U. S. Patent 2,222,264, issued November 19, 1940; Illingsworth U. S. Patent 3,320,06g issued May 16, 1967; and Mc~ride U. S. Patent 3,271,157 issued September 6, 1966. Surface-image emulsions can be used or internal-image emulsions can be used ~uch as those described in Davey et al U.S.
Patent 2,592,250 issued May 8, 1952; Porter et al U.S. Patent 3,206,313 issued September 14, 1965; Berriman U.S. Patent 3,367,778 issuea February 6, 1968; and Bacon et al U.S. Patent 3,447,927 issued June 3, 1969 The emulsions may be regular-grain emulsions such as the type described in Rlein and Moisar, J. Phot. Sci., Vol.
12, No. 5, Sept./Oct., 1964, (pp. 242-251). Negative~type emulsions may be used or direct-positive emulsions may be used such as those described in Leermakers U. S. Patent 2,184,013 issued December 19, 1939 Kendall et al U.S.
ll ~03~864 Patent 2,541,472 issued February 13, 1951; Berriman U.S. Pa~ent 3,367,778 issued February 6, 196~; Schouwenaars British Patent 723,019 issued February 2, 1955; Illingsworth et al French Patent 1,520,821 issued March 4, 1968; Il}ingsworth U.S. Patent 3,501,307 issued March 17, 1970; Ives U.S. Patent 2,563,785 issued August 7, 1951; Xnott et al U.S. Patent 2,456,953 issued December 21, 1948;
and Land U. S. Patent 2,861,885 issued November 25, 1958.
The rupturable container employed in this invention can be of the type disclosed in U. S. Patent Nos. 2,543,181; 2,643,886;
2,653,732; 2,723,051; 3,056,492; 3,056,491 and 3,152,515. In general, such containers comprise a rectangular sheet o~ fluid-and air-impervious material folded longitudinally upon itself to form two wall~ which are sealed to one another along their longi-tudinal and end margins to form a cavity in which processing solution is contained.
In a color film unit according to this invention, each silver halide emulsion layer containing a dye image-providing material or having the dye image-providing material present in a contiguous }ayer may be separated from the other silver halide emulsion layers in the image-forming portion of the film unit by materials including gelatin, calcium alginate, or any of those disclosed in U.S. Patent No. 3,384,483, polymeric materials such as polyvinylamides as disclosed in U.S. Patent 3,421,892, or any of those disclosed in French Patent 2,028,236 or U. S. Patent Nos.
2,992,104; 3,043,692; 3,Q4~.,873; 3,061,428; 3,069,263; 3,069,264;
3,121,011; and 3,427,158.
Generally speaking, except where noted otherwise, the silver halide emulsion layers in the invention comprise photo-sensitive silver halide dispersed in gelatin and are about 0.6 to 6 microns in thickness; the dye image-providing materials are dispersed in an aqueous alkaline ~(~,38~i4 ; ~
solution-permeable polymeric binder, such as gelatin, as a separate layer about l to 7 microns in thickness, and the alk~ine solution-permeable polymeric interlayers, e.g., gelatin, are about l to 5 microns in thickness. Of course, these thicknesses are approximate only and can be modified according to the product desired.
Any material can be employed as the image-receiving layer in this invention as long as the desired function of ; mordanting or otherwise fixing the dye images will be obtained.
The particular material chosen will, of course, depend upon the dye to be mordanted. If acid dyes are to be mordanted, the image-receiving layer can contain basic polymeric mordants such as polymers of amino guanidine derivatives of vinyl methyl ketone such as described in Minsk U. S. Patent 2,882,156, issued April 14, 1959, and basic polymeric mordants such as described in Cohen et al U. S. Patent No. 3,709,690, issued January 9, 1973.
Preferred mordants are cationic mordants such as poly-; meric compounds composed of a polymer having quaternary nitrogen groups and at least two aromatic nuclei for each quaternary nitrogen in the polymer cation (i.e., having at least two aromaticnuclei for each positively charged nitrogen atom), such polymeric compounds being substantially free of carboxy groups. Useful mordants of this type are comprised of units of the following formula in copolymeri~ed relationship with units of at least one other ethylenically unsaturated monomer:
- CH - C - _ R (Q) Rll- N~ - R9 X~
. R10 16)3~86~ ~
wherein R7 and R8 each represent a hydrogen atom or a lower a~kyl radical (of 1 to about 6 carbon atoms) and R8 can additionally be a group containing at least one aromatic nucleus~e.g.~ phenyl, naphthyl, tolyl); Q can be a divalent alkylene radical (of 1 to about 6 carbon atoms), a divalent arylene radical, a divalen-t aralkylene radical, a divalent arylenealkylene radical, O O O
,~ ,. .. .
-C-OR12-, -OC-R12-, or -C-NH-R12-, wherein R12 is an alkylene radical, or R8 can be taken together with Q to form a ~ ~; R9 R10 and Rll can be lower alkyl or aryl, --C
~ Q
or R9 and R10 and the nitrogen atom to which they are attached can together with Q represent the atoms and bonds necessary to form a quaternized nitrogen-containing heterocyclic ring, and X9 is a monovalent negative salt forming radical or atom in ionic relationship with the positive salt forming radical, wherein said polymer is substantially free of carboxy groups and wherein the positive salt forming radical of said polymer comprises at least two aryl groups for each quaternary nitrogen atom in said polymer. These preferred polymeric cationic mordants are 20 described further in the above-mentioned U. S. Patent No.
3,709,690.
Other mordants useful in our invention include poly-
A photographic fiIm unit according to our invention which is adapted to be processed by passing the unit between a pair of juxtaposed pressure-applying members, comprises:
1) a photosensitive element as described above;
2) a dye image-receiving layer; and 3) means for discharging an alkaline processing co~position within the film unit such as a ruptur-able container which is adapted to be positioned during processing of the film unit so that a compressive force applied to the container by the - pressure-applying members will effect a discharge of the contents of the container within the film unit;
the film unit containing a silver halide developing agentO
~038~6~
The dye image-receiving layer in the above-described film unit can be located on a separate support adapted to be superposed on the photosensitive element after exposure thereof.
Such image-receiving elements are generally disclosed, for .
exàmple, in U. S. Patent 3,362,819. When the means for dis-charging the processing composition is a rupturable container, ; typically it is posi-tioned in relation to the photosensitive element and the image-receiving element so that a compressive force applied to the container by pressure-applying members, such as found in a camera designed for in-camera processing, will effect a discharge of the contents of the container between the image-receiving element and the outermost layer of the photo-sensitive element. After processing, the dye image-receiving element is separated from the photosensitive element.
The dye image-receiving layer in the above-described film unit can also be located integral with the photosensitive element between the support and the lowermost photosensitive silver halide emulsion layer~ One useful format for integral receiver-negative photosensitive elements is disclosed in Belgian Patent 757,960. In such an embodiment, the support for the photosensitive element is transparent and is coated with an image-receiving layer, a substantially opaque llght reflective layer, e.g., TiO2, and then the photosensitive layer of layers described above After exposure of the photosensitive element, a rupturable container containing an alkaline processing composi-- tion and an opaque process sheet are brought into superposedposition. Pressure-applying members in the camera rupture the container and spread processing composition over the photosensi-tive element as the film unit is withdrawn from the camera. The processing composition develops each exposed silver halide emul sion layer and dye images are formed as a function o-~ development i03886~
which diffuse to the image-receiving layer to provide a right-reading image which is viewed through the transparent support on the opaque reflecting layer backg~und.
Another format for integral negative-receiver photo- ;
sensitive elemen-ts in which the present invention can be employed is disclosed in Belgian Patent 757,959. In this embodiment~ the support for the photosensitive element is transparent and is coated with the image-receiving layer, a substantially opaque, light-reflective layer and the photosensitive layer or layers 10 described above. A rupturable container containing an alkaline processing composition and an opacifier is positioned adjacent to the top layer and a transparent top sheet. The film unit is placed in a camera, exposed through the transparent top sheet and then passed through a pair of pressure-applying members in the camera as it is being removed therefrom . The pressure- ~¦
applying members rupture the container and spread processing composition and opacifier over the negative portion of the film unit to render it light insensitive. The processing composition develops each silver halide layer and dye images are formed as 20 a result of development which dlffuse -to the image-receiving layer to provide a right-reading image that is viewed thrGugh the transparent support on the opaque reflecting layer background.
Still other useful integral fo~nats in which our sulfonamido compounds can be employed are described in U. S.
Patents 3,415,644; 3,415,645; 3,415,646; 3,647,437; and 3,635,707- -The film unit or assembly of the present inventioncan be used to produce positive images in single- or multi-colors. In a three-color system, each silver halide emulsion 30 layer of the film assembly will have associated therewith an image dye-providing material possessing a predominant spectral absorption within the region of the visible spectrum to which ~03~4 `~
said silver halide emulsion is sensitive, i.e., the blue-sensitive silver halide emulsion layer will have a yellow image dye-providing material associated therewith, the green-sensitive silver halide emulsion layer will have a magenta image dye-provicling material associated therewith, and the red-sensitive silver halide emulsion layer will have a cyan image dye-providing material associated therewith. The image dye-providing material associated with each silver halide emulsion layer can be contained either in the silver halide emulsion layer itself or in a layer contiguous to the silver halide emulsion layer. The magenta image dye-providing material will, of course, be a compound of this invention, and when G i8 an ester, the compound can be contained in the silver halide emulsion.
The concentration o the compounds which preferably are alkali-cleavable upon oxidation that are employed in the present ; invention can be varied over a wide range depending upon the particular compound employed and the results which are desired. For example, the image dye-providing compounds of the present invention can be coated in layers by using coating solutions containing between about 0.5 to about 8 percent by weight of the image dye-providing compound distributed in a hydrophilic film-forming natural or synthetic polymer, such as gelatin, polyvinyl alcohol, etc., which is adapted to be permeated by aqueous alkaline processing composition. Typically, the present compounds are incorporated in a coupler solvent Ce.g., a high boiling, water immiscible organic solvent2 prior to distribution in the gelatin by techniques known in the art.
" ~
~03~
Depending upon which Car is used on the present com-pounds, a variety of silver halide developing agents can be employed in our invention. If the carrier used is that of Formula IV, any silver halide developing agent can be used as long as it cross-oxidizes with the image dye-providing compounds used herein.
The developer can be employed in the photosensitive element to be activated by the alkaline processing composition. Specific examples of developers which can be employed in our invention include: hydroquinone, N-methylaminophenol, Phenidone (l-phenyl-3-pyrazolidone), Dimezone ~l-phenyl-4,4-dimethyl-3-pyrazolidone), l-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, ascorbic acid, aminophenols, N,N-diethyl-~-phenylenediamine, 3-methyl-N,N-diethyl-~-phenylenediamine, 3-methoxy-N-ethyl-N-ethoxy- p-phenylenediamine, etc. The black-and-white developers in this list are preferred, in that they have a reduced propensity of staining the dye image-receiving layer.
In a preferred embodiment of our invention, the silver halide developer in our process becomes oxidized upon development and reduces silver halide to silver metal. The oxidized developer then cross-oxidizes the sulfonamido phenol dye-releasing compound.
The product of cross-oxidation then undergoes alkaline hydrolysis, thus releasing an imagewise distribution of diffusible anionic dye which then diffuses to the receiving layer to provide the positive dye image. The diffusible moiety is transferrable in alkaline processing composition either by virtue of its self-diffusivity or by having attached to it one or more solubilizing - groups such as COOH, S03H, So2NR5R6, OH, etc (where R5 and R6 are as described previously with at least one being hydrogen).
In using the especially preferred dye-releasing compour,ds according to our invention, the production of diffus-ible dye images is a function of the reduction of developable silver halide images which may irvolve direct or reversal ~03~3864 ~
development of the silver halide emulsions with a silverhalide developing agent. If the silver halide emulsion employed is a direct~positive silver halide emulsion, such as an internal-image emulsion or a solarizing emulsion, which is developable in unexposed areas, a positive image can be obtained on the dye image-receiving layer. After exposure of the film unit, the ,.:
alkaline processing composition pçrmeates the various layers to initiate development o* the exposed photosensitive silver halide emulsion layers. The developing agent present in the film unit develops each of the silver halide emulsion layers in the un-exposed areas (since the silver halide emulsions are direct-positive ones)~ thus causing the developing agent to become oxidized imagewise corresponding to the une~posed areas of the direct-positive silver halide emulsion layers. The oxidized ; developing agent then cross-oxidizes the dye-releasing compounds and the oxidized form of the compounds then undergoes a base-catalyzed reaction in a preferred embodiment of our invention, to release the preformed dyes imagewise as a function of the imagewise exposure of each of the silver halide emulsion layers. At least a portion of the imagewise distributions of diffusible dyes diffuse to the image-receiving layer to form a positive image of the original i subject. After being contacted by the alkaline processing com-position, a pH-lowering layer in the film unit or image-receiving unit (if such a layer is needed) lowers the pH of the film unit of image receiving to stabilize the image.
If photographic elements are used which contain com-pounds of this invention wherein Car is a silver halide developer as described, for example, in U. S. Patent No. 2,983,606, when ~03~86~ ~
the liquid processing composition is applied, it permeates the emulsion to provide a solution of the dye developer substantially uniformly distributed in the emulsion. As the exposed silver halide emulsion is developed, the oxidation product of the dye developer is immobilized or precipitated in situ with the developed sil~er, thereby providing an imagewise distribution of unoxidized dye developer dissolved in the liquid processing composition. This immobilization is apparently due, at least in part, to a change in the solubility characteristics of the dye developer upon oxidation. At least part of this imagewise distribution of unoxidized dye-developer is transferred to a superposed image-receiving layer to provide a transfer image.
Internal-image silver halide emulsions useful in those embodiments wherein a dye is released as a function of oxidation are direct-positive emulsions that form latent images predominantly ~ inside the silver halide grains, as distinguished from silver ; halide grains that form latent images predominantly on the sur-face thereof. Such inte m al-image emulsions are described by Davey et al in U. S. Patent 2,592,250, issued April 8, 1952, and elsewhere in the literature. Other useful emulsions are described in Belgian Patent No. 780,531, dated March 31, 1972. Inte m al-image silver halide emulsions can be defined in terms of the increased maximum density obtained when developed with "inte m al-type" developers over that obtained when developed with "surface-type" developers. Suitable inte m al-image emulsions are those which, ~hen measured according to normal photographic techniques ~038~64 by coating a test portion of the silver halide emulsion on a transparent support, exposing to a light-intensity scale having a fixed time between 0.01 and 1 second, and developing for 3 minutes at 20~C. in Developer A below ("internal-type'l developer), have a maximum density at least five times the maximum density obtained when an equally exposed silver halide emulsion is developed for 4 minutes at 20C. in Developer B described below ~"surface-type" developer). Preferably, the maximum density in Developer A
is at least 0.5 density unit greater than the maximum density in Developer B.
DEVELOPER A
Hydroquinone 15 g.
Monomethyl-p-aminophenol sulfate 15 g.
Sodium sulfite ~desiccated) 50 g.
Potassium bromide 10 g.
Sodium hydroxide 25 g.
Sodium thiosulfate 20 g.
Water to make one liter.
¦ P-hydroxyphenylglycine 10 g.
Sodium carbonate 100 g.
Water to make one liter The solarizing direct-positive silver halide emulsions useful in the above-described embodiment are well-known ` 20 silver halide emulsions which have been effectively fogged either chemically or by radiation to a point which corresponds approximately to the maximum density of the reversal curve as shown by Mees, The Theory of the Photographic Process, published by the Macmillan Co., New York, New York, 1942, pages 261-297. Typical methods ~or the preparation of solarizing emulsions are shown by Groves British Patent 443,245, February 25, 1936, who subjected emulsions to Roentgen rays "until an emulsion layer formed therefrom, when developed without preliminary exposure, is blackened up to the apex of its graduation curve"; Szaz British Patent 462,730, March 15, 1937, the use of ei~her light or chemicals sush as silver nitrate, organic sulfur compounds and dyes to 1C~313864 convert ordinary silver halide emulsions to solarizing direct positive emulsions; and Arens U. S. Patent 2,005,837, June 25, 1935, the use of silver nitrate and other compounds in conjunction with heat to effect solarization. Kendall and Hill U. S. Patent 2,541~472, February 13, 1951, shows useful solarized emulsions particularly susceptible to exposure with long wavelength light and initial development to produce the Herschel effect described by Mees above, produced by adding benzo-thiazoles and other compounds to the emulsions which are fogged either chemically or with white light. In using the emulsions a sufficient reversal image exposure i5 employed using minus blue light of from about 500-700 m~ wavelength preferably 520-554 m~, to substantially destroy ; the latent lmage in the silver halide grains in the region of the image exposure. Particularly useful are the fogged direct-positive emulsions of Berriman U. S. Patent 3,367,778; Illingsworth U. S. Patents 3,501,305, 3,501,306 and 3,501,307; and combinations thereof.
Internal-image silver halide emulsions which contain or which are processed in the presence of fogging or nucleating agents are particularly useful in the above-described embodiment since the use of fogging agents is a convenient way to inject electrons into the silver halide grains. Suitable fogging agents include the hydrazines disclosed in Ives U. S. Patents 2,588,982 issued March 11, 1952 and 2,563,785 issued August 7, 1951; the hydrazides and hydrazones disclosed in Whitmore U. S. Patent 3,227,552 issued January 4, 1966; or mixtures thereof. The quantity of fogging agent employed can be widely varied depending upon the results desired. Generally, the concentration of fogging agent is from about 1 to about 20 mg. per square foot of photo-sensitive layer in the photosensitive element or from about 0.1 to ~03886~
about 2 grams per liter of developer if it is located in the developer.
Other embodiments in which our imaging chemistry can be employed include the techniques described in U.S. Patents 3,227,550, 3,227,551, 3,227,552 and 3,364,022, and in British Patent 904,364, p. 19, lines }-41, wherein our dye image-providing materials are substituted for the nondiffusible dye-providing couplers described therein. For example, a film unit using development inhibitor-releasing couplers as described in U.S. Patent 3,227,551 may be employed in conjunction with the dye image-providing materials described herein. In this method, however, the developing agent employed must include one which oxidatively couples to release the inhibitor compounds. These developing agents are genera~ly selected from the class of aromatic primary amino develop-ing agents such as ~-aminophenols or ~-phenylenediamines.
Another embodiment of our invention uses the image-~ reversing technique disclosed in British Patent 904,364, page 19, ; lines 1-41. In this system our dye-providing compounds are used in combination with physical development nuclei in a nuclei layer contiguous to the photosensitive silver halide emulsion layer.
The film unit contains a silver halide solvent, preferably in a : rupturable container with the alkaline processing composition, and the photosensitive element contains an immobilizing coupler, which is capable of reacting with oxidized developer to form an immobile product. This embodiment also must include developing agents which are reactive with the immobilizing coupler. Preferred compounds include the primary aromatic amines described above.
me various silver halide emulsion layers of a color film assembly of the invention can be disposed in the usual order, i.e., the blue-sensitive silver halide emulsion layer first with respect to the exposure side, ~038~64 followed by the green-sensitive and red-sensitive silver halide emulsion layess. If desired, a yellow dye layer or a Carey Lea silver layer can be present between the blua-sensitive and green-sensitive silver halide emulsion layer for absorbing or filtering blue radiation that may be transmitted through the blue-sensitive layer. If desired, the selectively sensitized silver halide emulsion layers can be disposed in a different order, e.g., the blue-sensitive layer first with respect to the exposure side, followed by the rad-sensitive and green-sensitive layers.
The silver halide emulsions used in this invention can comprise, for example, silver chloride, silver bromide, silver ~ chlorobromide, silver bromoiodide, silver chlorobromoiodide or ; mixtures thereof. The emulsions can be coarse- or fine-grain and can be prepared by any of the well-known procedures, e.g., single-jet emulsions such as those described in Trivelli and Smith, The Photographic Journal, Vol. LXXIX, May, 1939 (pp 330-338), double-jet emulsions, such as Lippmann emulsions, ammoniacal emulsions, thiocyanate or thioether ripened emulsions such as those described in Nietz et al, U. S. Patent 2,222,264, issued November 19, 1940; Illingsworth U. S. Patent 3,320,06g issued May 16, 1967; and Mc~ride U. S. Patent 3,271,157 issued September 6, 1966. Surface-image emulsions can be used or internal-image emulsions can be used ~uch as those described in Davey et al U.S.
Patent 2,592,250 issued May 8, 1952; Porter et al U.S. Patent 3,206,313 issued September 14, 1965; Berriman U.S. Patent 3,367,778 issuea February 6, 1968; and Bacon et al U.S. Patent 3,447,927 issued June 3, 1969 The emulsions may be regular-grain emulsions such as the type described in Rlein and Moisar, J. Phot. Sci., Vol.
12, No. 5, Sept./Oct., 1964, (pp. 242-251). Negative~type emulsions may be used or direct-positive emulsions may be used such as those described in Leermakers U. S. Patent 2,184,013 issued December 19, 1939 Kendall et al U.S.
ll ~03~864 Patent 2,541,472 issued February 13, 1951; Berriman U.S. Pa~ent 3,367,778 issued February 6, 196~; Schouwenaars British Patent 723,019 issued February 2, 1955; Illingsworth et al French Patent 1,520,821 issued March 4, 1968; Il}ingsworth U.S. Patent 3,501,307 issued March 17, 1970; Ives U.S. Patent 2,563,785 issued August 7, 1951; Xnott et al U.S. Patent 2,456,953 issued December 21, 1948;
and Land U. S. Patent 2,861,885 issued November 25, 1958.
The rupturable container employed in this invention can be of the type disclosed in U. S. Patent Nos. 2,543,181; 2,643,886;
2,653,732; 2,723,051; 3,056,492; 3,056,491 and 3,152,515. In general, such containers comprise a rectangular sheet o~ fluid-and air-impervious material folded longitudinally upon itself to form two wall~ which are sealed to one another along their longi-tudinal and end margins to form a cavity in which processing solution is contained.
In a color film unit according to this invention, each silver halide emulsion layer containing a dye image-providing material or having the dye image-providing material present in a contiguous }ayer may be separated from the other silver halide emulsion layers in the image-forming portion of the film unit by materials including gelatin, calcium alginate, or any of those disclosed in U.S. Patent No. 3,384,483, polymeric materials such as polyvinylamides as disclosed in U.S. Patent 3,421,892, or any of those disclosed in French Patent 2,028,236 or U. S. Patent Nos.
2,992,104; 3,043,692; 3,Q4~.,873; 3,061,428; 3,069,263; 3,069,264;
3,121,011; and 3,427,158.
Generally speaking, except where noted otherwise, the silver halide emulsion layers in the invention comprise photo-sensitive silver halide dispersed in gelatin and are about 0.6 to 6 microns in thickness; the dye image-providing materials are dispersed in an aqueous alkaline ~(~,38~i4 ; ~
solution-permeable polymeric binder, such as gelatin, as a separate layer about l to 7 microns in thickness, and the alk~ine solution-permeable polymeric interlayers, e.g., gelatin, are about l to 5 microns in thickness. Of course, these thicknesses are approximate only and can be modified according to the product desired.
Any material can be employed as the image-receiving layer in this invention as long as the desired function of ; mordanting or otherwise fixing the dye images will be obtained.
The particular material chosen will, of course, depend upon the dye to be mordanted. If acid dyes are to be mordanted, the image-receiving layer can contain basic polymeric mordants such as polymers of amino guanidine derivatives of vinyl methyl ketone such as described in Minsk U. S. Patent 2,882,156, issued April 14, 1959, and basic polymeric mordants such as described in Cohen et al U. S. Patent No. 3,709,690, issued January 9, 1973.
Preferred mordants are cationic mordants such as poly-; meric compounds composed of a polymer having quaternary nitrogen groups and at least two aromatic nuclei for each quaternary nitrogen in the polymer cation (i.e., having at least two aromaticnuclei for each positively charged nitrogen atom), such polymeric compounds being substantially free of carboxy groups. Useful mordants of this type are comprised of units of the following formula in copolymeri~ed relationship with units of at least one other ethylenically unsaturated monomer:
- CH - C - _ R (Q) Rll- N~ - R9 X~
. R10 16)3~86~ ~
wherein R7 and R8 each represent a hydrogen atom or a lower a~kyl radical (of 1 to about 6 carbon atoms) and R8 can additionally be a group containing at least one aromatic nucleus~e.g.~ phenyl, naphthyl, tolyl); Q can be a divalent alkylene radical (of 1 to about 6 carbon atoms), a divalent arylene radical, a divalen-t aralkylene radical, a divalent arylenealkylene radical, O O O
,~ ,. .. .
-C-OR12-, -OC-R12-, or -C-NH-R12-, wherein R12 is an alkylene radical, or R8 can be taken together with Q to form a ~ ~; R9 R10 and Rll can be lower alkyl or aryl, --C
~ Q
or R9 and R10 and the nitrogen atom to which they are attached can together with Q represent the atoms and bonds necessary to form a quaternized nitrogen-containing heterocyclic ring, and X9 is a monovalent negative salt forming radical or atom in ionic relationship with the positive salt forming radical, wherein said polymer is substantially free of carboxy groups and wherein the positive salt forming radical of said polymer comprises at least two aryl groups for each quaternary nitrogen atom in said polymer. These preferred polymeric cationic mordants are 20 described further in the above-mentioned U. S. Patent No.
3,709,690.
Other mordants useful in our invention include poly-
4-vinylpyridine, the 2-vinyl pyridine polymer metho-p-toluene sulfonate and similar compounds described in Sprague et al U. S.
Patent 2,484,430, issued October 11, 1949, and cetyl trimethyl-ammonium bromide, etc. Effective mordanting compositions are also described in Whitmore U. S. Patent 3,271,148 and Bush U. S.
Patent 3,271,147, both issued September 6, 1966.
~038~36~ `
Furthermore, the image-receiving layer can be sufficient by itself to mordant the dye as in the case of use of an alkaline solution-permeable polymeric layer such as N-methoxy-methyl polyhexylmethylene adipamide; partially hydrolyzed polyvinyl acetate, polyvinyl alcohol with or without plasticizersj cellu-lose acetatej gelatin, and other materials of a similar nature.
~enerally, good results are obtained when the image-receiving layer, preferably alkaline solution-permeable, is transparent and about 0.25 to about 0.40 mil in thickness. This thickness, of course, can be modified depending upon the result desired.
The image-receiving layer can also contain ultraviolet absorbing materials to protect the mordanted dye images from ~ad-lng due to utlraviolet light, brightening agents such as the stilbenes, coumarins, triazines, oxazoles, dye stabilizers such as the chromanols, alkylphenols, etc. ~, Use of a pH-lowering material in the dye image-receiving element of a film unit according to the invention will usually increase the stability of the transferred image. Generally, the pH-lowering material will effect a reduction in the pH of the image layer from about 13 or 14 to at least 11 and preferably
Patent 2,484,430, issued October 11, 1949, and cetyl trimethyl-ammonium bromide, etc. Effective mordanting compositions are also described in Whitmore U. S. Patent 3,271,148 and Bush U. S.
Patent 3,271,147, both issued September 6, 1966.
~038~36~ `
Furthermore, the image-receiving layer can be sufficient by itself to mordant the dye as in the case of use of an alkaline solution-permeable polymeric layer such as N-methoxy-methyl polyhexylmethylene adipamide; partially hydrolyzed polyvinyl acetate, polyvinyl alcohol with or without plasticizersj cellu-lose acetatej gelatin, and other materials of a similar nature.
~enerally, good results are obtained when the image-receiving layer, preferably alkaline solution-permeable, is transparent and about 0.25 to about 0.40 mil in thickness. This thickness, of course, can be modified depending upon the result desired.
The image-receiving layer can also contain ultraviolet absorbing materials to protect the mordanted dye images from ~ad-lng due to utlraviolet light, brightening agents such as the stilbenes, coumarins, triazines, oxazoles, dye stabilizers such as the chromanols, alkylphenols, etc. ~, Use of a pH-lowering material in the dye image-receiving element of a film unit according to the invention will usually increase the stability of the transferred image. Generally, the pH-lowering material will effect a reduction in the pH of the image layer from about 13 or 14 to at least 11 and preferably
5-8 within a short time after imbibi~on. For example, polymeric acids as disclosed in U. S. Patent 3,362,819 or solid acids or metallic salts, e.g., zinc acetate, zinc sulfate, magnesium acetate, etc, as disclosed in U. S. Patent 2,584,o30 may be employed with good results. Such pH-lowering materials reduce the pH of the film unit after development to terminate deyelop-ment and substantially reduce further dye transfer and thus stabilize the dye image.
An inert timing or spacer layer can be employed in the ; 30 practice of our invention over the pH-lowering layer which "times"
or controls the pH reduction as a function of the rate at which .
~03~64 alkali diffuses through the inert spacer layer. Examples of such timing layers include gelatin, polyvinyl alcohol or a~y of those disclosed in U. S. Patent 3,455,686. The timing layer may be effective in evening out the various reaction rates over a wide range of temperatures, e.g., premature pH reduction is prevented when imbibition is effected at temperatures above room temperature, for example, at 95-100Fo The timing layer is usually about 0.1 to about 0.7 mil in thickness. Especially good results are obtained when the timing layer comprises a hydro-lyzable polymer or a mixture of such polymers which are slowlyhydrolyzed by the processing composition. Examples of such hydrolyzable polymers include polyvinyl acetate, polyamides, cellulose esters, etc.
The alkaline processing composition employed in this invention is the conventional aqueous solution of an alkaline material, e.g., sodium hydroxide, sodium carbonate or an amine such as diethylamine, preferably possessing a pH in excess of 11, and preferably containing a developing agent as described previously. The solution also preferably contains a viscosity-increasing compound such as a high-molecular~weight polymer, e.g., a water-soluble ether inert to alkaline solutions such as hydroxyethyl cellulose or alkali metal salts of carboxymethyl ; cellulose such as sodium carboxymethyl cellulose. A concentration of viscosity-increasing compound of about 1 to about 5~ by weight of the processing composition is preferred which will impart thereto a viscosity of about 100 cps. to about 200,000 cps. In certain embodiments of our invention, an opacifying agent, e.g., TiO2, carbon black, etc, may be added to the processing composition.
While the alkaline processing composition used in this invention can be employed in a rupturable container, as described previously, to conveniently facilitate the introduction of pro-1038~6~
cessing composition into the film unit, other methods of insertingprocessing composition into the film unit could also be employed, e.g., interjecting processing solution with communicating members similar to hypodermic syringes which are attached either to a camera or camera cartridge.
The alkaline solution-permeable, substantially opaque, light-reflective layer employed in certain embodiments of photo-graphic film units of our invention can generally comprise any opacifier dispersed in a binder as long as it has the desired properties. Particularly desirable are white light-reflective layers since they would be esthetically pleasing backgrounds on which to view a transferred dye image and would also possess the optical properties desired for re~lection of incident radia-tion. Suitable opacifying agents include titanium dioxide, barium sulfate, zinc oxide, barium stearate, silver flake, silicates, alumina, zirconium oxide, zirconium acetyl acetate, sodium zirconium sulfate, kaolin, mica, or mixtures thereof in widely varying amounts depending upon the degree of opacity desired. The opacifying agents may be dispersed in any binder such as an alkaline solution-permeable polymeric matrix such as, for example, gelatin, polyvinyl alcohol, and the like.
Brightening agents such as the stilbenes, coumarins, triazines and oxazoles can also be added to the light-reflective layer, if desired. Wn~en it is desired to increase the opacifying capacity of the light-reflective layer, dark-colored opacifying agents, e.g., carbon black, nigrosine dyes, etc, may be added to it, or coated in a separate layer adjacent to the light-reflective layer.
The supports for the photographic elements of this invention can be any material as long as it does not deleteriously 3 effect the photographic properties of the film unit and is dimen-sionally stable. Typical flexible sheet materials include cellulose nitrate film, cellulose acetate film, poly(viny; acetal) 1~3~ 4 fi~m, polystyrene film, poly(ethyleneterephthalate) film, poly-carbonate film, poly-a-olefins such as polyethylene and poly-propylene film, and related films or resinous materials. The support is usually about 2 to 6 mils in thickness.
While the invention has been described with reference to layers of silver halide emulsions and dye image-providing materials, dotwise coating, such as would be obtained using a gravure printing technique, could also be employed. In this technique, small dots of blue-, green- and red-sensitive emulsions have associated therewith, respec-tively, dots of yellow, magenta and cyan color-providing substances. After development, the trans-ferred d~es would tend to ~use together -Lnto a con~inuous tone.
The sil~er halide emulsions useful in our invention are well known to those skilled in the art and are described in Product Licensing Index, Vol. 92, December, 1971, publication 9232, p. 107, paragraph I, "Emulsion types"; they may be chemi-cally and spectrally sensitized as described on Rage 107, para-graph III, "Chemical sensitization", and pp. 108-109, paragraph X~, "Spectral sensitization", o~ the above article; they can be p~otected against the production of fog and can be stabilized against loss of sensitivity during keeping by employing the materials described on p. 107, paragraph V, "Antifoggants and ~- stabilizers", of the above article; they can contain development modi~iers, hardeners, and coating aids as described on pp. 107-108, paragraph IV, "Development modifiers"; paragraph VII, "Har-deners"; and paragraph XII, "Coating aids", of the above article;
they and other layers in the photographic elements used in this invention can contain plasticizers, vehicles and filter dyes described on p. 108, paragraph XI, "Plasticizers and lubricants", and paragraph VIII, "Vehiclesi', and p. 109, paragraph XVI, "Absorbing and filter dyes", of the above article; they and other r.,~
~L03886~L .
layers in the photographic elements used in this invention m~.y contain addenda which are incorporated by using the procedures described on p. 109, paragraph XVII, "Methods of addition", of the above article; and they can be coated by using the various techniques described on p. 109, paragraph ~VIII, "Coat:Lng pro-cedùres", of the above article, the disclosures of which are hereby incorporated by referenceO
It will be appreciated that there remains in the photo-graphic element after transfer has taken place an imagewise distrlbution of dye in addition to developed silver. A color image comprls~ng residual nondif~usible compound may be obta~.ned in this element if the residual silver and silver halide are removed by any conventional manner well known to those skilled in the photographic art, such as a bleach bath followed by a fix bath, a bleach-fix bath, etc. The imagewise distribution of dye may also diffuse out of the element into these baths~ if desired, rather than to an image-receiving element. If a negative-working silver halide emulsion is employed in such photosensitive element, then a positive color image, such as a color transparency or motion-picture film, may be produced in this manner. If a direct-positive silver halide e~ulsion is ` e~ployed in such photosensitive element, then a negative color image may be produced.
The following examples are provided for a further understanding of the invention. The structures of all of the c~mpounds were confirmed by their infrared and NMR spectra and in some cases by elemental analysis. The notation C5Hll-t is an abbreviation for t-pentyl.
~0388G4 Example 1 - Preparation of Compound No. 1 ilO~II=N~SOaN=CH-II( CH3) 2 CH3CONH ¢0~ SO2NH
[~0~ (CHa),,-O~sHll-t I OH
To 90 ml. of dry pyridine, under nitrogen, at 0C. was added 2.95 g. (o.o6 mol) of 4-amino-N-C4-(2,4-di-tert-pentyl-phenoxy)butyl]-l-hydroxy-2-naphthamide. To this solution 2.9 g.
(o .o6 mol) of 4-acetamido-8-~5-N-(dimethylaminomethylene)sulf-amoylphenylazo]-5-hydroxy-1-naphthalenesulfonyl chloride was added. The reaction mixture was stîrred at room temperature for ninety minutes and then poured into a mixture of ice and concentrated hydrochloric acid. The resulting solid was collected on a filter funnel and dried to yield 5.8 g. (> 100~). It was purified by chromatography using a silica ~column, with ethyl acetate being used to elute the product. The yield was 30~, m.p. 237C. PREPARATION OF INTERMEDIATES: The sulfonyl chloride compound above was prepared from the sodium salt of the corresponding sulfonic acid compound by adding 3.0 g. (0.01 mol) of N,N-dimethylformamide to a slurry of 4.85 g. (0.01 mol) of sodium 4-acetamido-5-hydroxy-6-(4-sulfamoylphenylazo)-1-naphtha-lenesulfonate in 600 ml. of thionyl chlorideg The mixture was stirred for 90 minutes at room temperature and filtered. The filtrate was poured onto ice, the solid collected on a filter funnel and dried to yield 1.3 g. (24~), m.p. 140C. The sodium salt of the dye above was obtained as follows: 300 ml. of lN
, , , ~L03~86~ ;
hydrochloric acid was added to a solution of 17.2 g. (0.1 mol) of sulfanilamide in 100 ml. of 1~ sodium hydroxide. The solu-tion was cooled to 0C and a solution of 6.9 g. (0.1 mol) of sodium nitrite in 80 ml. of water was added at <3C. This mixture was then added to a solution of 8-acetamido-1-acetoxy-5-naphthalenesulfonic acid, pyridine salt in 300 ml. of lN
sodium hydroxide at < 3C. The reaction mixture was stirred for one hour, solid collected on a filter funnel and dried to yield 35.2 g. (72~), m.p. 7300C. The pyridine salt above was obtained by the acetylation of "S acid" in acetic anhydride and pyridine at 80C.
Example 2 - PreParation of Compound No. 2 ;~ HO ~ -N=N ~
CH~CON~ ~ SO2NH SO2N=CH-N(CH3)2 1 C5HlL-t ~ CO~H~(cH2)~-O ~ -CsHL -t This compound was prepared in a manner similar to that used in Example 1. The yield was 20~, m.p. 163-6C.
The 4-acetamido-8-~5-(N-dime-thylaminomethylene)sulfamoyl-2-methoxyphenylazo]-5-hydroxy-1-naphthalenesulfonyl chlori.de was -~ prepared in a manner similar to that used in Example 1.
~03~3864 ' ~
Example 3 - Preparation of Compound No. 3 OCH~
H ~ N-N- ~
~ SO2N=CH-N(CH3)2 C~H5CO~ ~ SO2NH
@$LCON~l-(cH~4-o~asHl~-t OH
The method used in Example 1 was utilized to prepare this compound. The yield was 26~, m.p. 168-72C dec. m e 4- ;
benzamido-8-[5-N-(dimethylaminomethylene)sulfamoyl-2-methoxy-phenylazo]-5-hydroxy-1-naphthalenesulfonyl chloride was prepared by the method used for Example 1 in 68~ yield. Sodium 4-benzamido-5-hydroxy-8-(2-methoxy-5-æulfamoylphenylazo)-1-naphthalenesulfonate was also prepared similarly to Example 1 ~! lo in 35% yield.
Example 4 - Preparation of Compound No. 4 :
~O~N=I~SO2NHSO2 C~H5CONH- ~ -SO2NH
~ CONH-(CH2)~-O ~ CsHlL-t .. . . .
,~
The method used for Example 1 was used to prepare this compound. The yield was 15~, m.p. 155-60C dec. The sulfonyl chloride was prepared from 1.0 g. (.0014 mol.) of 4-benzamido-8-[4-(N-benzenesulfonylsulfamoyl)phenylazo]-5-hydroxy-1-naphthalene-sulfonic acid, sodium salt which was stirred overnight in 25 ml.
of chlorobenzene containing o.8 g. of phosphorous pentachloride.
The solid was collected on a filter funnel and dried to yield 1.0 g. (100~). The sodium 4-benzamido-8-~4-(benzenesulfonyl-sulfamoyl)phenylazo]-5-hydroxy-1-naphthalene sulfonate was pre-pared in a manner similar to Example 1 in 15~ yield.
Example 5 - Preparation of Compound No. 5 CONH( CH2) 4,-0~C5H~ t ~: ~ }IO~N=N~S02~1~_011 Cs~l~~t CH3COI~H~S02NH ~) --CO~H-( CH2 ) " -0- ~CsH l ~,- t Cs l-t ......
To a solution of 1.95 g. (.004 mol) of ~-amino-N-[4-~2~4-di-tert-pentylphenoxy)butyl~-1-hydroxy-2-naphthamide in 50 ml. of dry pyridine at 0C, under nitrogen, was added 1.95 g.
', (.004 mol) of 4-acetamido-8-(4-chlorosulfonylphenylazo)-5-hydroxy-l-naphthalenesulfonyl chloride. The solution was stirred at 0C for one hour, poured into 75 ml. of concentrated hydro-chloric acid and 75 ml. of ice. The solid was collected on a filter funnel and dried. It was then chromatographed on a silica column, eluting with ethyl acetate to remo~e the product. The eluents were concentrated to dryness and the resulting solid reprecipitated from chloroform with hexane. The solid was collected on a filter funnel and dried to yield 1.1 g. (39%), m.p. 220-2C dec. The 4-acetamido-8-(4-chlorosulfonylphenylazo)-5-hydroxy-1-naphthalenesulfonyl chloride was prepared by heating a solution of 9.7 g. (.02 mol) of sodium 4-acetamido-5-hydroxy--3l~-~38864
An inert timing or spacer layer can be employed in the ; 30 practice of our invention over the pH-lowering layer which "times"
or controls the pH reduction as a function of the rate at which .
~03~64 alkali diffuses through the inert spacer layer. Examples of such timing layers include gelatin, polyvinyl alcohol or a~y of those disclosed in U. S. Patent 3,455,686. The timing layer may be effective in evening out the various reaction rates over a wide range of temperatures, e.g., premature pH reduction is prevented when imbibition is effected at temperatures above room temperature, for example, at 95-100Fo The timing layer is usually about 0.1 to about 0.7 mil in thickness. Especially good results are obtained when the timing layer comprises a hydro-lyzable polymer or a mixture of such polymers which are slowlyhydrolyzed by the processing composition. Examples of such hydrolyzable polymers include polyvinyl acetate, polyamides, cellulose esters, etc.
The alkaline processing composition employed in this invention is the conventional aqueous solution of an alkaline material, e.g., sodium hydroxide, sodium carbonate or an amine such as diethylamine, preferably possessing a pH in excess of 11, and preferably containing a developing agent as described previously. The solution also preferably contains a viscosity-increasing compound such as a high-molecular~weight polymer, e.g., a water-soluble ether inert to alkaline solutions such as hydroxyethyl cellulose or alkali metal salts of carboxymethyl ; cellulose such as sodium carboxymethyl cellulose. A concentration of viscosity-increasing compound of about 1 to about 5~ by weight of the processing composition is preferred which will impart thereto a viscosity of about 100 cps. to about 200,000 cps. In certain embodiments of our invention, an opacifying agent, e.g., TiO2, carbon black, etc, may be added to the processing composition.
While the alkaline processing composition used in this invention can be employed in a rupturable container, as described previously, to conveniently facilitate the introduction of pro-1038~6~
cessing composition into the film unit, other methods of insertingprocessing composition into the film unit could also be employed, e.g., interjecting processing solution with communicating members similar to hypodermic syringes which are attached either to a camera or camera cartridge.
The alkaline solution-permeable, substantially opaque, light-reflective layer employed in certain embodiments of photo-graphic film units of our invention can generally comprise any opacifier dispersed in a binder as long as it has the desired properties. Particularly desirable are white light-reflective layers since they would be esthetically pleasing backgrounds on which to view a transferred dye image and would also possess the optical properties desired for re~lection of incident radia-tion. Suitable opacifying agents include titanium dioxide, barium sulfate, zinc oxide, barium stearate, silver flake, silicates, alumina, zirconium oxide, zirconium acetyl acetate, sodium zirconium sulfate, kaolin, mica, or mixtures thereof in widely varying amounts depending upon the degree of opacity desired. The opacifying agents may be dispersed in any binder such as an alkaline solution-permeable polymeric matrix such as, for example, gelatin, polyvinyl alcohol, and the like.
Brightening agents such as the stilbenes, coumarins, triazines and oxazoles can also be added to the light-reflective layer, if desired. Wn~en it is desired to increase the opacifying capacity of the light-reflective layer, dark-colored opacifying agents, e.g., carbon black, nigrosine dyes, etc, may be added to it, or coated in a separate layer adjacent to the light-reflective layer.
The supports for the photographic elements of this invention can be any material as long as it does not deleteriously 3 effect the photographic properties of the film unit and is dimen-sionally stable. Typical flexible sheet materials include cellulose nitrate film, cellulose acetate film, poly(viny; acetal) 1~3~ 4 fi~m, polystyrene film, poly(ethyleneterephthalate) film, poly-carbonate film, poly-a-olefins such as polyethylene and poly-propylene film, and related films or resinous materials. The support is usually about 2 to 6 mils in thickness.
While the invention has been described with reference to layers of silver halide emulsions and dye image-providing materials, dotwise coating, such as would be obtained using a gravure printing technique, could also be employed. In this technique, small dots of blue-, green- and red-sensitive emulsions have associated therewith, respec-tively, dots of yellow, magenta and cyan color-providing substances. After development, the trans-ferred d~es would tend to ~use together -Lnto a con~inuous tone.
The sil~er halide emulsions useful in our invention are well known to those skilled in the art and are described in Product Licensing Index, Vol. 92, December, 1971, publication 9232, p. 107, paragraph I, "Emulsion types"; they may be chemi-cally and spectrally sensitized as described on Rage 107, para-graph III, "Chemical sensitization", and pp. 108-109, paragraph X~, "Spectral sensitization", o~ the above article; they can be p~otected against the production of fog and can be stabilized against loss of sensitivity during keeping by employing the materials described on p. 107, paragraph V, "Antifoggants and ~- stabilizers", of the above article; they can contain development modi~iers, hardeners, and coating aids as described on pp. 107-108, paragraph IV, "Development modifiers"; paragraph VII, "Har-deners"; and paragraph XII, "Coating aids", of the above article;
they and other layers in the photographic elements used in this invention can contain plasticizers, vehicles and filter dyes described on p. 108, paragraph XI, "Plasticizers and lubricants", and paragraph VIII, "Vehiclesi', and p. 109, paragraph XVI, "Absorbing and filter dyes", of the above article; they and other r.,~
~L03886~L .
layers in the photographic elements used in this invention m~.y contain addenda which are incorporated by using the procedures described on p. 109, paragraph XVII, "Methods of addition", of the above article; and they can be coated by using the various techniques described on p. 109, paragraph ~VIII, "Coat:Lng pro-cedùres", of the above article, the disclosures of which are hereby incorporated by referenceO
It will be appreciated that there remains in the photo-graphic element after transfer has taken place an imagewise distrlbution of dye in addition to developed silver. A color image comprls~ng residual nondif~usible compound may be obta~.ned in this element if the residual silver and silver halide are removed by any conventional manner well known to those skilled in the photographic art, such as a bleach bath followed by a fix bath, a bleach-fix bath, etc. The imagewise distribution of dye may also diffuse out of the element into these baths~ if desired, rather than to an image-receiving element. If a negative-working silver halide emulsion is employed in such photosensitive element, then a positive color image, such as a color transparency or motion-picture film, may be produced in this manner. If a direct-positive silver halide e~ulsion is ` e~ployed in such photosensitive element, then a negative color image may be produced.
The following examples are provided for a further understanding of the invention. The structures of all of the c~mpounds were confirmed by their infrared and NMR spectra and in some cases by elemental analysis. The notation C5Hll-t is an abbreviation for t-pentyl.
~0388G4 Example 1 - Preparation of Compound No. 1 ilO~II=N~SOaN=CH-II( CH3) 2 CH3CONH ¢0~ SO2NH
[~0~ (CHa),,-O~sHll-t I OH
To 90 ml. of dry pyridine, under nitrogen, at 0C. was added 2.95 g. (o.o6 mol) of 4-amino-N-C4-(2,4-di-tert-pentyl-phenoxy)butyl]-l-hydroxy-2-naphthamide. To this solution 2.9 g.
(o .o6 mol) of 4-acetamido-8-~5-N-(dimethylaminomethylene)sulf-amoylphenylazo]-5-hydroxy-1-naphthalenesulfonyl chloride was added. The reaction mixture was stîrred at room temperature for ninety minutes and then poured into a mixture of ice and concentrated hydrochloric acid. The resulting solid was collected on a filter funnel and dried to yield 5.8 g. (> 100~). It was purified by chromatography using a silica ~column, with ethyl acetate being used to elute the product. The yield was 30~, m.p. 237C. PREPARATION OF INTERMEDIATES: The sulfonyl chloride compound above was prepared from the sodium salt of the corresponding sulfonic acid compound by adding 3.0 g. (0.01 mol) of N,N-dimethylformamide to a slurry of 4.85 g. (0.01 mol) of sodium 4-acetamido-5-hydroxy-6-(4-sulfamoylphenylazo)-1-naphtha-lenesulfonate in 600 ml. of thionyl chlorideg The mixture was stirred for 90 minutes at room temperature and filtered. The filtrate was poured onto ice, the solid collected on a filter funnel and dried to yield 1.3 g. (24~), m.p. 140C. The sodium salt of the dye above was obtained as follows: 300 ml. of lN
, , , ~L03~86~ ;
hydrochloric acid was added to a solution of 17.2 g. (0.1 mol) of sulfanilamide in 100 ml. of 1~ sodium hydroxide. The solu-tion was cooled to 0C and a solution of 6.9 g. (0.1 mol) of sodium nitrite in 80 ml. of water was added at <3C. This mixture was then added to a solution of 8-acetamido-1-acetoxy-5-naphthalenesulfonic acid, pyridine salt in 300 ml. of lN
sodium hydroxide at < 3C. The reaction mixture was stirred for one hour, solid collected on a filter funnel and dried to yield 35.2 g. (72~), m.p. 7300C. The pyridine salt above was obtained by the acetylation of "S acid" in acetic anhydride and pyridine at 80C.
Example 2 - PreParation of Compound No. 2 ;~ HO ~ -N=N ~
CH~CON~ ~ SO2NH SO2N=CH-N(CH3)2 1 C5HlL-t ~ CO~H~(cH2)~-O ~ -CsHL -t This compound was prepared in a manner similar to that used in Example 1. The yield was 20~, m.p. 163-6C.
The 4-acetamido-8-~5-(N-dime-thylaminomethylene)sulfamoyl-2-methoxyphenylazo]-5-hydroxy-1-naphthalenesulfonyl chlori.de was -~ prepared in a manner similar to that used in Example 1.
~03~3864 ' ~
Example 3 - Preparation of Compound No. 3 OCH~
H ~ N-N- ~
~ SO2N=CH-N(CH3)2 C~H5CO~ ~ SO2NH
@$LCON~l-(cH~4-o~asHl~-t OH
The method used in Example 1 was utilized to prepare this compound. The yield was 26~, m.p. 168-72C dec. m e 4- ;
benzamido-8-[5-N-(dimethylaminomethylene)sulfamoyl-2-methoxy-phenylazo]-5-hydroxy-1-naphthalenesulfonyl chloride was prepared by the method used for Example 1 in 68~ yield. Sodium 4-benzamido-5-hydroxy-8-(2-methoxy-5-æulfamoylphenylazo)-1-naphthalenesulfonate was also prepared similarly to Example 1 ~! lo in 35% yield.
Example 4 - Preparation of Compound No. 4 :
~O~N=I~SO2NHSO2 C~H5CONH- ~ -SO2NH
~ CONH-(CH2)~-O ~ CsHlL-t .. . . .
,~
The method used for Example 1 was used to prepare this compound. The yield was 15~, m.p. 155-60C dec. The sulfonyl chloride was prepared from 1.0 g. (.0014 mol.) of 4-benzamido-8-[4-(N-benzenesulfonylsulfamoyl)phenylazo]-5-hydroxy-1-naphthalene-sulfonic acid, sodium salt which was stirred overnight in 25 ml.
of chlorobenzene containing o.8 g. of phosphorous pentachloride.
The solid was collected on a filter funnel and dried to yield 1.0 g. (100~). The sodium 4-benzamido-8-~4-(benzenesulfonyl-sulfamoyl)phenylazo]-5-hydroxy-1-naphthalene sulfonate was pre-pared in a manner similar to Example 1 in 15~ yield.
Example 5 - Preparation of Compound No. 5 CONH( CH2) 4,-0~C5H~ t ~: ~ }IO~N=N~S02~1~_011 Cs~l~~t CH3COI~H~S02NH ~) --CO~H-( CH2 ) " -0- ~CsH l ~,- t Cs l-t ......
To a solution of 1.95 g. (.004 mol) of ~-amino-N-[4-~2~4-di-tert-pentylphenoxy)butyl~-1-hydroxy-2-naphthamide in 50 ml. of dry pyridine at 0C, under nitrogen, was added 1.95 g.
', (.004 mol) of 4-acetamido-8-(4-chlorosulfonylphenylazo)-5-hydroxy-l-naphthalenesulfonyl chloride. The solution was stirred at 0C for one hour, poured into 75 ml. of concentrated hydro-chloric acid and 75 ml. of ice. The solid was collected on a filter funnel and dried. It was then chromatographed on a silica column, eluting with ethyl acetate to remo~e the product. The eluents were concentrated to dryness and the resulting solid reprecipitated from chloroform with hexane. The solid was collected on a filter funnel and dried to yield 1.1 g. (39%), m.p. 220-2C dec. The 4-acetamido-8-(4-chlorosulfonylphenylazo)-5-hydroxy-1-naphthalenesulfonyl chloride was prepared by heating a solution of 9.7 g. (.02 mol) of sodium 4-acetamido-5-hydroxy--3l~-~38864
6-(4-sulfamoylphenylazo)-l-naphthalenesulfonate in 150 ml. of chlorosulfonic acid on a steam bath for ninety minutes. The solution was cooled and poured onto ice. 'rhe solid was collected on a filter funnel and dried to yield 9.4 g. (94~). The sodium 4-acetamido-5-hydroxy-8-~4-sulfamoylphenylazo)-1-naphthalene-sulfonate was prepared as in Example l.
.. . . . ~ . ...... . .... .. . . _ _ . . . . .
Example 6 - Preparation of Compound No. 6 CH30 CONH-(CH2)~-0 ~ sHll-t HO ~ -N~N ~ -SO2NH ~ OH C t CH3CO~ ~ SO2~
C01~ t CH2 ~ 4-0~5Hll-t ~ OH Hll-t . . .
This compound was prepared in a manner similar to that used for Example 5. The yield was 74~, m.p. 138-42C. The 4-acetamido-8-(5-chlorosulfonyl-2-methoxyphenylazo)-5-hydroxy-1-naphthalenesulfonyl chloride was prepared according to the method of Example 5. The sodium 4-acetamido-5-hydroxy-8-(5-sulfamoyl-2-methoxyphenylazo)-1-naphthalenesulfonate was prepared in a manner similar to that used in Example 1.
Example 7 - Preparation of Compound No. 7 .~
HO ~ -N=N ~ SozNHCtCH3) 3 CH3GOi~H ~ ,SOz .
--CONH-(C~I2)~-O ~ CsHll-t OH C5Hll-t ~03~3S1~4 ~
The method shown for Example 1 was also u6ed to prepare this example in 40~ yield, m.p. 169-72C dec. The 4-acetamido-8-[4-(N-t-butyl)sulfamoylphenylazo~-5-hydroxy-1-naphthalenesuIfonyl chloride was prepared, in 89% yield, similarly to Example 1.
Sodium 4-acetamido-8-[4-(N-t-butyl)sulfamo~ylphenylazo]-5~hydroxy-l-naphthalenesulfonic acid was prepared in a manner similar to Example 1. The yield was 395~.
Exam~le 8 - Preparation of Compound No. 8 S ~ OH
NH
~CONH(CH2)~,-O~CsN~1-t Cs}~ l L - t : , To a solution of 2.50 g. (3.8 n~nol) of 4-m-aminobenzene-sulfonamido-N-~4-(2,4-di-tert-pentylphenoxy)butyl]-1-hydroxy-2-naphthamide in 20 ml. of trifluoroacetic acid (under nitrogen) in an ice-methanol bath was added a cold solution of 0.28 g.
(4 mmol) of sodium nitrite in 3 ml. of water. The green-yellow diazonium solution, which formed immediately, was poured into a stirred solution (under nitrogen) of 0.62 g. (3.8 mmol) of 1,8-dihydroxynaphthalene in 10 ml. pyridine and 50 ml. mixed acid (1:5 propionic/acetic acids). The magenta-colored mixture was stirred at 0 for 45 minutes and then poured into 600 g. of 20 ice water. The crude product was filtered, washed with water, and dried. It weighed 3.32 g. The crude material was recrystal-lized once from a mixture of tetrahydrofuran, methanol, and water and again from ethyl acetate/hexane to give 2.35 g.
m.p. 232-234C.
_36-103~864 Example 9 - Pre~aration of Compound No. 9 SO~ ~ N=N ~ H
NH . <~
[~L-CONH-( CH2 ) 4_0~>~5H~l- t , OH CsHll-t ~, To a solution of 1.3 g. (2.0 mmol) of 4-p-aminobenzene-sulfonamido-N-~4-(2,4-di-tert-pentylphenoxy)butyl]-1-hydroxy-2-naphthamide in 10 ml. of trifluoroacetic acid (under nitrogen) was added a cold solution of 0.14 g. (2 mmol) of sodium nltrite in 1 ml. of water. The deep brown-green diazonium solution thus formed was poured into a solution of l-naphthol 6-sulfonamide in 9 ml. pyridine/45 ml. of 1:5 propionic/acetic acid. Because coupling occurred rather slowly, the red-orange solution was stirred 1.5 hours and then poured into 400 g. of ice water.
The resulting orange solid was filtered, washed with water and air dried. The crude product was recrystallized from ethanol/
tetrahydrofuran/hexane and again ~rom tetrahydro~uran/hexane -to give 1.07 g. (61~) of magenta dye, m.p. 164-166C.
Example 10 - Preparation of Compound No. 10 CONH(CH,)~-O~CsHll~'i ~ID38~
A solution of 6.45 g. ~10 mmol) ~-m-aminobenzenesulfon-amido-N-[4-(2,4-di-t-pentylphenoxy)butyl]-1-hydroxy-2-naphthamide in 100 ml. tetrahydrofuran was cooled to 3C and treated dropwise with 1.2 g. of isopentyl nitrite. The mixture was stirred one-` ; half hour and then poured slowly into a co:Ld solution of 1.6 g.
(10 mmol) of 1,5-naphthalenediol in 250 ml. of 20~o solution of propionic acid in acetic acid followed by 10 drops of pyridine.
' The mix~ure was left in the refrigerator overnight, filtered, and diluted with water to give a tar, which was solidified by heating in glacial acetic acid followed by cooling. The solid was filtered off, washed with water and air dried. On standing an additional product precipitated from the supernatant, yielding a total of 6.5 g. (80%). The product was recrystallized from acetic acid to give 2.8 g. of orange powder, m.p. 232-5.
Example 11 - Preparation of Compound No. 11 ;~
, . S02~N=N~_oH i'~
NH ~ ~
-CO~H-(CHæ)4~0~ ~ CsHl-t OH C5 ~1- t `~ A solution of O.65 g. (1 mmol) of 4-m-aminobenzene-sulfonamido-N-[4-(2,4-di-t-pentylphenoxy)butyl]~l-hydroxy-2-naphthamide and 0.14 ml. of isopentyl nitrite in 10 ml. of tetra-20 hydrofuran was added to a solution of 0.175 g. (1 mmol) of 1-naphthol in 25 ml. of a 5:1 mixture of acetic acid and propionic acid at 0C. The reaction mixture was stirred for one hour during which time a red solid precipitated. The solid was col-lected and washed with aqueous acetic acid. This provlded o.6 g.
of pure product in 72~ yield, m.p. 212-215.
_38-.
~03~864 Example 12 - Photographic Testing The dye-releasing redox (DRR) compounds were tested for reactivity and diffusibility of their released dyes to a receiving element. Each DRR compound was ais solved in an equal weight of diethylauramide and finely dispersed in gelatin. me dispersion was added to a o.8 ~m monodispersed negative-working gelatino-silver bromide emulsion which was coated on a polyester film 9upport, the coverage of DRR being about 1.1 x 10 5 moles/dm2;
silver - 9.2 mg/dm2; and gelatin - 32 mgjdm2. An overcoat layer of 8.6 g/dm of gelatin, hardened by formaldehyde was then applied.
A. Image discrimination - A sample of the above coating was exposed through a step-wedge and then laminated to a mordant-containing receiving element with a viscous processing composi-; tion (goo) by passing the "sandwich" between a pair of juxtaposed pressure-applying rollers. The receiving element consisted of a paper support on which was coated a mixture of gelatin (21 mg/dm2) and a mordant, poly~styrene-co-N-benzyl-N,N-dimethyl-N-(3-maleimidopropyl)ammonium chloride] (21 mg/dm2). The goo contained per liter of solution: 20 g. sodium hydroxide, 0.75 g. 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone, 10 g.
potassium bromide, and 25 g. hydroxyethylcellulose. After 60 seconds, the receiver was peeled apart and washed in water to adjust the pH to about 7. Good image density in the exposed areas was obtained with practically no transfer of dye in the unexposed areas. The Dmax and Dmin for each transfer is given under image discrimination in the table.
B. Spectrophotometry - The spectra of the released dyes when adsorbed to the mordant on a transparent support were measured spectrophotometrically. The maximum wavelength ( A max) and -3g-1038~364 the bandwidth in nm at one-half the density at the ~ max of the curve for each dye is also given in the table. This "half band width" along with the ~ max is indicative of hue, the brightness and purity of color being greater, the smaller the half band width.
C. Dye-transfer in receiving element - Another sample of an emulsion coating containing the DRR compound was fogged by exposure to light and processed by passing it as a "sandwich"
with an image receiving element and viscous developing composi-tion (goo) between a pair of juxtaposed pressure-applying rollers.
The developer layer thickness of the resulting laminate ranged from about .075 to .10 mm. The recei~ing element had -the following structure (the coverages in mg/dm2 are shown ln parenthesis):
Carbon (27) ~ Gelatin (17) TiO2 (215) ~ Gelatin (21) .
Mordant* (21) + Gelatin 111) Cellulose acetate support The "goo" contained 20 g. sodium hydroxlde, 0.75 g. 4-hydroxy-20 methyl-4-methyl-1-phenyl-3-pyrazolidone, 10 g. potassium bromide and 25 g. hydroxyethylcellulose, all per liter of solution.
Upon application of the goo to the fogged emulsion layer, the dyes are released and diffuse through the carbon and titania layers to the mordant layer. The density of the dyes on the mordant layer was read through the support by means of a reflec-tion densitometer after intervals of 30, 60 and 120 seconds at 24C. The increase in density as indicated by the values in the table, is a measure of the rate of release and also of the diffusivity of the dyes.
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Example 13 - Preparation of Compound No. 12 OH
-N ~ 52NH ~ OH
CONH-(CH2)4-O ~ C5Hll t ~ ' C5Hll-t - CH
A solution of 1 mole 5-amino-1-naphthol in dr~ pyridine was stirred at 0C and treated portionwise with 1 mole o~ p-toluenesulfonyl chloride. When anaylsis showed that the 5-amino-; l-naphthol was consumed the reaction mixture was poured onto a sufficient quantity of aqueous hydrogen chloride to neutralize the excess pyridine and allow separation of the product as a fine powder which was filtered, washed with water, and recrystal-lized from ethanol to obtain (96~ yield) analytically pure 5-p-toluenesulfonamido-1-naphthol having a melting point of 182-194C. Next, 2.58 g. (4000 mmol) of 4-(m-aminophenylsulfon-amido)-N-~4-(2,4~di-tert-pentylphenoxy)butyl]-1-hydroxy-2-naphthamide were dissolved in 10 ml. dry pyridine and treated with 50 ml. 5:1 acid and 10 ml. concentrated hydrochloric acid.
The clear solution was cooled to 0C. and treated with a solu-tion of 284 mg. (4.00 mmol) sodium nitrite in 3 ml. of ice water.
The resulting orange solution was added rapidly to a solution of 1.25 g. (4.00 mmol) of the above sulfonamidonaphthol dissolved 20 in 8 ml. dry pyridine and 50 ml. 5:1 acid, and cooled to 5C.
The orange dye formed immediately. After 40 minutes at 5-10, the dye was precipitated by adding 300 ml. ice water and adjusting the pH to 2 with concentrated HCl. The orange powder obtained - 1~2 -~03~36q~
by filtration was washed with 8 liters of water and dried to gi~e 3.31 g. Compound 12. This compound was tested in a manner similar to that of Example 12A and the released dye was found to have a A max of 555 nm. The Dmax of transferred image was 0.97-E le 14 - Pre aration of C ound No. 13 xamp _p omp OH
~ .
NH N=N ~ SO H
C=O ~_J 3 S02~U ~ OH
C=O
(CH2)4 ~ C5Hll t C5Hll-t . .
A solution of 8.1 g. (.05 mmol) 5-amino-1-naphthol, 6.1 g. (.05 mmol) N,N-dimethylaniline, and in 100 ml. tetrahydro-furan was added dropwise at -10-0C to a solution of 12.1 g.
(.05 mmol) m-chlorosulfonylbenzoyl chloride in tetrahydrofuran (200 ml.). The addition required 1 hour. The reaction was nearly complete after the addition but was stirred at -10C
~or 2 hours, treated with .05 mole of Compound A, 4-amino-N-~-4-(2,4-di-tert-pentylphenoxy)butyl]-1-hydroxy-2-naphthamide~
and .05 mole pyridine, and stirred at 25C until ~ompound A had reacted. The reaction mixture was poured into 2 liters of water and the dark oil which separated induced to crystallize by adding 200 ml. 10~ hydrogen chloride solution. The crude product was filtered, washed with water, and air dried to give 42.96 g.
of crude product (102~ yield). Recrystallization from 500 ml.
1~3886~a boiling benzene gave, after filtration and a slow recrystalliza-tion 39 g. of product 2 (92~) having m.p. 21~-219C with satis-factory IR and NMR analyses. Next, a solution of 8.28 g. (.Ol mol) Compound 2 in 4.0 g. 50~ sodium hydroxide solution and 50 ml. water was added at 0 to a solution of diazotized sulfanilic acid (.O1 mol) prepared in the usual manner at 0C. Coupling at 0C was conducted for 1 hour at pH 10 by proper adjustment of the pH with sodium carbonate solution. The red solution was acidified with 10~ hydrogen chloride solution, filtered, and washed thoroughly with cold water. The crude dye-providing com-pound weighed 9.24 g. (92~) when dried and was purified suffi-clently for image transfer testing by repeated trituration from boiling acetonitrile. After washing thoroughly with cold aceto-nitrile and diethyl ether, it was thoroughly vacuum dried. The resultant Compound 13 was tested as in Example 12A and the transferred magenta dye image was found to have a Dmax of about 2.2.
Example 15 - Preparation of Compound No. 14 OH
N=N ~
52 ` ~ CONH-(CH2)4-o ~ C5H11 t 1~4 .
~ ~ .
~03~64 10.3 g. (.025 mol) of N-[5-hydroxy-6-(m-fluorosulfonyl-phenylazo)-l-naphthyl~methanesulfonamide was added to 8.o g.
(.Og5 mol) of sodium bicar~onate and 12.2 g. (.025 mol) of 4-amino-N-~4-(2~4-di-tert-pentylphenoxy)butyl]-1-hydroxy-2-naphthamide in 80 ml. of dimethylsulfoxide, under nitrogen. The mixture was heated on a steam bath for ninety minutes and poured into 1 liter of ice water containing 25 ml. of concentrated hydrochloric acid. The solid was collected on a filter funnel and dried. After one slurry in L~oO ml. of hot toluene and one slurry in 100 ml. of acetic acid, the yield of dye was 12.0 g.
(55%). PREPARATION OF INTERMEDIATES: A cooled solutlon Of 2.0 g. (0.29 mol) of sodium nitrite ln 12 ml. of water was added portionwise, at ~ 5C to a solution of 6.o5 g. (.029 mol) of 3-aminobenzenesulfonyl fluoride in 50 ml. of 10% hydrochloric acid. This solution was added at 10C to a cooled solution of 6 .o8 g. ( .026 mol) of N-(5-hydroxy-1-naphthyl)methanesulfonamide in 75 ml. of a mixture of 1 part by volume propionic acid to 5 parts acetic acid and 18 ml. of pyridine. The final solution was stirred at < 10C for ninety minutes and poured into 1 liter of ice water. The pH of the aqueous solution was adjusted to 2, the solid collected on a filter funnel and dried to yield 10.3 g. (93~). For the preparation of the above sulfonamide, 20.0 g. (.125 mol) of 5-amino-1-naphthol was dissolved in 63 ml.
of acetone cont~ining 10 ml. (.13 mol) of pyridine. To this mixture 16.0 g. (.14 mol) of methanesulfonyl chloride was added dropwise. The temperature gradually rose to 55C and solution was effected. The solution was stirred for forty-five minutes and poured into 650 ml. of water containing 15 g. ~.375 mol) of sodium hydroxide. The temperature rose to 60C. The solution 30 was cooled, and acidified with concentrated hydrochloric acid.
The solid was collected on a filter funnel, washed with water, and dried to yield 25.7 g. (87~), m.p. 1l~3-7C. Compound No. 1 1(~38~36~ ~
was tested as in Exa~ple 12C and found to have transferred dye image densities of 1.86, 2.3 and 2.4 after 30, 60 and 120 seconds, respectively.
Example 16 Dyes such as those released from the previously discussed carriers (Car-) during alkaline processing were pre-pared and dissolved in 30 ml. of a 0.5N sodium hydroxide solu-tion containing 30 g/l of hydroxyethylcellulose~ Each solution was spread between a cellulose acetate cover sheet and a receiving 10 element so that the alkaline dye composition was 0.1 mm thick.
The receiving element was as described in Example 12 only having an additional layer o~ gelatin (43 mg/dm2) coated over the carbon-gelatin layer. The spectra of the dyes when adsorbed to the mordant were determined as in Example 12. The following Table II shows the general formula of the dyes tested and the . _ . . ... . . .
results obtained.
... . _ . . . . . . .
Table II
N= N ~ OH
1038~6~L
Table II (continued) Z R El Q
4 S2NH2 H 5-S02NH2 8-NHCoCH3 531 3-S02NH2 H ~ ,. 522 4-So2NH2 2-Cl -'' 543 3-S02NH2 6-Cl " " 528 3-S02NH2 4-Cl " ~ 52 3-S02NH2 6-oCH3 " ~ - 519 2-S02NH2 H n 510 2-S02NHCH3 .. 538 4-So2NH(cocH3) H .~ . n 542 2 S2CH3 H n 4-CN H ~ n 550 2-CN H ~ ,. 549 " - 524 2-CF H:
3 " " 520 2-Cl H
4-so2~H2 H H 5-OH 571 20 3-S02NH2 H H " 55600 3-S02NH2 H H 8-oH
4-So2NH2 H H 5 NHS02CH3 563 3-S02NH2 x H " 552 4-So2~H2 H 3-S02NH2 H . 518 3-S02NH2 H 6-S03Na 8-NHCoCH3 533 4-So2NH2 H 5-S03Na " 54 .
' ' ' ' ' - :~L03~864 Table II (continued) _ Rl El Q ~ (nm) : 4-So2NH2 2-C1 8-N~CoCH3 535 4-So2NH2 2-C1 3-SO~Na 5-NHCOCH3 53 3-S02N~I2 H H 8-~HS02CH3 517 4-So2NH2 ~ 5-so2N~ 8-~HCoCE3 533 ; S2NH2 2-S02CH3 ~ 6-S2NH2 H 576 4-So2CH3 H 6-S2N~I2 H 576 .....
10 Example 17_- Preparatlon of Compo~d No. 15 OCO2CH2CH3 ' CONH(CH2)4-O ~ C5Hll t S2 ~ S02NH C5Ell t The above Compound 15 was prepared in a manner similar to Example 15 only using N-~5-ethoxycarbonyloxy-6-(m-chloro-sulfonylphenylazo)-l-naphthyl]methanesulfamide which was prepared from the 5-hydroxy counterpart (made as in Example 15) by reac-tion with ethyl chloroformate. Compound 15 was tested as in Example 15 and found to have a A max in the coating of 440 nm . and a ~ max of transferred dye of 555 nm and densities of 1.87 ;~ ~30 seconds), 2.5 (60 seconds) and 2.6 (120 seconds).
..
:
.. . . . ~ . ...... . .... .. . . _ _ . . . . .
Example 6 - Preparation of Compound No. 6 CH30 CONH-(CH2)~-0 ~ sHll-t HO ~ -N~N ~ -SO2NH ~ OH C t CH3CO~ ~ SO2~
C01~ t CH2 ~ 4-0~5Hll-t ~ OH Hll-t . . .
This compound was prepared in a manner similar to that used for Example 5. The yield was 74~, m.p. 138-42C. The 4-acetamido-8-(5-chlorosulfonyl-2-methoxyphenylazo)-5-hydroxy-1-naphthalenesulfonyl chloride was prepared according to the method of Example 5. The sodium 4-acetamido-5-hydroxy-8-(5-sulfamoyl-2-methoxyphenylazo)-1-naphthalenesulfonate was prepared in a manner similar to that used in Example 1.
Example 7 - Preparation of Compound No. 7 .~
HO ~ -N=N ~ SozNHCtCH3) 3 CH3GOi~H ~ ,SOz .
--CONH-(C~I2)~-O ~ CsHll-t OH C5Hll-t ~03~3S1~4 ~
The method shown for Example 1 was also u6ed to prepare this example in 40~ yield, m.p. 169-72C dec. The 4-acetamido-8-[4-(N-t-butyl)sulfamoylphenylazo~-5-hydroxy-1-naphthalenesuIfonyl chloride was prepared, in 89% yield, similarly to Example 1.
Sodium 4-acetamido-8-[4-(N-t-butyl)sulfamo~ylphenylazo]-5~hydroxy-l-naphthalenesulfonic acid was prepared in a manner similar to Example 1. The yield was 395~.
Exam~le 8 - Preparation of Compound No. 8 S ~ OH
NH
~CONH(CH2)~,-O~CsN~1-t Cs}~ l L - t : , To a solution of 2.50 g. (3.8 n~nol) of 4-m-aminobenzene-sulfonamido-N-~4-(2,4-di-tert-pentylphenoxy)butyl]-1-hydroxy-2-naphthamide in 20 ml. of trifluoroacetic acid (under nitrogen) in an ice-methanol bath was added a cold solution of 0.28 g.
(4 mmol) of sodium nitrite in 3 ml. of water. The green-yellow diazonium solution, which formed immediately, was poured into a stirred solution (under nitrogen) of 0.62 g. (3.8 mmol) of 1,8-dihydroxynaphthalene in 10 ml. pyridine and 50 ml. mixed acid (1:5 propionic/acetic acids). The magenta-colored mixture was stirred at 0 for 45 minutes and then poured into 600 g. of 20 ice water. The crude product was filtered, washed with water, and dried. It weighed 3.32 g. The crude material was recrystal-lized once from a mixture of tetrahydrofuran, methanol, and water and again from ethyl acetate/hexane to give 2.35 g.
m.p. 232-234C.
_36-103~864 Example 9 - Pre~aration of Compound No. 9 SO~ ~ N=N ~ H
NH . <~
[~L-CONH-( CH2 ) 4_0~>~5H~l- t , OH CsHll-t ~, To a solution of 1.3 g. (2.0 mmol) of 4-p-aminobenzene-sulfonamido-N-~4-(2,4-di-tert-pentylphenoxy)butyl]-1-hydroxy-2-naphthamide in 10 ml. of trifluoroacetic acid (under nitrogen) was added a cold solution of 0.14 g. (2 mmol) of sodium nltrite in 1 ml. of water. The deep brown-green diazonium solution thus formed was poured into a solution of l-naphthol 6-sulfonamide in 9 ml. pyridine/45 ml. of 1:5 propionic/acetic acid. Because coupling occurred rather slowly, the red-orange solution was stirred 1.5 hours and then poured into 400 g. of ice water.
The resulting orange solid was filtered, washed with water and air dried. The crude product was recrystallized from ethanol/
tetrahydrofuran/hexane and again ~rom tetrahydro~uran/hexane -to give 1.07 g. (61~) of magenta dye, m.p. 164-166C.
Example 10 - Preparation of Compound No. 10 CONH(CH,)~-O~CsHll~'i ~ID38~
A solution of 6.45 g. ~10 mmol) ~-m-aminobenzenesulfon-amido-N-[4-(2,4-di-t-pentylphenoxy)butyl]-1-hydroxy-2-naphthamide in 100 ml. tetrahydrofuran was cooled to 3C and treated dropwise with 1.2 g. of isopentyl nitrite. The mixture was stirred one-` ; half hour and then poured slowly into a co:Ld solution of 1.6 g.
(10 mmol) of 1,5-naphthalenediol in 250 ml. of 20~o solution of propionic acid in acetic acid followed by 10 drops of pyridine.
' The mix~ure was left in the refrigerator overnight, filtered, and diluted with water to give a tar, which was solidified by heating in glacial acetic acid followed by cooling. The solid was filtered off, washed with water and air dried. On standing an additional product precipitated from the supernatant, yielding a total of 6.5 g. (80%). The product was recrystallized from acetic acid to give 2.8 g. of orange powder, m.p. 232-5.
Example 11 - Preparation of Compound No. 11 ;~
, . S02~N=N~_oH i'~
NH ~ ~
-CO~H-(CHæ)4~0~ ~ CsHl-t OH C5 ~1- t `~ A solution of O.65 g. (1 mmol) of 4-m-aminobenzene-sulfonamido-N-[4-(2,4-di-t-pentylphenoxy)butyl]~l-hydroxy-2-naphthamide and 0.14 ml. of isopentyl nitrite in 10 ml. of tetra-20 hydrofuran was added to a solution of 0.175 g. (1 mmol) of 1-naphthol in 25 ml. of a 5:1 mixture of acetic acid and propionic acid at 0C. The reaction mixture was stirred for one hour during which time a red solid precipitated. The solid was col-lected and washed with aqueous acetic acid. This provlded o.6 g.
of pure product in 72~ yield, m.p. 212-215.
_38-.
~03~864 Example 12 - Photographic Testing The dye-releasing redox (DRR) compounds were tested for reactivity and diffusibility of their released dyes to a receiving element. Each DRR compound was ais solved in an equal weight of diethylauramide and finely dispersed in gelatin. me dispersion was added to a o.8 ~m monodispersed negative-working gelatino-silver bromide emulsion which was coated on a polyester film 9upport, the coverage of DRR being about 1.1 x 10 5 moles/dm2;
silver - 9.2 mg/dm2; and gelatin - 32 mgjdm2. An overcoat layer of 8.6 g/dm of gelatin, hardened by formaldehyde was then applied.
A. Image discrimination - A sample of the above coating was exposed through a step-wedge and then laminated to a mordant-containing receiving element with a viscous processing composi-; tion (goo) by passing the "sandwich" between a pair of juxtaposed pressure-applying rollers. The receiving element consisted of a paper support on which was coated a mixture of gelatin (21 mg/dm2) and a mordant, poly~styrene-co-N-benzyl-N,N-dimethyl-N-(3-maleimidopropyl)ammonium chloride] (21 mg/dm2). The goo contained per liter of solution: 20 g. sodium hydroxide, 0.75 g. 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone, 10 g.
potassium bromide, and 25 g. hydroxyethylcellulose. After 60 seconds, the receiver was peeled apart and washed in water to adjust the pH to about 7. Good image density in the exposed areas was obtained with practically no transfer of dye in the unexposed areas. The Dmax and Dmin for each transfer is given under image discrimination in the table.
B. Spectrophotometry - The spectra of the released dyes when adsorbed to the mordant on a transparent support were measured spectrophotometrically. The maximum wavelength ( A max) and -3g-1038~364 the bandwidth in nm at one-half the density at the ~ max of the curve for each dye is also given in the table. This "half band width" along with the ~ max is indicative of hue, the brightness and purity of color being greater, the smaller the half band width.
C. Dye-transfer in receiving element - Another sample of an emulsion coating containing the DRR compound was fogged by exposure to light and processed by passing it as a "sandwich"
with an image receiving element and viscous developing composi-tion (goo) between a pair of juxtaposed pressure-applying rollers.
The developer layer thickness of the resulting laminate ranged from about .075 to .10 mm. The recei~ing element had -the following structure (the coverages in mg/dm2 are shown ln parenthesis):
Carbon (27) ~ Gelatin (17) TiO2 (215) ~ Gelatin (21) .
Mordant* (21) + Gelatin 111) Cellulose acetate support The "goo" contained 20 g. sodium hydroxlde, 0.75 g. 4-hydroxy-20 methyl-4-methyl-1-phenyl-3-pyrazolidone, 10 g. potassium bromide and 25 g. hydroxyethylcellulose, all per liter of solution.
Upon application of the goo to the fogged emulsion layer, the dyes are released and diffuse through the carbon and titania layers to the mordant layer. The density of the dyes on the mordant layer was read through the support by means of a reflec-tion densitometer after intervals of 30, 60 and 120 seconds at 24C. The increase in density as indicated by the values in the table, is a measure of the rate of release and also of the diffusivity of the dyes.
*same a3 above ~3886~
o . . t`~O~O~
,, . O ~ ~ ~ ~
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h ~H ~ O d- ~ ~ O O 00 If~
u~ ul ~ ~ ~ oo ~ u~ ~ o C
~ ...........
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h S~ ~
E~ ~
a) 4~ ,,~
I
~ou~ln~e~a~
~ V~ ~ ` 1--~ ~ 1--`D ~ oo l u~
4~ l ...........
On~ o ,~ooooooooo . , I ~') ~ I
~1 ~ ~O
~ O~_ ~0~
X~ ~1~000~0~1~0~1 ~i O~i p ~0 ~ .
~ ~ I d 00 u7 L~ O O CO 0~ ~O O 00 P< ~3 O ~ ~ 00000000000 ~ O
~4 ~ .
cd X ou~ooo~, ~d ~ ~O ~ GO I~ O ~
E~
h ~ ~.) O V~ ~O
E~ ~ ,_ O ~ 0 a~
~d h h `D ~ -1 ~ 1--l ~1 `D ~1~ ~1 -1 ~ a~ u~ ~ ~1 ~ ~1 ~ ~1 ~ ~ .
., ~ :~ ~ P
~O
3 o ~ U~ o ,~
I '~ ~1 ~1 ~1 0 0 ~1 0 ~ O 0 ~1 ~d ~
X
,_ o o o U~ o o ~ Ln oo o ~.
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p~ O ~ ~ ~ ~ ~ U~
o x t~ ~
,.` .
Example 13 - Preparation of Compound No. 12 OH
-N ~ 52NH ~ OH
CONH-(CH2)4-O ~ C5Hll t ~ ' C5Hll-t - CH
A solution of 1 mole 5-amino-1-naphthol in dr~ pyridine was stirred at 0C and treated portionwise with 1 mole o~ p-toluenesulfonyl chloride. When anaylsis showed that the 5-amino-; l-naphthol was consumed the reaction mixture was poured onto a sufficient quantity of aqueous hydrogen chloride to neutralize the excess pyridine and allow separation of the product as a fine powder which was filtered, washed with water, and recrystal-lized from ethanol to obtain (96~ yield) analytically pure 5-p-toluenesulfonamido-1-naphthol having a melting point of 182-194C. Next, 2.58 g. (4000 mmol) of 4-(m-aminophenylsulfon-amido)-N-~4-(2,4~di-tert-pentylphenoxy)butyl]-1-hydroxy-2-naphthamide were dissolved in 10 ml. dry pyridine and treated with 50 ml. 5:1 acid and 10 ml. concentrated hydrochloric acid.
The clear solution was cooled to 0C. and treated with a solu-tion of 284 mg. (4.00 mmol) sodium nitrite in 3 ml. of ice water.
The resulting orange solution was added rapidly to a solution of 1.25 g. (4.00 mmol) of the above sulfonamidonaphthol dissolved 20 in 8 ml. dry pyridine and 50 ml. 5:1 acid, and cooled to 5C.
The orange dye formed immediately. After 40 minutes at 5-10, the dye was precipitated by adding 300 ml. ice water and adjusting the pH to 2 with concentrated HCl. The orange powder obtained - 1~2 -~03~36q~
by filtration was washed with 8 liters of water and dried to gi~e 3.31 g. Compound 12. This compound was tested in a manner similar to that of Example 12A and the released dye was found to have a A max of 555 nm. The Dmax of transferred image was 0.97-E le 14 - Pre aration of C ound No. 13 xamp _p omp OH
~ .
NH N=N ~ SO H
C=O ~_J 3 S02~U ~ OH
C=O
(CH2)4 ~ C5Hll t C5Hll-t . .
A solution of 8.1 g. (.05 mmol) 5-amino-1-naphthol, 6.1 g. (.05 mmol) N,N-dimethylaniline, and in 100 ml. tetrahydro-furan was added dropwise at -10-0C to a solution of 12.1 g.
(.05 mmol) m-chlorosulfonylbenzoyl chloride in tetrahydrofuran (200 ml.). The addition required 1 hour. The reaction was nearly complete after the addition but was stirred at -10C
~or 2 hours, treated with .05 mole of Compound A, 4-amino-N-~-4-(2,4-di-tert-pentylphenoxy)butyl]-1-hydroxy-2-naphthamide~
and .05 mole pyridine, and stirred at 25C until ~ompound A had reacted. The reaction mixture was poured into 2 liters of water and the dark oil which separated induced to crystallize by adding 200 ml. 10~ hydrogen chloride solution. The crude product was filtered, washed with water, and air dried to give 42.96 g.
of crude product (102~ yield). Recrystallization from 500 ml.
1~3886~a boiling benzene gave, after filtration and a slow recrystalliza-tion 39 g. of product 2 (92~) having m.p. 21~-219C with satis-factory IR and NMR analyses. Next, a solution of 8.28 g. (.Ol mol) Compound 2 in 4.0 g. 50~ sodium hydroxide solution and 50 ml. water was added at 0 to a solution of diazotized sulfanilic acid (.O1 mol) prepared in the usual manner at 0C. Coupling at 0C was conducted for 1 hour at pH 10 by proper adjustment of the pH with sodium carbonate solution. The red solution was acidified with 10~ hydrogen chloride solution, filtered, and washed thoroughly with cold water. The crude dye-providing com-pound weighed 9.24 g. (92~) when dried and was purified suffi-clently for image transfer testing by repeated trituration from boiling acetonitrile. After washing thoroughly with cold aceto-nitrile and diethyl ether, it was thoroughly vacuum dried. The resultant Compound 13 was tested as in Example 12A and the transferred magenta dye image was found to have a Dmax of about 2.2.
Example 15 - Preparation of Compound No. 14 OH
N=N ~
52 ` ~ CONH-(CH2)4-o ~ C5H11 t 1~4 .
~ ~ .
~03~64 10.3 g. (.025 mol) of N-[5-hydroxy-6-(m-fluorosulfonyl-phenylazo)-l-naphthyl~methanesulfonamide was added to 8.o g.
(.Og5 mol) of sodium bicar~onate and 12.2 g. (.025 mol) of 4-amino-N-~4-(2~4-di-tert-pentylphenoxy)butyl]-1-hydroxy-2-naphthamide in 80 ml. of dimethylsulfoxide, under nitrogen. The mixture was heated on a steam bath for ninety minutes and poured into 1 liter of ice water containing 25 ml. of concentrated hydrochloric acid. The solid was collected on a filter funnel and dried. After one slurry in L~oO ml. of hot toluene and one slurry in 100 ml. of acetic acid, the yield of dye was 12.0 g.
(55%). PREPARATION OF INTERMEDIATES: A cooled solutlon Of 2.0 g. (0.29 mol) of sodium nitrite ln 12 ml. of water was added portionwise, at ~ 5C to a solution of 6.o5 g. (.029 mol) of 3-aminobenzenesulfonyl fluoride in 50 ml. of 10% hydrochloric acid. This solution was added at 10C to a cooled solution of 6 .o8 g. ( .026 mol) of N-(5-hydroxy-1-naphthyl)methanesulfonamide in 75 ml. of a mixture of 1 part by volume propionic acid to 5 parts acetic acid and 18 ml. of pyridine. The final solution was stirred at < 10C for ninety minutes and poured into 1 liter of ice water. The pH of the aqueous solution was adjusted to 2, the solid collected on a filter funnel and dried to yield 10.3 g. (93~). For the preparation of the above sulfonamide, 20.0 g. (.125 mol) of 5-amino-1-naphthol was dissolved in 63 ml.
of acetone cont~ining 10 ml. (.13 mol) of pyridine. To this mixture 16.0 g. (.14 mol) of methanesulfonyl chloride was added dropwise. The temperature gradually rose to 55C and solution was effected. The solution was stirred for forty-five minutes and poured into 650 ml. of water containing 15 g. ~.375 mol) of sodium hydroxide. The temperature rose to 60C. The solution 30 was cooled, and acidified with concentrated hydrochloric acid.
The solid was collected on a filter funnel, washed with water, and dried to yield 25.7 g. (87~), m.p. 1l~3-7C. Compound No. 1 1(~38~36~ ~
was tested as in Exa~ple 12C and found to have transferred dye image densities of 1.86, 2.3 and 2.4 after 30, 60 and 120 seconds, respectively.
Example 16 Dyes such as those released from the previously discussed carriers (Car-) during alkaline processing were pre-pared and dissolved in 30 ml. of a 0.5N sodium hydroxide solu-tion containing 30 g/l of hydroxyethylcellulose~ Each solution was spread between a cellulose acetate cover sheet and a receiving 10 element so that the alkaline dye composition was 0.1 mm thick.
The receiving element was as described in Example 12 only having an additional layer o~ gelatin (43 mg/dm2) coated over the carbon-gelatin layer. The spectra of the dyes when adsorbed to the mordant were determined as in Example 12. The following Table II shows the general formula of the dyes tested and the . _ . . ... . . .
results obtained.
... . _ . . . . . . .
Table II
N= N ~ OH
1038~6~L
Table II (continued) Z R El Q
4 S2NH2 H 5-S02NH2 8-NHCoCH3 531 3-S02NH2 H ~ ,. 522 4-So2NH2 2-Cl -'' 543 3-S02NH2 6-Cl " " 528 3-S02NH2 4-Cl " ~ 52 3-S02NH2 6-oCH3 " ~ - 519 2-S02NH2 H n 510 2-S02NHCH3 .. 538 4-So2NH(cocH3) H .~ . n 542 2 S2CH3 H n 4-CN H ~ n 550 2-CN H ~ ,. 549 " - 524 2-CF H:
3 " " 520 2-Cl H
4-so2~H2 H H 5-OH 571 20 3-S02NH2 H H " 55600 3-S02NH2 H H 8-oH
4-So2NH2 H H 5 NHS02CH3 563 3-S02NH2 x H " 552 4-So2~H2 H 3-S02NH2 H . 518 3-S02NH2 H 6-S03Na 8-NHCoCH3 533 4-So2NH2 H 5-S03Na " 54 .
' ' ' ' ' - :~L03~864 Table II (continued) _ Rl El Q ~ (nm) : 4-So2NH2 2-C1 8-N~CoCH3 535 4-So2NH2 2-C1 3-SO~Na 5-NHCOCH3 53 3-S02N~I2 H H 8-~HS02CH3 517 4-So2NH2 ~ 5-so2N~ 8-~HCoCE3 533 ; S2NH2 2-S02CH3 ~ 6-S2NH2 H 576 4-So2CH3 H 6-S2N~I2 H 576 .....
10 Example 17_- Preparatlon of Compo~d No. 15 OCO2CH2CH3 ' CONH(CH2)4-O ~ C5Hll t S2 ~ S02NH C5Ell t The above Compound 15 was prepared in a manner similar to Example 15 only using N-~5-ethoxycarbonyloxy-6-(m-chloro-sulfonylphenylazo)-l-naphthyl]methanesulfamide which was prepared from the 5-hydroxy counterpart (made as in Example 15) by reac-tion with ethyl chloroformate. Compound 15 was tested as in Example 15 and found to have a A max in the coating of 440 nm . and a ~ max of transferred dye of 555 nm and densities of 1.87 ;~ ~30 seconds), 2.5 (60 seconds) and 2.6 (120 seconds).
..
:
7 '~ . 1'.~
~L03~864 m e invention has been described in detail with par-ticular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.
`:
_~9_
~L03~864 m e invention has been described in detail with par-ticular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.
`:
_~9_
Claims (36)
1. A photosensitive element comprising a support having thereon at least one layer containing a photosensitive silver halide emulsion and at least one layer containing an image magenta dye-providing compound having a formula as follows:
I.
II.
or III.
wherein:
Ball represents an organic ballasting group of such size and configuration as to render said compound nondiffusible during development in an alkaline processing composition;
Y represents the carbon atoms necessary to complete a benzene or naphthalene nucleus;
X represents a bivalent linking group of the formula:
-R2-Lm-R2p- where each R2 can be the same or different and each represents an alkylene radical having 1 to 8 carbon atoms; or a phenylene radical;
L represents a bivalent radical selected from oxy, carbonyl, carboxamido, carbamoyl, sulfonamido, sulfamoyl, sulfinyl or sulfonyl; m is an integer having a value of 0 or 1; p is 1 when n equals 1 and p is 1 or 0 when n equals 0, provided that when p is 1 the carbon content of the sum of both R2 radicals does not exceed 14 carbon atoms;
R represents a hydrogen atom, an alkyl radical having 1 to 6 carbon atoms;
J represents a bivalent radical selected from sulfonyl or carbonyl;
m and q each represent an integer having a value of 0 or 1;
Q represents a hydrogen atom, a hydroxy radical or a radical having the formula -NHCOR3 or -NHSO2R3 wherein R3 is an alkyl radical having 1 to 6 carbon atoms, an alkyl radical having 1 to 4 carbon atoms substituted with hydroxy, cyano, sulfamoyl, carboxy or sulfo, benzyl, phenyl or phenyl substituted with carboxy, chloro, methyl, methoxy or sulfamoyl;
G represents a hydroxy radical, a salt thereof, or a hydrolyzable acyloxy group of the formula:
or wherein R4 is an alkyl radical having 1 to 18 carbon atoms or phenyl;
Z represents one or more electron-withdrawing groups selected from a cyano radical, a trihalomethyl radical, a carboxy radical, a carboxylic acid ester, a sulfo radical, an alkylsulfonyl radical, a sulfamoyl radical of the formula -SO2NR5R6 wherein R5 is hydrogen, alkyl or aryl and R6 can represent the same substituents as R5 or alkyl- or arylcarbonyl or alkyl- or arylsulfonyl and R5 and R6 together can represent 1-(dialkylamino)-alkylidene, a carbamoyl radical of the formula -CON(R5)2 (wherein each R5 can be the same or different and R5 is as described previously), or a halogen atom, as well as a radical of the formula:
wherein each member is as described above;
R1 represents a hydrogen atom, a halogen atom, an alkyl radical, an alkoxy radical or the carbon atoms necessary to form a fused benzo ring attached at the 2- and 3-position or at the 3- and 4-positions;
E which can be in the 3-, 5-, 6- or 7-position, represents a halogen atom, a carboxy radical, a carboxylic acid ester, a sulfo radical, a sulfamoyl radical or a carbamoyl radical, all as described for Z as well as a hydrogen atom, an alkoxy radical or an alkyl radical;
Z1 represents a hydrogen atom or any of the electron-withdrawing groups described for Z; and all the compounds herein are with the proviso that there can be only one sulfo or carboxy radical present.
I.
II.
or III.
wherein:
Ball represents an organic ballasting group of such size and configuration as to render said compound nondiffusible during development in an alkaline processing composition;
Y represents the carbon atoms necessary to complete a benzene or naphthalene nucleus;
X represents a bivalent linking group of the formula:
-R2-Lm-R2p- where each R2 can be the same or different and each represents an alkylene radical having 1 to 8 carbon atoms; or a phenylene radical;
L represents a bivalent radical selected from oxy, carbonyl, carboxamido, carbamoyl, sulfonamido, sulfamoyl, sulfinyl or sulfonyl; m is an integer having a value of 0 or 1; p is 1 when n equals 1 and p is 1 or 0 when n equals 0, provided that when p is 1 the carbon content of the sum of both R2 radicals does not exceed 14 carbon atoms;
R represents a hydrogen atom, an alkyl radical having 1 to 6 carbon atoms;
J represents a bivalent radical selected from sulfonyl or carbonyl;
m and q each represent an integer having a value of 0 or 1;
Q represents a hydrogen atom, a hydroxy radical or a radical having the formula -NHCOR3 or -NHSO2R3 wherein R3 is an alkyl radical having 1 to 6 carbon atoms, an alkyl radical having 1 to 4 carbon atoms substituted with hydroxy, cyano, sulfamoyl, carboxy or sulfo, benzyl, phenyl or phenyl substituted with carboxy, chloro, methyl, methoxy or sulfamoyl;
G represents a hydroxy radical, a salt thereof, or a hydrolyzable acyloxy group of the formula:
or wherein R4 is an alkyl radical having 1 to 18 carbon atoms or phenyl;
Z represents one or more electron-withdrawing groups selected from a cyano radical, a trihalomethyl radical, a carboxy radical, a carboxylic acid ester, a sulfo radical, an alkylsulfonyl radical, a sulfamoyl radical of the formula -SO2NR5R6 wherein R5 is hydrogen, alkyl or aryl and R6 can represent the same substituents as R5 or alkyl- or arylcarbonyl or alkyl- or arylsulfonyl and R5 and R6 together can represent 1-(dialkylamino)-alkylidene, a carbamoyl radical of the formula -CON(R5)2 (wherein each R5 can be the same or different and R5 is as described previously), or a halogen atom, as well as a radical of the formula:
wherein each member is as described above;
R1 represents a hydrogen atom, a halogen atom, an alkyl radical, an alkoxy radical or the carbon atoms necessary to form a fused benzo ring attached at the 2- and 3-position or at the 3- and 4-positions;
E which can be in the 3-, 5-, 6- or 7-position, represents a halogen atom, a carboxy radical, a carboxylic acid ester, a sulfo radical, a sulfamoyl radical or a carbamoyl radical, all as described for Z as well as a hydrogen atom, an alkoxy radical or an alkyl radical;
Z1 represents a hydrogen atom or any of the electron-withdrawing groups described for Z; and all the compounds herein are with the proviso that there can be only one sulfo or carboxy radical present.
2. A photosensitive element as described in claim 1 wherein n and p each have a value of 0.
3. A photosensitive element as described in claim 1 wherein m has a value of 0.
4. A photosensitive element as described in claim 1 wherein G is a hydroxy radical or salt thereof.
5. A photosensitive element as described in claim 1 wherein R1 represents a hydrogen atom, an alkoxy radical or a halogen atom.
6. A photosensitive element as described in claim 1 wherein E represents a hydrogen atom or an N,N-substituted sulfamoyl radical as described above.
7. A photosensitive element as described in claim 1 wherein Z represents a halogen atom, a cyano radical, a trihalomethyl radical, sulfamoyl radical or an alkylsulfonyl radical as described above.
8. A photosensitive element comprising a support having thereon a layer containing a red-sensitive silver halide emulsion having associated therewith a cyan image dye-providing material, a layer con-taining a green-sensitive silver halide emulsion having associated therewith a magenta image dye-providing material, and a layer containing a blue-sensitive silver halide emulsion having associated therewith a yellow image dye-providing material, said magenta image dye-providing material having a formula as follows:
I.
II.
or III.
wherein:
Ball represents an organic ballasting group of such size and configuration as to render said compound nondiffusible during development in an alkaline processing composition;
Y represents the carbon atoms necessary to complete a benzene or naphthalene nucleus;
X represents a bivalent linking group of the formula:
-R2-Lm-R2p- where each R2 can be the same or different and each repre-sents an alkylene radical having 1 to 8 carbon atoms; or a phenylene radical; L represents a bivalent radical selected from oxy, carbonyl, carboxamido, carbamoyl, sulfonamido, sulfamoyl, sulfinyl or sulfonyl; m is an integer having a value of 0 or 1; p is 1 when n equals 1 and p is 1 or 0 when n equals 0, provided that when p is 1 the carbon content of the sum of both R2 radicals does not exceed 14 carbon atoms;
R represents a hydrogen atom, an alkyl radical having 1 to 6 carbon atoms;
J represents a bivalent radical selected from sulfonyl or carbonyl;
m and q each represent an integer having a value of 0 or 1;
Q represents a hydrogen atom, a hydroxy radical or a radical having the formula -NHCOR3 or -NHSO2R3 wherein R3 is an alkyl radical having 1 to 6 carbon atoms, an alkyl radical having 1 to 4 carbon atoms substituted with hydroxy, cyano, sulfamoyl, carboxy or sulfo, benzyl, phenyl or phenyl substituted with carboxy, chloro, methyl, methoxy or sulfamoyl;
G represents a hydroxy radical, a salt thereof, or a hydrolyzable acyloxy group of the formula:
or wherein R4 is an alkyl radical having 1 to 18 carbon atoms or phenyl;
Z represents one or more electron-withdrawing groups selected from a cyano radical, a trihalomethyl radical, a carboxy radical, a carboxylic acid ester, a sulfo radical, an alkylsulfonyl radical, a sulfamoyl radical of the formula -SO2NR5R6 wherein R5 is hydrogen, alkyl or aryl and R6 can represent the same substituents as R5 or alkyl- or arylcarbonyl or alkyl- or arylsulfonyl and R5 and R6 together can repre-sent 1-(dialkylamino)-alkylidene, a carbamoyl radical of the formula -CON(R5)2 (wherein each R5 can be the same or different and R5 is as described previously), or a halogen atom, as well as a radical of the formula:
wherein each member is as described above;
R1 represents a hydrogen atom, a halogen atom, an alkyl radical, an alkoxy radical or the carbon atoms necessary to form a fused benzo ring attached at the 2- and 3-position or at the 3- and 4-positions;
E which can be in the 3-, 5-, 6- or 7-position, represents a halogen atom, a carboxy radical, a carboxylic acid ester, a sulfo radical, a sulfamoyl radical or a carbamoyl radical, all as described for Z as well as a hydrogen atom, an alkoxy radical or an alkyl radical;
and Z1 represents a hydrogen atom or any of the electron-withdrawing groups described for Z; and all the compounds herein are with the proviso that there can be only one sulfo or carboxy radical present.
I.
II.
or III.
wherein:
Ball represents an organic ballasting group of such size and configuration as to render said compound nondiffusible during development in an alkaline processing composition;
Y represents the carbon atoms necessary to complete a benzene or naphthalene nucleus;
X represents a bivalent linking group of the formula:
-R2-Lm-R2p- where each R2 can be the same or different and each repre-sents an alkylene radical having 1 to 8 carbon atoms; or a phenylene radical; L represents a bivalent radical selected from oxy, carbonyl, carboxamido, carbamoyl, sulfonamido, sulfamoyl, sulfinyl or sulfonyl; m is an integer having a value of 0 or 1; p is 1 when n equals 1 and p is 1 or 0 when n equals 0, provided that when p is 1 the carbon content of the sum of both R2 radicals does not exceed 14 carbon atoms;
R represents a hydrogen atom, an alkyl radical having 1 to 6 carbon atoms;
J represents a bivalent radical selected from sulfonyl or carbonyl;
m and q each represent an integer having a value of 0 or 1;
Q represents a hydrogen atom, a hydroxy radical or a radical having the formula -NHCOR3 or -NHSO2R3 wherein R3 is an alkyl radical having 1 to 6 carbon atoms, an alkyl radical having 1 to 4 carbon atoms substituted with hydroxy, cyano, sulfamoyl, carboxy or sulfo, benzyl, phenyl or phenyl substituted with carboxy, chloro, methyl, methoxy or sulfamoyl;
G represents a hydroxy radical, a salt thereof, or a hydrolyzable acyloxy group of the formula:
or wherein R4 is an alkyl radical having 1 to 18 carbon atoms or phenyl;
Z represents one or more electron-withdrawing groups selected from a cyano radical, a trihalomethyl radical, a carboxy radical, a carboxylic acid ester, a sulfo radical, an alkylsulfonyl radical, a sulfamoyl radical of the formula -SO2NR5R6 wherein R5 is hydrogen, alkyl or aryl and R6 can represent the same substituents as R5 or alkyl- or arylcarbonyl or alkyl- or arylsulfonyl and R5 and R6 together can repre-sent 1-(dialkylamino)-alkylidene, a carbamoyl radical of the formula -CON(R5)2 (wherein each R5 can be the same or different and R5 is as described previously), or a halogen atom, as well as a radical of the formula:
wherein each member is as described above;
R1 represents a hydrogen atom, a halogen atom, an alkyl radical, an alkoxy radical or the carbon atoms necessary to form a fused benzo ring attached at the 2- and 3-position or at the 3- and 4-positions;
E which can be in the 3-, 5-, 6- or 7-position, represents a halogen atom, a carboxy radical, a carboxylic acid ester, a sulfo radical, a sulfamoyl radical or a carbamoyl radical, all as described for Z as well as a hydrogen atom, an alkoxy radical or an alkyl radical;
and Z1 represents a hydrogen atom or any of the electron-withdrawing groups described for Z; and all the compounds herein are with the proviso that there can be only one sulfo or carboxy radical present.
9. A photosensitive element as described in claim 8 wherein each silver halide emulsion is a direct positive silver halide emulsion.
10. A photosensitive element as described in claim 8 wherein m has a value of 0; and G represents a hydroxy radical or salt thereof.
11. A photosensitive element as described in claim 10 wherein E represents a hydrogen atom or a sulfamoyl radical as above and Z
represents a halogen atom, a cyano radical, a trihalomethyl radical, an alkylsulfonyl radical, or a sulfamoyl radical as above.
represents a halogen atom, a cyano radical, a trihalomethyl radical, an alkylsulfonyl radical, or a sulfamoyl radical as above.
12. A photographic film unit which is adapted to be processed by passing said unit between a pair of juxtaposed pressure-applying members comprising:
a) a photosensitive element comprising a support having thereon a photosensitive silver halide emulsion layer having associated therewith an image dye-providing compound;
b) a dye image-receiving layer; and c) means for discharging an alkaline processing composition within said film unit;
said film unit containing a silver halide developing agent and said compound having a formula as follows:
I.
II.
or III.
wherein:
Ball represents an organic ballasting group of such size and configuration as to render said compound nondiffusible during development in an alkaline processing composition;
Y represents the carbon atoms necessary to complete a benzene or naphthalene nucleus;
X represents a bivalent linking group of the formula:
-R2-Lm-R2p- where each R2 can be the same or different and each repre-sents an alkylene radical having 1 to 8 carbon atoms; or a phenylene radical; L represents a bivalent radical selected from oxy, carbonyl, carboxamido, carbamoyl, sulfonamido, sulfamoyl, sulfinyl or sulfonyl; m is an integer having a value of 0 or 1; p is 1 when n equals 1 and p is 1 or 0 when n equals 0, provided that when p is 1 the carbon content of the sum of both R2 radicals does not exceed 14 carbon atoms;
R represents a hydrogen atom, an alkyl radical having 1 to 6 carbon atoms;
J represents a bivalent radical selected from sulfonyl or carbonyl;
m and q each represent an integer having a value of 0 or 1;
Q represents a hydrogen atom, a hydroxy radical or a radical having the formula -NHCOR3 or -NHSO2R3 wherein R3 is an alkyl radical having 1 to 6 carbon atoms, an alkyl radical having 1 to 4 carbon atoms substituted with hydroxy, cyano, sulfamoyl, carboxy or sulfo, benzyl, phenyl or phenyl substituted with carboxy, chloro, methyl, methoxy or sulfamoyl;
G represents a hydroxy radical, a salt thereof, or a hydrolyzable acyloxy group of the formula:
or wherein R4 is an alkyl radical having 1 to 18 carbon atoms or phenyl;
Z represents one or more electron-withdrawing groups selected from a cyano radical, a trihalomethyl radical, a carboxy radical, a carboxylic acid ester, a sulfo radical, an alkylsulfonyl radical, a sulfamoyl radical of the formula -SO2NR5R6 wherein R5 is hydrogen, alkyl or aryl and R6 can represent the same substituents as R5 or alkyl- or arylcarbonyl or alkyl- or arylsulfonyl and R5 and R6 together can repre-sent 1-(dialkylamino)-alkylidene, a carbamoyl radical of the formula -CON(R5)2 (wherein each R5 can be the same or different and R5 is as described previously), or a halogen atom, as well as a radical of the formula:
wherein each member is as described above;
R1 represents a hydrogen atom, a halogen atom, an alkyl radical, an alkoxy radical or the carbon atoms necessary to form a fused benzo ring attached at the 2- and 3-position or at the 3- and 4-positions;
E which can be in the 3-, 5-, 6- or 7-position, represents a halogen atom, a carboxy radical, a carboxylic acid ester, a sulfo radical, a sulfamoyl radical or a carbamoyl radical, all as described for Z as well as a hydrogen atom, an alkoxy radical or an alkyl radical;
Z1 represents a hydrogen atom or any of the electron-withdrawing groups described for Z; and all the compounds herein are with the proviso that there can be only one sulfo or carboxy radical present.
a) a photosensitive element comprising a support having thereon a photosensitive silver halide emulsion layer having associated therewith an image dye-providing compound;
b) a dye image-receiving layer; and c) means for discharging an alkaline processing composition within said film unit;
said film unit containing a silver halide developing agent and said compound having a formula as follows:
I.
II.
or III.
wherein:
Ball represents an organic ballasting group of such size and configuration as to render said compound nondiffusible during development in an alkaline processing composition;
Y represents the carbon atoms necessary to complete a benzene or naphthalene nucleus;
X represents a bivalent linking group of the formula:
-R2-Lm-R2p- where each R2 can be the same or different and each repre-sents an alkylene radical having 1 to 8 carbon atoms; or a phenylene radical; L represents a bivalent radical selected from oxy, carbonyl, carboxamido, carbamoyl, sulfonamido, sulfamoyl, sulfinyl or sulfonyl; m is an integer having a value of 0 or 1; p is 1 when n equals 1 and p is 1 or 0 when n equals 0, provided that when p is 1 the carbon content of the sum of both R2 radicals does not exceed 14 carbon atoms;
R represents a hydrogen atom, an alkyl radical having 1 to 6 carbon atoms;
J represents a bivalent radical selected from sulfonyl or carbonyl;
m and q each represent an integer having a value of 0 or 1;
Q represents a hydrogen atom, a hydroxy radical or a radical having the formula -NHCOR3 or -NHSO2R3 wherein R3 is an alkyl radical having 1 to 6 carbon atoms, an alkyl radical having 1 to 4 carbon atoms substituted with hydroxy, cyano, sulfamoyl, carboxy or sulfo, benzyl, phenyl or phenyl substituted with carboxy, chloro, methyl, methoxy or sulfamoyl;
G represents a hydroxy radical, a salt thereof, or a hydrolyzable acyloxy group of the formula:
or wherein R4 is an alkyl radical having 1 to 18 carbon atoms or phenyl;
Z represents one or more electron-withdrawing groups selected from a cyano radical, a trihalomethyl radical, a carboxy radical, a carboxylic acid ester, a sulfo radical, an alkylsulfonyl radical, a sulfamoyl radical of the formula -SO2NR5R6 wherein R5 is hydrogen, alkyl or aryl and R6 can represent the same substituents as R5 or alkyl- or arylcarbonyl or alkyl- or arylsulfonyl and R5 and R6 together can repre-sent 1-(dialkylamino)-alkylidene, a carbamoyl radical of the formula -CON(R5)2 (wherein each R5 can be the same or different and R5 is as described previously), or a halogen atom, as well as a radical of the formula:
wherein each member is as described above;
R1 represents a hydrogen atom, a halogen atom, an alkyl radical, an alkoxy radical or the carbon atoms necessary to form a fused benzo ring attached at the 2- and 3-position or at the 3- and 4-positions;
E which can be in the 3-, 5-, 6- or 7-position, represents a halogen atom, a carboxy radical, a carboxylic acid ester, a sulfo radical, a sulfamoyl radical or a carbamoyl radical, all as described for Z as well as a hydrogen atom, an alkoxy radical or an alkyl radical;
Z1 represents a hydrogen atom or any of the electron-withdrawing groups described for Z; and all the compounds herein are with the proviso that there can be only one sulfo or carboxy radical present.
13. The film unit of claim 12 wherein said dye image-receiving layer is located in said photosensitive element between said support and the lowermost photosensitive silver halide emulsion layer.
14. The film unit of claim 12 wherein said dye image-receiving layer is coated on a separate support and is adapted to be superposed on said photosensitive element after exposure thereof.
15. The film unit of claim 12 wherein said discharging means is a rupturable container and is so positioned during processing of said film unit that a compressive force applied to said container by said pressure-applying members will effect a discharge of the contents of said container between said image dye-receiving layer and the layer most remote from the support of said photosensitive element.
16. The film unit of claim 12 wherein said dye image-receiving layer comprises a polymeric cationic mordant.
17. The film unit of claim 12 wherein said dye image-receiving layer comprises a polymer having units represented by the following formula in copolymerized relationship with units of at least one other ethylenically unsaturated monomer:
wherein R7 and R8 each represent a hydrogen atom or a lower alkyl radical and R8 can additionally be a group containing at least one aromatic nucleus; Q can be a divalent alkylene radical, a divalent arylene radical, a divalent aralkylene radical, a divalent arylenealkylene radical, wherein R12 is an alkylene radical, or R8 can be taken together with Q to form a group, R9, R10 and R11 can be lower alkyl or aryl, or R9 and R10 and the nitrogen atom to which they are attached can together with Q represent the atoms and bonds necessary to form a quaternized nitrogen-containing heterocyclic ring, and X- is a mono-valent negative salt forming radical or atom in ionic relationship with the positive salt forming radical; wherein said polymer is substantially free of carboxy groups and wherein the positive salt forming radical of said polymer comprises at least two aryl groups for each quaternary nitrogen atom in said polymer.
wherein R7 and R8 each represent a hydrogen atom or a lower alkyl radical and R8 can additionally be a group containing at least one aromatic nucleus; Q can be a divalent alkylene radical, a divalent arylene radical, a divalent aralkylene radical, a divalent arylenealkylene radical, wherein R12 is an alkylene radical, or R8 can be taken together with Q to form a group, R9, R10 and R11 can be lower alkyl or aryl, or R9 and R10 and the nitrogen atom to which they are attached can together with Q represent the atoms and bonds necessary to form a quaternized nitrogen-containing heterocyclic ring, and X- is a mono-valent negative salt forming radical or atom in ionic relationship with the positive salt forming radical; wherein said polymer is substantially free of carboxy groups and wherein the positive salt forming radical of said polymer comprises at least two aryl groups for each quaternary nitrogen atom in said polymer.
18. A photosensitive element comprising a support having thereon at least one photosensitive silver halide emulsion layer and one of said layers having associated therewith a nondiffusible magenta image dye-providing compound, said compound having a formula as follows:
wherein:
Ball represents an organic ballasting group of such size and configuration as to render said compound nondiffusible during development in an alkaline processing composition;
Y represents the carbon atoms necessary to complete a benzene or naphthalene nucleus;
X represents a bivalent linking group of the formula:
-R2-Lm-R2p- where each R2 can be the same or different and each repre-sents an alkylene radical having 1 to 8 carbon atoms; or a phenylene radical; L represents a bivalent radical selected from oxy, carbonyl, carboxamido, carbamoyl, sulfonamido, sulfamoyl, sulfinyl or sulfonyl; m is an integer having a value of 0 or 1; p is 1 when n equals 1 and p is 1 or 0 when n equals 0, provided that when p is 1 the carbon content of the sum of both R2 radicals does not exceed 14 carbon atoms;
R represents a hydrogen atom, an alkyl radical having 1 to 6 carbon atoms;
J represents a bivalent radical selected from sulfonyl or carbonyl;
m and q each represent an integer having a value of O or l;
Q represents a hydrogen atom, a hydroxy radical or a radical having the formula -NHCOR3 or wherein R3 is an alkyl radical having 1 to 6 carbon atoms, an alkyl radical having 1 to 4 carbon atoms substituted with hydroxy, cyano, sulfamoyl, carboxy or sulfo, benzyl, phenyl or phenyl substituted with carboxy, chloro, methyl, methoxy or sulfamoyl;
G represents a hydroxy radical, a salt thereof, or a hydrolyzable acyloxy group of the formula:
or wherein R4 is an alkyl radical having 1 to 18 carbon atoms or phenyl;
Z represents one or more electron-withdrawing groups selected from a cyano radical, a trihalomethyl radical, a carboxy radical, a carboxylic acid ester, a sulfo radical, an alkylsulfonyl radical, a sulfamoyl radical of the formula -SO2NR5R6 wherein R5 is hydrogen, alkyl or aryl and R6 can represent the same substituents as R5 or alkyl- or arylcarbonyl or alkyl- or arylsulfonyl and R5 and R6 together can repre-sent 1-(dialkylamino)-alkylidene, a carbamoyl radical of the formula -CON(R5)2 (wherein each R5 can be the same or different and R5 is as described previously), or a halogen atom, as well as a radical of the formula:
wherein each member is as described above;
R1 represents a hydrogen atom, a halogen atom, an alkyl radical, an alkoxy radical or the carbon atoms necessary to form a fused benzo ring attached at the 2- and 3-position or at the 3- and 4-positions; and all the compounds herein are with the proviso that there can be only one sulfo or carboxy radical present.
wherein:
Ball represents an organic ballasting group of such size and configuration as to render said compound nondiffusible during development in an alkaline processing composition;
Y represents the carbon atoms necessary to complete a benzene or naphthalene nucleus;
X represents a bivalent linking group of the formula:
-R2-Lm-R2p- where each R2 can be the same or different and each repre-sents an alkylene radical having 1 to 8 carbon atoms; or a phenylene radical; L represents a bivalent radical selected from oxy, carbonyl, carboxamido, carbamoyl, sulfonamido, sulfamoyl, sulfinyl or sulfonyl; m is an integer having a value of 0 or 1; p is 1 when n equals 1 and p is 1 or 0 when n equals 0, provided that when p is 1 the carbon content of the sum of both R2 radicals does not exceed 14 carbon atoms;
R represents a hydrogen atom, an alkyl radical having 1 to 6 carbon atoms;
J represents a bivalent radical selected from sulfonyl or carbonyl;
m and q each represent an integer having a value of O or l;
Q represents a hydrogen atom, a hydroxy radical or a radical having the formula -NHCOR3 or wherein R3 is an alkyl radical having 1 to 6 carbon atoms, an alkyl radical having 1 to 4 carbon atoms substituted with hydroxy, cyano, sulfamoyl, carboxy or sulfo, benzyl, phenyl or phenyl substituted with carboxy, chloro, methyl, methoxy or sulfamoyl;
G represents a hydroxy radical, a salt thereof, or a hydrolyzable acyloxy group of the formula:
or wherein R4 is an alkyl radical having 1 to 18 carbon atoms or phenyl;
Z represents one or more electron-withdrawing groups selected from a cyano radical, a trihalomethyl radical, a carboxy radical, a carboxylic acid ester, a sulfo radical, an alkylsulfonyl radical, a sulfamoyl radical of the formula -SO2NR5R6 wherein R5 is hydrogen, alkyl or aryl and R6 can represent the same substituents as R5 or alkyl- or arylcarbonyl or alkyl- or arylsulfonyl and R5 and R6 together can repre-sent 1-(dialkylamino)-alkylidene, a carbamoyl radical of the formula -CON(R5)2 (wherein each R5 can be the same or different and R5 is as described previously), or a halogen atom, as well as a radical of the formula:
wherein each member is as described above;
R1 represents a hydrogen atom, a halogen atom, an alkyl radical, an alkoxy radical or the carbon atoms necessary to form a fused benzo ring attached at the 2- and 3-position or at the 3- and 4-positions; and all the compounds herein are with the proviso that there can be only one sulfo or carboxy radical present.
19. A photosensitive element as described in claim 18 wherein G is a hydroxy radical or salt thereof.
20. A photosensitive element comprising a support having thereon at least one photosensitive silver halide emulsion layer and one of said layers having associated therewith a nondiffusible magenta image dye-providing compound, said compound having a formula as follows:
wherein:
Ball represents an organic ballasting group of such size and configuration as to render said compound nondiffusible during development in an alkaline processing composition;
Y represents the carbon atoms necessary to complete a benzene or naphthalene nucleus;
X represents a bivalent linking group of the formula:
-R2-Lm-R2p - where each R2 can be the same or different and each repre-sents an alkylene radical having 1 to 8 carbon atoms; or a phenylene radical; L represents a bivalent radical selected from oxy, carbonyl, carboxamido, carbamoyl, sulfonamido, sulfamoyl, sulfinyl or sulfonyl; m is an integer having a value of 0 or 1; p is 1 when n equals 1 and p is 1 or Q when n equals 0, provided that when p is 1 the carbon content of the sum of both R2 radicals does not exceed 14 carbon atoms;
R represents a hydrogen atom, an alkyl radical having 1 to 6 carbon atoms;
J represents a bivalent radical selected from sulfonyl or carbonyl;
G represents a hydroxy radical, a salt thereof, or a hydrolyzable acyloxy group of the formula:
or wherein R4 is an alkyl radical having 1 to 18 carbon atoms or phenyl;
Z represents one or more electron-withdrawing groups selected from a cyano radical, a trihalomethyl radical, a carboxy radical, a carboxylic acid ester, a sulfo radical, an alkylsulfonyl radical, a sulfamoyl radical of the formula -SO2NR5R6 wherein R5 is hydrogen, alkyl or aryl and R6 can represent the same substituents as R5 or alkyl- or arylcarbonyl or alkyl- or arylsulfonyl and R5 and R6 together can repre-sent 1-(dialkylamino)-alkylidene, a carbamoyl radical of the formula -CON(R5)2 (wherein each R5 can be the same or different and R5 is as described previously), or a halogen atom, as well as a radical of the formula:
wherein each member is as described above;
R1 represents a hydrogen atom, a halogen atom, an alkyl radical, an alkoxy radical or the carbon atoms necessary to form a fused benzo ring attached at the 2- and 3-position or at the 3- and 4-positions;
E which can be in the 3-, 5-, 6- or 7-position, represents a halogen atom, a carboxy radical, a carboxylic acid ester, a sulfo radical, a sulfamoyl radical or a carbamoyl radical, all as described for Z as well as a hydrogen atom, an alkoxy radical or an alkyl radical;
and all the compounds herein are with the proviso that there can be only one sulfo or carboxy radical present.
wherein:
Ball represents an organic ballasting group of such size and configuration as to render said compound nondiffusible during development in an alkaline processing composition;
Y represents the carbon atoms necessary to complete a benzene or naphthalene nucleus;
X represents a bivalent linking group of the formula:
-R2-Lm-R2p - where each R2 can be the same or different and each repre-sents an alkylene radical having 1 to 8 carbon atoms; or a phenylene radical; L represents a bivalent radical selected from oxy, carbonyl, carboxamido, carbamoyl, sulfonamido, sulfamoyl, sulfinyl or sulfonyl; m is an integer having a value of 0 or 1; p is 1 when n equals 1 and p is 1 or Q when n equals 0, provided that when p is 1 the carbon content of the sum of both R2 radicals does not exceed 14 carbon atoms;
R represents a hydrogen atom, an alkyl radical having 1 to 6 carbon atoms;
J represents a bivalent radical selected from sulfonyl or carbonyl;
G represents a hydroxy radical, a salt thereof, or a hydrolyzable acyloxy group of the formula:
or wherein R4 is an alkyl radical having 1 to 18 carbon atoms or phenyl;
Z represents one or more electron-withdrawing groups selected from a cyano radical, a trihalomethyl radical, a carboxy radical, a carboxylic acid ester, a sulfo radical, an alkylsulfonyl radical, a sulfamoyl radical of the formula -SO2NR5R6 wherein R5 is hydrogen, alkyl or aryl and R6 can represent the same substituents as R5 or alkyl- or arylcarbonyl or alkyl- or arylsulfonyl and R5 and R6 together can repre-sent 1-(dialkylamino)-alkylidene, a carbamoyl radical of the formula -CON(R5)2 (wherein each R5 can be the same or different and R5 is as described previously), or a halogen atom, as well as a radical of the formula:
wherein each member is as described above;
R1 represents a hydrogen atom, a halogen atom, an alkyl radical, an alkoxy radical or the carbon atoms necessary to form a fused benzo ring attached at the 2- and 3-position or at the 3- and 4-positions;
E which can be in the 3-, 5-, 6- or 7-position, represents a halogen atom, a carboxy radical, a carboxylic acid ester, a sulfo radical, a sulfamoyl radical or a carbamoyl radical, all as described for Z as well as a hydrogen atom, an alkoxy radical or an alkyl radical;
and all the compounds herein are with the proviso that there can be only one sulfo or carboxy radical present.
21. A photosensitive element as described in claim 20 wherein G is a hydroxy radical or salt thereof.
22. A photosensitive element comprising a support having thereon at least one photosensitive silver halide emulsion layer and one of said layers having associated therewith a nondiffusible magenta image dye-providing compound, said compound having a formula as follows:
wherein:
Ball represents an organic ballasting group of such size and configuration as to render said compound nondiffusible during development in an alkaline processing composition;
Y represents the carbon atoms necessary to complete a benzene or naphthalene nucleus;
X represents a bivalent linking group of the formula:
-R2-Lm-R2p- where each R2 can be the same or different and each repre-sents an alkylene radical having 1 to 8 carbon atoms; or a phenylene radical; L represents a bivalent radical selected from oxy, carbonyl, carboxamido, carbamoyl, sulfonamido, sulfamoyl, sulfinyl or sulfonyl; m is an integer having a value of 0 or 1; p is 1 when n equals 1 and p is 1 or 0 when n equals 0, provided that when p is 1 the carbon content of the sum of both R2 radicals does not exceed 14 carbon atoms, R represents a hydrogen atom, an alkyl radical having 1 to 6 carbon atoms;
J represents a bivalent radical selected from sulfonyl or carbonyl;
m and q each represent an integer having a value of 0 or 1;
Q represents a hydrogen atom, a hydroxy radical or a radical having the formula -NHCOR3 or -NHSO2R3 wherein R3 is an alkyl radical having 1 to 6 carbon atoms, an alkyl radical having 1 to 4 carbon atoms substituted with hydroxy, cyano, sulfamoyl, carboxy or sulfo, benzyl, phenyl or phenyl substituted with carboxy, chloro, methyl, methoxy or sulfamoyl;
G represents a hydroxy radical, a salt thereof, or a hydrolyzable acyloxy group of the formula:
or wherein R4 is an alkyl radical having 1 to 18 carbon atoms or phenyl;
Z1 represents one or more electron-withdrawing groups selected from a cyano radical, a trihalomethyl radical, a carboxy radical, a carboxylic acid ester, a sulfo radical, an alkylsulfonyl radical, a sulfamoyl radical of the formula -SO2NR5R6 wherein R5 is hydrogen, alkyl or aryl and R6 can represent the same substituents as R5 or alkyl- or arylcarbonyl or alkyl- or arylsulfonyl and R5 and R6 together can represent 1-(dialkylamino)-alkylidene, a carbamoyl radical of the formula -CON(R5)2 (wherein each R5 can be the same or different and R5 is as described previously), or a halogen atom, as well as a radical of the formula:
wherein each member is as described above;
R1 represents a hydrogen atom, a halogen atom, an alkyl radical, an alkoxy radical or the carbon atoms necessary to form a fused benzo ring attached at the 2- and 3-position or at the 3- and 4-positions;
E which can be in the 3-, 5-, 6- or 7-position, represents a halogen atom, a carboxy radical, a carboxylic acid ester, a sulfo radical, a sulfamoyl radical or a carbamoyl radical, all as described for Z as well as a hydrogen atom, an alkoxy radical or an alkyl radical;
and all the compounds herein are with the proviso that there can be only one sulfo or carboxy radical present.
wherein:
Ball represents an organic ballasting group of such size and configuration as to render said compound nondiffusible during development in an alkaline processing composition;
Y represents the carbon atoms necessary to complete a benzene or naphthalene nucleus;
X represents a bivalent linking group of the formula:
-R2-Lm-R2p- where each R2 can be the same or different and each repre-sents an alkylene radical having 1 to 8 carbon atoms; or a phenylene radical; L represents a bivalent radical selected from oxy, carbonyl, carboxamido, carbamoyl, sulfonamido, sulfamoyl, sulfinyl or sulfonyl; m is an integer having a value of 0 or 1; p is 1 when n equals 1 and p is 1 or 0 when n equals 0, provided that when p is 1 the carbon content of the sum of both R2 radicals does not exceed 14 carbon atoms, R represents a hydrogen atom, an alkyl radical having 1 to 6 carbon atoms;
J represents a bivalent radical selected from sulfonyl or carbonyl;
m and q each represent an integer having a value of 0 or 1;
Q represents a hydrogen atom, a hydroxy radical or a radical having the formula -NHCOR3 or -NHSO2R3 wherein R3 is an alkyl radical having 1 to 6 carbon atoms, an alkyl radical having 1 to 4 carbon atoms substituted with hydroxy, cyano, sulfamoyl, carboxy or sulfo, benzyl, phenyl or phenyl substituted with carboxy, chloro, methyl, methoxy or sulfamoyl;
G represents a hydroxy radical, a salt thereof, or a hydrolyzable acyloxy group of the formula:
or wherein R4 is an alkyl radical having 1 to 18 carbon atoms or phenyl;
Z1 represents one or more electron-withdrawing groups selected from a cyano radical, a trihalomethyl radical, a carboxy radical, a carboxylic acid ester, a sulfo radical, an alkylsulfonyl radical, a sulfamoyl radical of the formula -SO2NR5R6 wherein R5 is hydrogen, alkyl or aryl and R6 can represent the same substituents as R5 or alkyl- or arylcarbonyl or alkyl- or arylsulfonyl and R5 and R6 together can represent 1-(dialkylamino)-alkylidene, a carbamoyl radical of the formula -CON(R5)2 (wherein each R5 can be the same or different and R5 is as described previously), or a halogen atom, as well as a radical of the formula:
wherein each member is as described above;
R1 represents a hydrogen atom, a halogen atom, an alkyl radical, an alkoxy radical or the carbon atoms necessary to form a fused benzo ring attached at the 2- and 3-position or at the 3- and 4-positions;
E which can be in the 3-, 5-, 6- or 7-position, represents a halogen atom, a carboxy radical, a carboxylic acid ester, a sulfo radical, a sulfamoyl radical or a carbamoyl radical, all as described for Z as well as a hydrogen atom, an alkoxy radical or an alkyl radical;
and all the compounds herein are with the proviso that there can be only one sulfo or carboxy radical present.
23. A photosensitive element as described in claim 22 wherein G is a hydroxy radical or salt thereof.
24. An image dye-providing compound having the formula I.
II. or III. wherein:
Ball represents an organic ballasting group of such size and configuration as to render said compound nondiffusible during develop-ment in an alkaline processing composition;
Y represents the carbon atoms necessary to complete a benzene or naphthalene nucleus;
X represents a bivalent linking group of the formula:
-R2-Lm-R2p- where each R2 can be the same or different and each repre-sents an alkylene radical having 1 to 8 carbon atoms; or a phenylene radical; L represents a bivalent radical selected from oxy, carbonyl, carboxamido, carbamoyl, sulfonamido, sulfamoyl, sulfinyl or sulfonyl; m is an integer having a value of 0 or 1; p is 1 when n equals 1 and p is 1 or 0 when n equals 0, provided that when p is 1 the carbon content of the sum of both R2 radicals does not exceed 14 carbon atoms;
R represents a hydrogen atom, an alkyl radical having 1 to 6 carbon atoms;
J represents a bivalent radical selected from sulfonyl or carbonyl;
m and q each represent an integer having a value of 0 or 1;
Q represents a hydrogen atom, a hydroxy radical or a radical having the formula -NHCOR3 or -NHSO2R3 wherein R3 is an alkyl radical having 1 to 6 carbon atoms, an alkyl radical having 1 to 4 carbon atoms substituted with hydroxy, cyano, sulfamoyl, carboxy or sulfo, benzyl, phenyl or phenyl substituted with carboxy, chloro, methyl, methoxy or sulfamoyl;
G represents a hydroxy radical, a salt thereof, or a hydrolyz-able acyloxy group of the formula:
or wherein R4 is an alkyl radical having 1 to 18 carbon atoms or phenyl;
Z represents one or more electron-withdrawing groups selected from a cyano radical, a trihalomethyl radical, a carboxy radical, a carboxylic acid ester, a sulfo radical, an alkylsulfonyl radical, a sulfamoyl radical of the formula -SO2NR5R6 wherein R5 is hydrogen, alkyl or aryl and R6 can represent the same substituents as R5 or alkyl- or arylcarbonyl or alkyl- or arylsulfonyl and R5 and R6 together can represent 1-(dialkylamino)-alkylidene, a carbamoyl radical of the formula -CON(R5)2 (wherein each R5 can be the same or different and R5 is as described previously), or a halogen atom, as well as a radical of the formula:
wherein each member is as described above;
R1 represents a hydrogen atom, a halogen atom, an alkyl radical, an alkoxy radical or the carbon atoms necessary to form a fused benzo ring attached at the 2- and 3-position or at the 3- and 4-positions;
E which can be in the 3-, 5-, 6- or 7-position, represents a halogen atom, a carboxy radical, a carboxylic acid ester, a sulfo radical, a sulfamoyl radical or a carbamoyl radical, all as described for Z as well as a hydrogen atom, an alkoxy radical or an alkyl radical;
Z1 represents a hydrogen atom or any of the electron-withdrawing groups described for Z; and all the compounds herein are with the proviso that there can be only one sulfo or carboxy radical present.
II. or III. wherein:
Ball represents an organic ballasting group of such size and configuration as to render said compound nondiffusible during develop-ment in an alkaline processing composition;
Y represents the carbon atoms necessary to complete a benzene or naphthalene nucleus;
X represents a bivalent linking group of the formula:
-R2-Lm-R2p- where each R2 can be the same or different and each repre-sents an alkylene radical having 1 to 8 carbon atoms; or a phenylene radical; L represents a bivalent radical selected from oxy, carbonyl, carboxamido, carbamoyl, sulfonamido, sulfamoyl, sulfinyl or sulfonyl; m is an integer having a value of 0 or 1; p is 1 when n equals 1 and p is 1 or 0 when n equals 0, provided that when p is 1 the carbon content of the sum of both R2 radicals does not exceed 14 carbon atoms;
R represents a hydrogen atom, an alkyl radical having 1 to 6 carbon atoms;
J represents a bivalent radical selected from sulfonyl or carbonyl;
m and q each represent an integer having a value of 0 or 1;
Q represents a hydrogen atom, a hydroxy radical or a radical having the formula -NHCOR3 or -NHSO2R3 wherein R3 is an alkyl radical having 1 to 6 carbon atoms, an alkyl radical having 1 to 4 carbon atoms substituted with hydroxy, cyano, sulfamoyl, carboxy or sulfo, benzyl, phenyl or phenyl substituted with carboxy, chloro, methyl, methoxy or sulfamoyl;
G represents a hydroxy radical, a salt thereof, or a hydrolyz-able acyloxy group of the formula:
or wherein R4 is an alkyl radical having 1 to 18 carbon atoms or phenyl;
Z represents one or more electron-withdrawing groups selected from a cyano radical, a trihalomethyl radical, a carboxy radical, a carboxylic acid ester, a sulfo radical, an alkylsulfonyl radical, a sulfamoyl radical of the formula -SO2NR5R6 wherein R5 is hydrogen, alkyl or aryl and R6 can represent the same substituents as R5 or alkyl- or arylcarbonyl or alkyl- or arylsulfonyl and R5 and R6 together can represent 1-(dialkylamino)-alkylidene, a carbamoyl radical of the formula -CON(R5)2 (wherein each R5 can be the same or different and R5 is as described previously), or a halogen atom, as well as a radical of the formula:
wherein each member is as described above;
R1 represents a hydrogen atom, a halogen atom, an alkyl radical, an alkoxy radical or the carbon atoms necessary to form a fused benzo ring attached at the 2- and 3-position or at the 3- and 4-positions;
E which can be in the 3-, 5-, 6- or 7-position, represents a halogen atom, a carboxy radical, a carboxylic acid ester, a sulfo radical, a sulfamoyl radical or a carbamoyl radical, all as described for Z as well as a hydrogen atom, an alkoxy radical or an alkyl radical;
Z1 represents a hydrogen atom or any of the electron-withdrawing groups described for Z; and all the compounds herein are with the proviso that there can be only one sulfo or carboxy radical present.
25. A compound as described in claim 24 wherein n and p each have a value of 0.
26. A compound as described in claim 24 wherein m has a value of 0.
27. A compound as described in claim 24 wherein G is a hydroxy radical or salt thereof.
28. A compound as described in claim 24 wherein R1 represents a hydrogen atom, an alkoxy radical or a halogen atom.
29. A compound as described in claim 24 wherein E represents a hydrogen atom or an N,N-substituted sulfamoyl radical as described above.
30. A compound as described in claim 24 wherein Z represents a halogen atom, a cyano radical, a trihalomethyl radical, a sulfamoyl radical or an alkylsulfonyl radical as described above.
31. An image dye-providing compound having the formula:
wherein:
Ball represents an organic ballasting group of such size and configuration as to render said compound nondiffusible during develop-ment in an alkaline processing composition;
Y represents the carbon atoms necessary to complete a benzene or naphthalene nucleus;
X represents a bivalent linking group of the formula:
-R2-Lm-R2p- where each R2 can be the same or different and each repre-sents an alkylene radical having 1 to 8 carbon atoms; or a phenylene radical; L represents a bivalent radical selected from oxy, carbonyl, carboxamido, carbamoyl, sulfonamido, sulfamoyl, sulfinyl or sulfonyl; m is an integer having a value of 0 or 1; p is 1 when n equals 1 and p is 1 or 0 when n equals 0, provided that when p is 1 the carbon content of the sum of both R2 radicals does not exceed 14 carbon atoms;
R represents a hydrogen atom, an alkyl radical having 1 to 6 carbon atoms;
J represents a bivalent radical selected from sulfonyl or carbonyl;
m and q each represent an integer having a value of 0 or 1;
Q represents a hydrogen atom, a hydroxy radical or a radical having the formula -NHCOR3 or -NHSO2R3 wherein R3 is an alkyl radical having 1 to 6 carbon atoms, an alkyl radical having 1 to 4 carbon atoms substituted with hydroxy, cyano, sulfamoyl, carboxy or sulfo, benzyl, phenyl or phenyl substituted with carboxy, chloro, methyl, methoxy or sulfamoyl;
G represents a hydroxy radical, a salt thereof, or a hydrolyzable acyloxy group of the formula:
or wherein R4 is an alkyl radical having 1 to 18 carbon atoms or phenyl;
Z represents one or more electron-withdrawing groups selected from a cyano radical, a trihalomethyl radical, a carboxy radical, a carboxylic acid ester, a sulfo radical, an alkylsulfonyl radical, a sulfamoyl radical of the formula -SO2NR5R6 wherein R5 is hydrogen, alkyl or aryl and R6 can represent the same substituents as R5 or alkyl- or arylcarbonyl or alkyl- or arylsulfonyl and R5 and R6 together can represent 1-(dialkylamino)-alkylidene, a carbamoyl radical of the formula -CON(R5)2 (wherein each R5 can be the same or different and R5 is as described previously), or a halogen atom, as well as a radical of the formula:
wherein each member is as described above;
R1 represents a hydrogen atom, a halogen atom, an alkyl radical, an alkoxy radical or the carbon atoms necessary to form a fused benzo ring attached at the 2- and 3-position or at the 3- and 4-positions; and all the compounds herein are with the proviso that there can be only one sulfo or carboxy radical present.
wherein:
Ball represents an organic ballasting group of such size and configuration as to render said compound nondiffusible during develop-ment in an alkaline processing composition;
Y represents the carbon atoms necessary to complete a benzene or naphthalene nucleus;
X represents a bivalent linking group of the formula:
-R2-Lm-R2p- where each R2 can be the same or different and each repre-sents an alkylene radical having 1 to 8 carbon atoms; or a phenylene radical; L represents a bivalent radical selected from oxy, carbonyl, carboxamido, carbamoyl, sulfonamido, sulfamoyl, sulfinyl or sulfonyl; m is an integer having a value of 0 or 1; p is 1 when n equals 1 and p is 1 or 0 when n equals 0, provided that when p is 1 the carbon content of the sum of both R2 radicals does not exceed 14 carbon atoms;
R represents a hydrogen atom, an alkyl radical having 1 to 6 carbon atoms;
J represents a bivalent radical selected from sulfonyl or carbonyl;
m and q each represent an integer having a value of 0 or 1;
Q represents a hydrogen atom, a hydroxy radical or a radical having the formula -NHCOR3 or -NHSO2R3 wherein R3 is an alkyl radical having 1 to 6 carbon atoms, an alkyl radical having 1 to 4 carbon atoms substituted with hydroxy, cyano, sulfamoyl, carboxy or sulfo, benzyl, phenyl or phenyl substituted with carboxy, chloro, methyl, methoxy or sulfamoyl;
G represents a hydroxy radical, a salt thereof, or a hydrolyzable acyloxy group of the formula:
or wherein R4 is an alkyl radical having 1 to 18 carbon atoms or phenyl;
Z represents one or more electron-withdrawing groups selected from a cyano radical, a trihalomethyl radical, a carboxy radical, a carboxylic acid ester, a sulfo radical, an alkylsulfonyl radical, a sulfamoyl radical of the formula -SO2NR5R6 wherein R5 is hydrogen, alkyl or aryl and R6 can represent the same substituents as R5 or alkyl- or arylcarbonyl or alkyl- or arylsulfonyl and R5 and R6 together can represent 1-(dialkylamino)-alkylidene, a carbamoyl radical of the formula -CON(R5)2 (wherein each R5 can be the same or different and R5 is as described previously), or a halogen atom, as well as a radical of the formula:
wherein each member is as described above;
R1 represents a hydrogen atom, a halogen atom, an alkyl radical, an alkoxy radical or the carbon atoms necessary to form a fused benzo ring attached at the 2- and 3-position or at the 3- and 4-positions; and all the compounds herein are with the proviso that there can be only one sulfo or carboxy radical present.
32. The compound as described in claim 31 wherein Y repre-sents the atoms necessary to complete a naphthalene nucleus and G
represents a hydroxy radical or salt thereof.
represents a hydroxy radical or salt thereof.
33. An image dye-providing compound having the formula:
wherein:
Ball represents an organic ballasting group of such size and configuration as to render said compound nondiffusible during develop-ment in an alkaline processing composition;
Y represents the carbon atoms necessary to complete a benzene or naphthalene nucleus;
X represents a bivalent linking group of the formula:
-R2-Lm-R2p- where each R2 can be the same or different and each represents an alkylene radical having 1 to 8 carbon atoms; or a phenylene radical; L represents a bivalent radical selected from oxy, carbonyl, carboxamido, carbamoyl, sulfonamido, sulfamoyl, sulfinyl or sulfonyl; m is an integer having a value of 0 or 1; p is 1 when n equals 1 and p is 1 or 0 when n equals 0, provided that when p is 1 the carbon content of the sum of both R2 radicals does not exceed 14 carbon atoms;
R represents a hydrogen atom, an alkyl radical having 1 to 6 carbon atoms;
J represents a bivalent radical selected from sulfonyl or carbonyl;
G represents a hydroxy radical, a salt thereof, or a hydrolyzable acyloxy group of the formula:
or wherein R4 is an alkyl radical having 1 to 18 carbon atoms or phenyl;
Z represents one or more electron-withdrawing groups selected from a cyano radical, a trihalomethyl radical, a carboxy radical, a carboxylic acid ester, a sulfo radical, an alkylsulfonyl radical, a sulfamoyl radical of the formula -SO2NR5R6 wherein R5 is hydrogen, alkyl or aryl and R6 can represent the same substituents as R5 or alkyl- or arylcarbonyl or alkyl- or arylsulfonyl and R5 and R6 together can represent 1-(dialkylamino)-alkylidene, a carbamoyl radical of the formula -CON(R5)2 (wherein each R5 can be the same or different and R5 is as described previously), or a halogen atom, as well as a radical of the formula:
wherein each member is as described above;
R1 represents a hydrogen atom, a halogen atom, an alkyl radical, an alkoxy radical or the carbon atoms necessary to form a fused benzo ring attached at the 2- and 3-position or at the 3- and 4-positions;
E which can be in the 3-, 5-, 6- or 7-position, represents a halogen atom, a carboxy radical, a carboxylic acid ester, a sulfo radical, a sulfamoyl radical or a carbamoyl radical, all as described for Z as well as a hydrogen atom, an alkoxy radical or an alkyl radical;
and all the compounds herein are with the proviso that there can be only one sulfo or carboxy radical present.
wherein:
Ball represents an organic ballasting group of such size and configuration as to render said compound nondiffusible during develop-ment in an alkaline processing composition;
Y represents the carbon atoms necessary to complete a benzene or naphthalene nucleus;
X represents a bivalent linking group of the formula:
-R2-Lm-R2p- where each R2 can be the same or different and each represents an alkylene radical having 1 to 8 carbon atoms; or a phenylene radical; L represents a bivalent radical selected from oxy, carbonyl, carboxamido, carbamoyl, sulfonamido, sulfamoyl, sulfinyl or sulfonyl; m is an integer having a value of 0 or 1; p is 1 when n equals 1 and p is 1 or 0 when n equals 0, provided that when p is 1 the carbon content of the sum of both R2 radicals does not exceed 14 carbon atoms;
R represents a hydrogen atom, an alkyl radical having 1 to 6 carbon atoms;
J represents a bivalent radical selected from sulfonyl or carbonyl;
G represents a hydroxy radical, a salt thereof, or a hydrolyzable acyloxy group of the formula:
or wherein R4 is an alkyl radical having 1 to 18 carbon atoms or phenyl;
Z represents one or more electron-withdrawing groups selected from a cyano radical, a trihalomethyl radical, a carboxy radical, a carboxylic acid ester, a sulfo radical, an alkylsulfonyl radical, a sulfamoyl radical of the formula -SO2NR5R6 wherein R5 is hydrogen, alkyl or aryl and R6 can represent the same substituents as R5 or alkyl- or arylcarbonyl or alkyl- or arylsulfonyl and R5 and R6 together can represent 1-(dialkylamino)-alkylidene, a carbamoyl radical of the formula -CON(R5)2 (wherein each R5 can be the same or different and R5 is as described previously), or a halogen atom, as well as a radical of the formula:
wherein each member is as described above;
R1 represents a hydrogen atom, a halogen atom, an alkyl radical, an alkoxy radical or the carbon atoms necessary to form a fused benzo ring attached at the 2- and 3-position or at the 3- and 4-positions;
E which can be in the 3-, 5-, 6- or 7-position, represents a halogen atom, a carboxy radical, a carboxylic acid ester, a sulfo radical, a sulfamoyl radical or a carbamoyl radical, all as described for Z as well as a hydrogen atom, an alkoxy radical or an alkyl radical;
and all the compounds herein are with the proviso that there can be only one sulfo or carboxy radical present.
34. The compound as described in claim 33 wherein Y repre-sents the atoms necessary to complete a naphthalene nucleus and G
represents a hydroxy radical or salt thereof.
represents a hydroxy radical or salt thereof.
35. An image dye-providing compound having the formula:
wherein:
Ball represents an organic ballasting group of such size and configuration as to render said compound nondiffusible during develop-ment in an alkaline processing composition;
Y represents the carbon atoms necessary to complete a benzene or naphthalene nucleus;
X represents a bivalent linking group of the formula:
-R2-Lm-R2p- where each R2 can be the same or different and each repre-sents an alkylene radical having 1 to 8 carbon atoms; or a phenylene radical; L represents a bivalent radical selected from oxy, carbonyl, carboxamido, carbamoyl, sulfonamido, sulfamoyl, sulfinyl or sulfonyl; m is an integer having a value of 0 or 1; p is 1 when n equals 1 and p is 1 or 0 when n equals 0, provided that when p is 1 the carbon content of the sum of both R2 radicals does not exceed 14 carbon atoms;
R represents a hydrogen atom, an alkyl radical having 1 to 6 carbon atoms;
J represents a bivalent radical selected from sulfonyl or carbonyl;
m and q each represent an integer having a value of 0 or 1;
Q represents a hydrogen atom, a hydroxy radical or a radical having the formula -NHCOR3 or -NHSO2R3 wherein R3 is an alkyl radical having 1 to 6 carbon atoms, an alkyl radical having 1 to 4 carbon atoms substituted with hydroxy, cyano, sulfamoyl, carboxy or sulfo, benzyl, phenyl or phenyl substituted with carboxy, chloro, methyl, methoxy or sulfamoyl;
G represents a hydroxy radical, a salt thereof, or a hydrolyzable acyloxy group of the formula:
or wherein R4 is an alkyl radical having 1 to 18 carbon atoms or phenyl;
Z1 represents one or more electron-withdrawing groups selected from a cyano radical, a trihalomethyl radical, a carboxy radical, a carboxylic acid ester, a sulfo radical, an alkylsulfonyl radical, a sulfamoyl radical of the formula -SO2NR5R6 wherein R5 is hydrogen, alkyl or aryl and R6 can represent the same substituents as R5 or alkyl- or arylcarbonyl or alkyl- or arylsulfonyl and R5 and R6 together can repre-sent 1-(dialkylamino)-alkylidene, a carbamoyl radical of the formula -CON(R5)2 (wherein each R5 can be the same or different and R5 is as described previously), or a halogen atom, as well as a radical of the formula:
wherein each member is as described above;
R1 represents a hydrogen atom, a halogen atom, an alkyl radical, an alkoxy radical or the carbon atoms necessary to form a fused benzo ring attached at the 2- and 3-position or at the 3- and 4-positions;
E which can be in the 3-, 5-, 6- or 7-position, represents a halogen atom, a carboxy radical, a carboxylic acid ester, a sulfo radical, a sulfamoyl radical or a carbamoyl radical, all as described for Z as well as a hydrogen atom, an alkoxy radical or an alkyl radical;
and all the compounds herein are with the proviso that there can be only one sulfo or carboxy radical present.
wherein:
Ball represents an organic ballasting group of such size and configuration as to render said compound nondiffusible during develop-ment in an alkaline processing composition;
Y represents the carbon atoms necessary to complete a benzene or naphthalene nucleus;
X represents a bivalent linking group of the formula:
-R2-Lm-R2p- where each R2 can be the same or different and each repre-sents an alkylene radical having 1 to 8 carbon atoms; or a phenylene radical; L represents a bivalent radical selected from oxy, carbonyl, carboxamido, carbamoyl, sulfonamido, sulfamoyl, sulfinyl or sulfonyl; m is an integer having a value of 0 or 1; p is 1 when n equals 1 and p is 1 or 0 when n equals 0, provided that when p is 1 the carbon content of the sum of both R2 radicals does not exceed 14 carbon atoms;
R represents a hydrogen atom, an alkyl radical having 1 to 6 carbon atoms;
J represents a bivalent radical selected from sulfonyl or carbonyl;
m and q each represent an integer having a value of 0 or 1;
Q represents a hydrogen atom, a hydroxy radical or a radical having the formula -NHCOR3 or -NHSO2R3 wherein R3 is an alkyl radical having 1 to 6 carbon atoms, an alkyl radical having 1 to 4 carbon atoms substituted with hydroxy, cyano, sulfamoyl, carboxy or sulfo, benzyl, phenyl or phenyl substituted with carboxy, chloro, methyl, methoxy or sulfamoyl;
G represents a hydroxy radical, a salt thereof, or a hydrolyzable acyloxy group of the formula:
or wherein R4 is an alkyl radical having 1 to 18 carbon atoms or phenyl;
Z1 represents one or more electron-withdrawing groups selected from a cyano radical, a trihalomethyl radical, a carboxy radical, a carboxylic acid ester, a sulfo radical, an alkylsulfonyl radical, a sulfamoyl radical of the formula -SO2NR5R6 wherein R5 is hydrogen, alkyl or aryl and R6 can represent the same substituents as R5 or alkyl- or arylcarbonyl or alkyl- or arylsulfonyl and R5 and R6 together can repre-sent 1-(dialkylamino)-alkylidene, a carbamoyl radical of the formula -CON(R5)2 (wherein each R5 can be the same or different and R5 is as described previously), or a halogen atom, as well as a radical of the formula:
wherein each member is as described above;
R1 represents a hydrogen atom, a halogen atom, an alkyl radical, an alkoxy radical or the carbon atoms necessary to form a fused benzo ring attached at the 2- and 3-position or at the 3- and 4-positions;
E which can be in the 3-, 5-, 6- or 7-position, represents a halogen atom, a carboxy radical, a carboxylic acid ester, a sulfo radical, a sulfamoyl radical or a carbamoyl radical, all as described for Z as well as a hydrogen atom, an alkoxy radical or an alkyl radical;
and all the compounds herein are with the proviso that there can be only one sulfo or carboxy radical present.
36. The compound as described in claim 35 wherein Y repre-sents the atoms necessary to complete a naphthalene nucleus and G
represents a hydroxy radical or salt thereof.
represents a hydroxy radical or salt thereof.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US33172973A | 1973-02-12 | 1973-02-12 | |
| US43979074A | 1974-02-05 | 1974-02-05 | |
| US05/439,810 US3932381A (en) | 1973-02-12 | 1974-02-05 | Magenta image-providing phenylazo-naphthyl dyes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1038864A true CA1038864A (en) | 1978-09-19 |
Family
ID=27406813
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA192,229A Expired CA1038864A (en) | 1973-02-12 | 1974-02-11 | Azo compounds and photographic materials |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1038864A (en) |
-
1974
- 1974-02-11 CA CA192,229A patent/CA1038864A/en not_active Expired
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