Nondiffusible 6-arylazo-3-pyridinol

This invention relates to photography and more particularly to color diffusion transfer photography employing certain nondiffusible azo dye-releasing compounds which, as a function of development of a silver halide emulsion layer, release a diffusible metallizable, 6-arylazo-3-pyridinol magenta dye or precursor thereof. Highly stable metal complexes of this dye are formed in an image-receiving layer.
U.S. Pat. No. 4,142,891 of Baigrie et al relates to various nondiffusible azo dye-releasing compounds, including compounds having a releasable 6-arylazo-3-pyridinol dye moiety. The dye moieties shown in column 5, lines 1 through 25 and Compounds 11 and 12 of that patent are cyan. The phenyl nucleus of these compounds have a nitro group para to the azo linkage, and a hydroxy ligand group ortho to the azo linkage. The compounds of our invention, however, do not have such a nitro group or a hydroxy ligand and the dye hue of our compound is magenta, instead of cyan. These magenta dyes in accordance with our invention have excellent hues, very little unwanted absorption, and very narrow bandwidths, as illustrated by the comparative tests shown hereinafter.
Research Disclosure 17334, September 1978, page 76, discloses various metallizable azo dye-releasing compounds. Compounds 3 and 4 in that disclosure have a 2-arylazo-3-pyridinol dye moiety. In the dye moieties of our invention, however, the coupling site is in the 6-position which is an essential feature to obtain the hue of the dye.
U.S. Pat. No. 4,195,994 of Chapman relates to various nondiffusible 6-arylazo-2-amino-3-pyridinols. The dye moiety in those compounds are cyan, however, and have in the ortho position of the arylazo moiety a ballasted carrier moiety attached thereto either through a sulfonamido linking group or through the oxygen of a: ##STR2## group. When the dye is released, the sulfonamido or hydroxyl group in that ortho position makes an important resonance contribution to the hue of the dye. The ortho position of the arylazo moiety of the compounds of our invention, however, comprise groups different from those in the Chapman patent which do not make a resonance contribution to the hue of the released dye. Thus, the compounds of our invention have a different hue, and unexpectedly have less unwanted absorption and narrower bandwidths.
U.S. Pat. Nos. 3,870,695 and 4,193,916, and German OLS Nos. 2,236,299; 2,236,269; 2,236,245 and 2,450,884 relate to metal-chelated textile dyes having arylazopyridinol dye moieties. There is no disclosure in these references, however, that these compounds could be attached to carriers and used in photographic elements.
It would be desirable to provide improved dye-releasing compounds containing chelating dye moieties, so that the dye which is released imagewise during processing can diffuse to an image-receiving layer containing metal ions to form a metal-complexed, dye transfer image having better hues, less unwanted absorption, narrower bandwidths, rapid diffusion rates and shorter access times than those of the prior art, as well as good stability to heat, light and chemical reagents.
A photographic element in accordance with the invention comprises a support having thereon at least one photosensitive silver halide emulsion layer, said emulsion layer having associated therewith a dye image-providing material comprising a nondiffusible compound having a releasable 6-arylazo-3-pyridinol magenta dye moiety or precursor thereof, said compound having the formula: ##STR3## wherein: P0 (a) R represents hydroxy or amino; (b) R.sup.1 represents hydrogen, a hydrolyzable moiety or CAR;
(c) G represents carboxy; a hydrolyzable ester group having the formula COOR.sup.2, wherein R.sup.2 is an alkyl or substituted alkyl group having 1 to about 8 carbon atoms or an aryl or substituted aryl group having 6 to about 10 carbon atoms, such as COOCH.sub.3, COOC.sub.6 H.sub.5, COOCH.sub.2 CH.sub.2 CN, COOC.sub.2 H.sub.5, COOC.sub.4 H.sub.9, or COOCH.sub.2 CF.sub.3 ; or a sulfamoyl group having the formula SO.sub.2 NHR.sup.3 wherein R.sup.3 represents hydrogen, alkyl or substituted alkyl having 1 to about 8 carbon atoms, aryl or substituted aryl having 6 to about 10 carbon atoms, or a carbacyl group having 1 to about 8 carbon atoms, such as SO.sub.2 NH.sub.2, SO.sub.2 NHCOC.sub.6 H.sub.5, SO.sub.2 NHC.sub.6 H.sub.5, SO.sub.2 NHCH.sub.2 C.sub.6 H.sub.5, ##STR4## or SO.sub.2 NHCH.sub.3 ; (d) CAR represents a ballasted carrier moiety capable of releasing said diffusible 6-arylazo-3-pyridinol magenta dye moiety or precursor thereof as a function of development of said silver halide emulsion layer under alkaline conditions, e.g., as a function of development of the silver halide emulsion; and
(e) n is 0, 1 or 2, with the proviso that when n is 0, then R.sup.1 is CAR.
Excellent magenta dyes are obtained in this embodiment when R is hydroxy, R.sup.1 is hydrogen, G is carboxy and n is 1. Other substituents may also be present in the two rings, such as alkyl of 1 to 6 carbon atoms, alkoxy, halogens, phenylsulfamoyl, solubilizing groups such as sulfonamido, sulfamoyl, carboxy, sulfo or hydrolyzable precursors thereof. The phenyl ring may not be substituted with a nitro group, however, which would adversely shift the hue of the dye bathochromically.
In another embodiment of the invention, CAR may have attached thereto two azo dye moieties, as shown by the formula above, in which case two dye moieties will be released from one CAR moiety.
When R.sup.1 is a CAR or a hydrolyzable moiety, the absorption of the dye-releasing compound is shifted out of the green region of the spectrum, so that the compound may be incorporated in the emulsion layer, which is very desirable in certain embodiments of the invention.
As stated above, R.sup.1 represents hydrogen, a hydrolyzable moiety or CAR. Hydrolyzable moieties which can be employed in our invention include acetate, benzoate, pivalate, carbamates, or any of the blocking groups which can be cleaved by an intramolecular nucleophilic displacement reaction, as disclosed in Mooberry and Archie U.S. Ser. No. 949,462, filed Oct. 10, 1978, now U.S. Pat. No. 4,310,612, issued Jan. 12, 1982, the disclosure of which is hereby incorporated by reference.
There is great latitude in selecting a CAR moiety which is attached to the dye-releasing compounds described above. Depending upon the nature of the ballasted carrier selected, various groups may be needed to attach or link the carrier moiety to the dye. Such linking groups are considered to be a part of the CAR moiety in the above definition. It should also be noted that, when the dye moiety is released from the compound, cleavage may take place in such a position that part or all of the linking group, if one is present, and even part of the ballasted moiety, may be transferred to the image-receiving layer, along with the dye moiety. In any event, the dye nucleus as shown above can be thought of as the minimum which is transferred.
CAR moieties useful in the invention are described in U.S. Pat. Nos. 3,227,550; 3,628,952; 3,227,552 and 3,844,785 (dye released by chromogenic coupling); U.S. Pat. Nos. 3,443,939 and 3,443,940 (dye released by intramolecular ring closure); U.S. Pat. Nos. 3,698,897 and 3,725,062 (dye released from hydroquinone derivatives); U.S. Pat. No. 3,728,113 (dye released from a hydroquinonylmethyl quaternary salt); U.S. Pat. Nos. 3,719,489 and 3,443,941 (silver ion induced dye release); British Patent Publication No. 2,017,950A (dye released by a dye bleach process); U.S. Pat. Nos. 4,053,312; 4,198,235; 4,179,231; 4,055,428 and 4,149,892 (dye released by oxidation and deamidation); and U.S. Pat. Nos. 3,245,789 and 3,980,497; Canadian Pat. No. 602,607; British Pat. No. 1,464,104; Research Disclosure 14447, April 1976; and U.S. Pat. No. 4,139,379 of Chasman et al (dye released by miscellaneous mechanisms), the disclosures of which are hereby incorporated by reference.
In a further preferred embodiment of the invention, the ballasted carrier moiety or CAR as described above may be represented by the following formula:
(Ballast-Carrier-Link)
wherein:
(a) Ballast is an organic ballasting radical of such molecular size and configuration as to render said compound nondiffusible in said photographic element during development in an alkaline processing composition;
(b) Carrier is an oxidizable acyclic, carbocyclic or heterocyclic moiety (see The Theory of the Photographic Process, by C. E. K. Mees and T. H. James, Third Edition, 1966, pages 282 to 283), e.g., moieties containing atoms according to the following configuration:
a(--C.dbd.C).sub.b --
wherein:
b is a positive integer of 1 to 2; and
a represents the radicals OH, SH, NH-- or hydrolyzable precursors thereof; and
(c) Link represents a group which, upon oxidation of said Carrier moiety, is capable of being hydrolytically cleaved to release the diffusible azo dye. For example, Link may be the following groups: ##STR5## wherein * represents the position of attachment to Carrier.
The Ballast group in the above formula is not critical, so long as it confers nondiffusibility to the compound. Typical Ballast groups include long-chain alkyl radicals, as well as aromatic radicals of the benzene and naphthalene series linked to the compound. Useful Ballast groups generally have at least 8 carbon compounds, such as substituted or unsubstituted alkyl groups of 8 to 22 carbon atoms; a carbamoyl radical having 8 to 30 carbon atoms, such as --CONH(CH.sub.2).sub.4 --O--C.sub.6 H.sub.3 (C.sub.5 H.sub.11).sub.2, or --CON(C.sub.12 H.sub.25).sub.2 ; or a keto radical having 8 to 30 carbon atoms, such as --CO--C.sub.11 H.sub.35 or --CO--C.sub.6 H.sub.4 (t--C.sub.12 H.sub.25).
For specific examples of Ballast-Carrier moieties useful as the CAR moiety in this invention, reference is made to the November 1976 edition of Research Disclosure, pages 68 through 74, and the April 1977 edition of Research Disclosure, pages 32 through 39, the disclosures of which are hereby incorporated by reference.
In a highly preferred embodiment of the invention, the ballasted carrier moiety or CAR in the above formula is a group having the formula: ##STR6## wherein:
(a) Ballast is an organic ballasting radical of such molecular size and configuration (e.g., simple organic groups or polymeric groups) as to render said compound nondiffusible in a photographic element during development in an alkaline processing composition;
(b) D is OR.sup.4 or NHR.sup.5 wherein R.sup.4 is hydrogen or a hydrolyzable moiety, such as acetyl, mono-, di- or trichloroacetyl radicals, perfluoroacyl, pyruvyl, alkoxyacyl, nitrobenzoyl, cyanobenzoyl, sulfonyl or sulfinyl, and R.sup.5 is hydrogen or a substituted or unsubstituted alkyl group of 1 to 22 carbon atoms, such as methyl, ethyl, hydroxyethyl, propyl, butyl, secondary butyl, tertbutyl, cyclopropyl, 4-chlorobutyl, cyclobutyl, 4-nitroamyl, hexyl, cyclohexyl, octyl, decyl, octadecyl, dodecyl, benzyl or phenethyl (when R.sup.5 is an alkyl group of greater than 8 carbon atoms, it can serve as a partial or sole Ballast);
(c) Y represents at least the atoms necessary to complete a benzene nucleus, a naphthalene nucleus, or a 5 to 7 membered heterocyclic ring, such as pyrazolone or pyrimidine; and
(d) j is a positive integer of 1 to 2 and is 2 when D is OR.sup.4 or when R.sup.5 is hydrogen or an alkyl group of less than 8 carbon atoms.
Especially good results are obtained in the above formula when D is OH, j is 2, and Y is a naphthalene nucleus.
Examples of the CAR moiety in this highly preferred embodiment are disclosed in U.S. Pat. Nos. 4,076,529; 3,993,638 and 3,928,312, the disclosures of which are hereby incorporated by reference, and include the following: ##STR7##
In another highly preferred embodiment of the invention, the ballasted carrier moiety or CAR in the above formulas is such that the diffusible azo dye is released as an inverse function of development of the silver halide emulsion layer under alkaline conditions. This is ordinarily referred to as positive-working dye-release chemistry. In one of these embodiments, the ballasted carrier moiety or CAR in the above formulas may be a group having the formula: ##STR8## wherein:
Ballast is an organic ballasting radical of such molecular size and configuration as to render said compound nondiffusible in a photographic element during development in an alkaline processing composition;
W.sup.2 represents at least the atoms necessary to complete a benzene nucleus (including various substituents thereon); and
R.sup.7 is an alkyl (including substituted alkyl) radical having 1 to about 4 carbon atoms.
Examples of the CAR moiety in this formula (I) include the following: ##STR9##
In a second embodiment of positive-working dye-release chemistry as referred to above, the ballasted carrier moiety or CAR in the above formulas may be a group having the formula: ##STR10## wherein:
Ballast is an organic ballasting radical of such molecular size and configuration as to render said compound nondiffusible in a photographic element during development in an alkaline processing composition;
W.sup.1 represents at least the atoms necessary to complete a quinone nucleus (including various substituents thereon);
r is a positive integer of 1 or 2;
R.sup.6 is an alkyl (including substituted alkyl) radical having 1 to about 40 carbon atoms or an aryl (including substituted aryl) radical having 6 to about 40 carbon atoms; and
k is a positive integer of 1 to 2 and is 2 when R.sup.6 is a radical of less than 8 carbon atoms.
Examples of the CAR moiety in this formula (II) include the following: ##STR11##
In using the compounds in formulas I and II above, they are employed in a photographic element similar to the other nondiffusible dye-releasers described previously. Upon reduction of the compound as a function of silver halide development under alkaline conditions, the metallizable azo dye is released. In this embodiment, conventional negative-working silver halide emulsions, as well as direct-positive emulsions, can be employed. For further details concerning these particular CAR moieties, including synthesis details, reference is made to U.S. Pat. No. 4,139,379 of Chasman et al, the disclosure of which is hereby incorporated by reference.
In a third embodiment of positive-working dye-release chemistry as referred to above, the ballasted carrier moiety or CAR in the above formulas may be a group having the formula: ##STR12## wherein:
Ballast, W.sup.2 and R.sup.7 are as defined for formula (I) above.
Examples of the CAR moiety in this formula (III) include the following: ##STR13##
For further details concerning this particular CAR moiety, including synthesis details, reference is made to U.S. Pat. No. 4,199,354 of Hinshaw et al, the disclosure of which is hereby incorporated by reference.
In a fourth embodiment of positive-working dye-release chemistry as referred to above, the ballasted carrier moiety or CAR in the above formulas may be a group having the formula: ##STR14## wherein:
Ballast, r, R.sup.6 and k are as defined for formula (II) above;
W.sup.2 is as defined for formula (I) above; and
K is OH or a hydrolyzable precursor thereof.
Examples of the CAR moiety in this formula (IV) include the following: ##STR15##
For further details concerning this particular CAR moiety, including synthesis details, reference is made to U.S. Pat. No. 3,980,479 of Fields et al, the disclosure of which is hereby incorporated by reference.
Representative compounds included within the scope of the invention include the following: ##STR16##
A process for producing a photographic transfer image in color according to the invention comprises:
(a) treating an imagewise-exposed photographic element as described above 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;
(b) the dye-releasing compound then releasing the diffusible azo dye as described above imagewise as a function of the development of each of the silver halide emulsion layers;
(c) at least a portion of the imagewise distribution of the azo dye diffusing to a dye image-receiving layer; and
(d) contacting the imagewise distribution of azo dye with metal ions, thereby forming a metal-complexed azo dye transfer image.
The tridentate azo dye ligand which is released from the dye-releasing compounds in accordance with the present invention will form a coordination complex in the image-receiving layer with polyvalent metal ions. The metal ions can be present in the image-receiving layer itself or in a layer adjacent thereto, or the image-receiving layer can be contacted with metal ions in a bath after diffusion of the dye has taken place. Metal ions most useful in the invention are those which are essentially colorless when incorporated into the image-receiving element, are inert with respect to the silver halide layers, react readily with the released dye to form a complex of the desired hue, are tightly coordinated to the dye in the complex, have a stable oxidation state, and form a dye complex which is stable to heat, light and chemical reagents. In general, good results are obtained with polyvalent metal ions such as copper (II), zinc (II), nickel (II), platinum (II), palladium (II) and cobalt (II) ions.
For example, it is believed that the coordination complex which is formed from the tridentate azo dye ligand according to the invention in one of the preferred embodiments thereof has the following structure: ##STR17## wherein:
R is as defined previously;
Me is metal; and
Lig is one or more ligand groups, depending upon the coordination number of the metal ion, such as H.sub.2 O, Cl or pyridine, or a second dye moiety.
Thus, in accordance with this preferred embodiment of the invention, a photographic element is provided which comprises a support having thereon a coordination complex of a polyvalent metal ion and a compound having the formula: ##STR18## wherein:
G and R are as described previously.
The element usually contains a photographic mordant or image-receiving layer to bind the dye or coordination complex thereto. The structures shown above may also, of course, be substituted in the same manner as described above for the starting compounds from which they are released.
It will be appreciated that, after processing the photographic element described above, there remains in it after transfer has taken place an imagewise distribution of azo dye in addition to developed silver. A color image comprising residual nondiffusible compound is obtained 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. Such a retained dye image should normally be treated with metal ions to metallize the dyes to increase their light fastness and shift their spectral absorption to the intended region. The imagewise distribution of azo 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 certain preferred photosensitive elements, described above, then a positive color image, such as a reflection print, a color transparency or motion picture film, is produced in this manner. If a direct-positive silver halide emulsion is employed in such photosensitive elements, then a negative color image is produced.
The photographic element in the above-described process is 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 rupturable container or pod which contains the composition. In general, the processing composition employed in this invention contains the developing agent for development, although the composition could also just be an alkaline solution where the developer is incorporated in the photographic element, image-receiving element or process sheet, in which case the alkaline solution serves to activate the incorporated developer.
A photographic film unit or assemblage in accordance with this invention is adapted to be processed by an alkaline processing composition, and comprises:
(1) a photographic element as described above; and
(2) a dye image-receiving layer. In this embodiment, the processing composition may be inserted into the film unit, such as by interjecting processing solution with communicating members similar to hypodermic syringes which are attached either to a camera or camera cartridge. The processing composition can also be applied by means of a swab or by dipping in a bath, if so desired.
In a preferred embodiment of the invention, the assemblage itself contains the alkaline processing composition and means containing same for discharge within the film unit, such as a rupturable container which is adapted to be positioned during processing of the film unit so that a compressive force applied to the container by pressure-applying members, such as would be found in a camera designed for in-camera processing, will effect a discharge of the container's contents within the film unit.
In the embodiment described above, the dye image-receiving layer may itself contain metal ions or the metal ions may be present in an adjacent layer, so that the tridentate azo dye ligand which is released will form a coordination complex therewith. The dye thus becomes immobilized in the dye image-receiving layer and metallized at the same time. Alternatively, the dye image in the dye image-receiving layer may be treated with a solution containing metal ions to effect metallization. The formation of the coordination complex shifts the absorption of the dye to the desired hue, usually to longer wavelengths, which have a different absorption than that of the initial dye-releasing compound. If this shift is large enough, then the dye-releasing compound may be incorporated in a silver halide emulsion layer without adversely affecting its sensitivity.
The dye image-receiving layer in the above-described film assemblage is optionally located on a separate support adapted to be superposed on the photographic element after exposure thereof. Such image-receiving elements are generally disclosed, for example, in U.S. Pat. No. 3,362,819. When the means for discharging the processing composition is a rupturable container, it is usually positioned in relation to the photographic element and the image-receiving element so that a compressive force applied to the container by pressure-applying members, such as would be found in a typical camera used for in-camera processing, will effect a discharge of the container's contents between the image-receiving element and the outermost layer of the photographic element. After processing, the dye image-receiving element is separated from the photographic element.
The dye image-receiving layer in the above-described film assemblage in another embodiment is located integral with the photographic element between the support and the lowermost photosensitive silver halide emulsion layer. One useful format for integral receiver-negative photographic elements is disclosed in Belgian Pat. No. 757,960. In such an embodiment, the support for the photographic element is transparent and is coated with an image-receiving layer, a substantially opaque light-reflective layer, e.g., TiO.sub.2, and then the photosensitive layer or layers described above. After exposure of the photographic element, a rupturable container containing an alkaline processing composition and an opaque process sheet are brought into superposed position. Pressure-applying members in the camera rupture the container and spread processing composition over the photographic element as the film unit is withdrawn from the camera. The processing composition develops each exposed silver halide emulsion layer and dye images are formed as a function of development which diffuse to the image-receiving layer to provide a positive, right-reading image which is viewed through the transparent support on the opaque reflecting layer background. For other details concerning the format of this particular integral film unit, reference is made to the above-mentioned Belgian Pat. No. 757,960.
Another format for integral negative-receiver photographic elements in which the present invention is employed is disclosed in Canadian Pat. No. 928,559. In this embodiment, the support for the photographic element is transparent and is coated with the image-receiving layer, a substantially opaque, light-reflective layer and the photosensitive layer or layers described above. A rupturable container containing an alkaline processing composition and an opacifier is positioned adjacent the top layer and a transparent top sheet which has thereon a neutralizing layer and a timing layer. 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 a result of development which diffuse to the image-receiving layer to provide a positive, right-reading image which is viewed through the transparent support on the opaque reflecting layer background. For further details concerning the format of this particular integral film unit, reference is made to the above-mentioned Canadian Pat. No. 928,559.
Still other useful integral formats in which this invention can be employed are described in U.S. Pat. Nos. 3,415,644; 3,415,645; 3,415,646; 3,647,437 and 3,635,707. In most of these formats, a photosensitive silver halide emulsion is coated on an opaque support and a dye image-receiving layer is located on a separate transparent support superposed over the layer outermost from the opaque support. In addition, this transparent support also preferably contains a neutralizing layer and a timing layer underneath the dye image-receiving layer.
Another embodiment of the invention uses the image-reversing technique disclosed in British Pat. No. 904,364, page 19, lines 1 through 41. In this process, the dye-releasing 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.
The film unit or assembly used in the present invention is used to produce positive images in single- or multicolors. In a three-color system, each silver halide emulsion layer of the fim assembly will have associated therewith a dye-releasing compound which releases a dye possessing a predominant spectral absorption within the region of the visible spectrum to which said silver halide emulsion is sensitive (initially or after forming the coordination complex), i.e., the blue-sensitive silver halide emulsion layer will have a yellow or yellow-forming dye-releaser associated therewith, the green-sensitive silver halide emulsion layer will have the magenta or magenta-forming dye-releaser of the invention associated therewith, and the red-sensitive silver halide emulsion layer will have a cyan or cyan-forming dye-releaser associated therewith. The dye-releaser associated with each silver halide emulsion layer is contained either in the silver halide emulsion layer itself or in a layer contiguous to the silver halide emulsion layer.
The concentration of the dye-releasing compounds that are employed in the present invention may be varied over a wide range, depending upon the particular compound employed and the results which are desired. For example, the dye-releasers of the present invention may be coated in layers by using coating solutions containing between about 0.5 and about 8 percent by weight of the dye-releaser distributed in a hydrophilic film-forming natural material or synthetic polymer, such as gelatin, polyvinyl alcohol, etc, which is adapted to be permeated by aqueous alkaline processing composition.
Depending upon which CAR is used in the present invention, a variety of silver halide developing agents or electron transfer agents (ETA's) are useful in this invention. In certain embodiments of the invention, any ETA can be employed as long as it cross-oxidizes with the dye-releasers described herein. The ETA may also be incorporated in the photosensitive element to be activated by the alkaline processing composition. Specific examples of ETA's useful in this invention include hydroquinone compounds, such as hydroquinone, 2,5-dichlorohydroquinone or 2-chlorohydroquinone; aminophenol compounds, such as 4-aminophenol, N-methylaminophenol, N,N-dimethylaminophenol, 3-methyl-4-aminophenol or 3,5-dibromoaminophenol; catechol compounds, such as catechol, 4-cyclohexylcatechol, 3-methoxycatechol or 4-(N-octadecylamino)catechol; and phenylenediamine compounds, such as N,N-diethyl-p-phenylenediamine, 3-methyl-N,N-diethyl-p-phenylenediamine, 3-methoxy-N-ethyl-N-ethoxy-p-phenylenediamine or N,N-N',N'-tetramethyl-p-phenylenediamine. In highly preferred embodiments, the ETA is a 3-pyrazolidinone compound, such as 1-phenyl-3-pyrazolidinone (Phenidone), 1-phenyl-4,4-dimethyl-3-pyrazolidinone (Dimezone), 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazoidinone, 4-hydroxymethyl-4-methyl-1-p-tolyl-3-pyrazolidinone, 4-hydroxymethyl-4-methyl-1-(3,4-dimethylphenyl)-3-pyrazolidinone, 1-m-tolyl-3-pyrazolidinone, 1-p-tolyl-3-pyrazolidinone, 1-phenyl-4-methyl-3-pyrazolidinone, 1-phenyl-5-methyl-3-pyrazolidinone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidinone, 1,4-dimethyl-3-pyrazolidinone, 4-methyl-3-pyrazolidinone, 4,4-dimethyl-3-pyrazolidinone, 1-(3-chlorophenyl)-4-methyl-3-pyrazolidinone, 1-(4-chlorophenyl)-4-methyl-3-pyrazolidinone, 1-(3-chlorophenyl)-3-pyrazolidinone, 1-(4-chlorophenyl)-3-pyrazolidinone, 1-(4-tolyl)-4-methyl-3-pyrazolidinone, 1-(2-tolyl)-4-methyl-3-pyrazolidinone, 1-(4-tolyl)-3-pyrazoidinone, 1-(3-tolyl)-3-pyrazolidinone, 1-(3-tolyl)-4,4-dimethyl-3-pyrazolidinone, 1-(2-trifluoroethyl)-4,4-dimethyl-3-pyrazolidinone or 5-methyl- 3-pyrazolidinone. A combination of different ETA's, such as those disclosed in U.S. Pat. No. 3,039,869, can also be employed. These ETA's are employed in the liquid processing composition or contained, at least in part, in any layer or layers of the photographic element or film unit to be activated by the alkaline processing composition, such as in the silver halide emulsion layers, the dye image-providing material layers, interlayers, image-receiving layer, etc.
In a preferred embodiment of the invention, the silver halide developer or ETA employed in the process becomes oxidized upon development and reduces silver halide to silver metal. The oxidized developer than cross-oxidizes the dye-releasing compound. The product of cross-oxidation then undergoes alkaline hydrolysis, thus releasing an imagewise distribution of diffusible azo dye which then diffuses to the receiving layer to provide the dye image. The diffusible moiety is transferable in alkaline processing composition either by virtue of its selfdiffusivity or by its having attached to it one or more solubilizing groups, for example, a carboxy, sulpho, sulphonamido, hydroxy or morpholino group.
In using the dye-releasing compounds according to the invention which produce diffusible dye images as a function of development, either conventional negative-working or direct-positive silver halide emulsions are employed. If the silver halide emulsion employed is a direct-positive silver halide emulsion, such as an internal-image emulsion designed for use in the internal image reversal process or a fogged, direct-positive emulsion such as a solarizing emulsion, which is developable in unexposed areas, a positive image can be obtained in certain embodiments on the dye image-receiving layer. After exposure of the film unit, the alkaline processing composition permeates the various layers to initiate development of 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 unexposed areas (since the silver halide emulsions are direct-positive ones), thus causing the developing agent to become oxidized imagewise corresponding to the unexposed 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 to release the 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 subject. After being contacted by the alkaline processing composition, a neutralizing layer in the film unit or image-receiving unit lowers the pH of the film unit or image receiver to stabilize the image.
Internal-image silver halide emulsions useful in this invention are described more fully in the November 1976 edition of Research Disclosure, pages 76 through 79, the disclosure of which is hereby incorporated by reference.
The various silver halide emulsion layers of a color film assembly employed in this invention are disposed in the usual order, i.e., the blue-sensitive silver halide emulsion layer first with respect to the exposure side, followed by the green-sensitive and red-sensitive silver halide emulsion layers. If desired, a yellow dye layer or a yellow colloidal silver layer can be present between the blue-sensitive and green-sensitive silver halide emulsion layers for absorbing or filtering blue radiation that is 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 red-sensitive and green-sensitive layers.
The rupturable container employed in certain embodiments of this invention is disclosed in U.S. Pat. Nos. 2,543,181; 2,643,886; 3,653,732; 3,723,051; 3,056,492; 3,056,491 and 3,152,515. In general, such containers comprise a rectangular sheet of fluid- and air-impervious material folded longitudinally upon itself to form two walls which are sealed to one another along their longitudinal and end margins to form a cavity in which processing solution is contained.
Generally speaking, except where noted otherwise, the silver halide emulsion layers employed in the invention comprise photosensitive silver halide dispersed in gelatin and are about 0.6 to 6 microns in thickness; the dye-releasers are dispersed in an aqueous alkaline solution-permeable polymeric binder, such as gelatin, as a separate layer about 0.2 to 7 microns in thickness; and the alkaline solution-permeable polymeric interlayers, e.g, gelatin, are about 0.2 to 5 microns in thickness. Of course, these thicknesses are approximate only and can be modified according to the product desired.
Scavengers for oxidized developing agent can be employed in various interlayers of the photographic elements of the invention. Suitable materials are disclosed on page 83 of the November 1976 edition of Research Disclosure, the disclosure of which is hereby incorporated by reference.
Any material is useful as the image-receiving layer in this invention as long as the desired function of mordanting or otherwise fixing the dye images is obtained. The particular material chosen will, of course, depend upon the dye to be mordanted. Suitable materials are disclosed on pages 80 through 82 of the November 1976 edition of Research Disclosure, the disclosure of which is hereby incorporated by reference.
Use of a neutralizing material in the film units employed in this invention will usually increase the stability of the transferred image. Generally, the neutralizing material will effect a reduction in the pH of the image layer from about 13 or 14 to at least 11 and preferably 5 to 8 within a short time after imbibition. Suitable materials and their functioning are disclosed on pages 22 and 23 of the July 1974 edition of Research Disclosure, and pages 35 through 37 of the July 1975 edition of Research Disclosure, the disclosures of which are hereby incorporated by reference.
A timing or inert spacer layer can be employed in the practice of this invention over the neutralizing layer which "times" of controls the pH reduction as a function of the rate at which alkali diffuses through the inert spacer layer. Examples of such timing layers and their functioning are disclosed in the Research Disclosure articles mentioned in the paragraph above concerning neutralizing layers.
The alkaline processing composition employed in this invention is the conventional aqueous solution of an alkaline material, e.g., alkali metal hydroxides or carbonates such as 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. Suitable materials and addenda frequently added to such compositions are disclosed on pages 79 and 80 of the November 1976 edition of Research Disclosure, the disclosure of which is hereby incorporated by reference.
The alkaline solution-permeable, substantially opaque, light-reflective layer employed in certain embodiments of photographic film units used in this invention is described more fully in the November 1976 edition of Research Disclosure, page 82, the disclosure of which is hereby incorporated by reference.
The supports for the photographic elements used in this invention can be any material as long as it does not deleteriously affect the photographic properties of the film unit and is dimensionally stable. Typical flexible sheet materials are described on page 85 of the November 1976 edition of Research Disclosure, the disclosure of which is hereby incorporated by reference.
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, respectively, dots of yellow, magenta and cyan color-providing substances. After development, the transferred dyes would tend to fuse together into a continuous tone.
The silver halide emulsions useful in this invention, both negative-working and direct-positive ones, are well known to those skilled in the art and are described in Research Disclosure, Volume 176, December 1978, Item No. 17643, pages 22 and 23, "Emulsion preparation and types"; they are usually chemically and spectrally sensitized as described on page 23, "Chemical sensitization", and "Spectral sensitization and desensitization", of the above article; they are optionally protected against the production of fog and stabilized against loss of sensitivity during keeping by employing the materials described on pages 24 and 25, "Antifoggants and stabilizers", of the above article; they usually contain hardeners and coating aids as described on page 26, "Hardeners", and pages 26 and 27, "Coating aids", of the above article; they and other layers in the photographic elements used in this invention usually contain plasticizers, vehicles and filter dyes described on page 27, "Plasticizers and lubricants"; page 26, "Vehicles and vehicle extenders"; and pages 25 and 26, "Absorbing and scattering materials", of the above article; they and other layers in the photographic elements used in this invention can contain addenda which are incorporated by using the procedures described on page 27, "Methods of addition", of the above article; and they are usually coated and dried by using the various techniques described on pages 27 and 28, "Coating and drying procedures", of the above article, the disclosures of which are hereby incorporated by reference.
The term "nondiffusing" used herein has the meaning commonly applied to the term in photography and denotes materials that, for all practical purposes, do not migrate or wander through organic colloid layers, such as gelatin, in the photographic elements of the invention in an alkaline medium and preferably when processed in a medium having a pH of 11 or greater. The same meaning is to be attached to the term "immobile". The term "diffusible" as applied to the materials of this invention has the converse meaning and denotes materials having the property of diffusing effectively through the colloid layers of the photographic elements in an alkaline medium. "Mobile" has the same meaning as "diffusible".
The term "associated therewith" as used herein is intended to mean that the materials can be in either the same or different layers, so long as the materials are accessible to one another.

The following examples are provided to further illustrate the invention.
EXAMPLE 1
Hue Test-Released Dyes
A receiving element was prepared comprising a poly(ethylene terephthalate) film support having thereon a nickel sulfate hexahydrate (0.58 g/m.sup.2)/gelatin (1.08 g/m.sup.2) metal complexing layer, and a poly(4-vinylpyridine)/gelatin mordant layer (each at 2.15 g/m.sup.2).
The receiving element was immersed in an alkaline solution of the azo dyes listed in the Table below. The receiver was removed from the dye solution, washed in distilled water, placed in a pH 7.0 buffer solution and dried. Transmission spectra obtained on each sample were normalized to a density of 1.0. The .lambda..sub.max at maximum density, along with the "half band width" (1/2 BW), the wavelength range of the curve at half the maximum density, are recorded in the Table below. A narrow 1/2 BW generally designates a pure hue.
TABLE__________________________________________________________________________ ##STR19##Compound .lambda..sub.max 1/2 BWNumber G R R.sup.8 (nm) (nm)__________________________________________________________________________14 COOH NH.sub.2 H 563 8215 COOH OH H 550 7616 COOH NH.sub.2 5-SO.sub.2 NH.sub.2 576 7817 COOH NH.sub.2 4-NHCOCH.sub.3 575 9218 COOH NH.sub.2 4-CH.sub.3 556 8619 COOH NH.sub.2 6-CH.sub.3 534 11020 COOH NH.sub.2 6-OCH.sub.3 540 9521 SO.sub.2 NH.sub.2 NH.sub.2 H 542 8222 SO.sub.2 NHCOC.sub.6 H.sub.5 NH.sub.2 H 547 8423 SO.sub.2 NHC.sub.6 H.sub.5 NH.sub.2 H 527 8024 SO.sub.2 NHCH.sub.2 C.sub.6 H.sub.5 NH.sub.2 H 548 8925 SO.sub.2 NH.sub.2 NH.sub.2 H 552 83(also has a 5-SO.sub.2 NH.sub.2 group on the pyridine ring)26 ##STR20## NH.sub.2 H 544 7627 SO.sub.2 NHCH.sub.3 NH.sub.2 H 542 7828 COOH OH 4-SO.sub.2 NH.sub.2 570 7629 COOH OH 5-SO.sub.2 NH.sub.2 557 7530 COOH OH 4-CH.sub.3 548 7931 COOCH.sub.3 OH H 570 10032 COOH OH 4-Cl 560 8333 COOH OH 5-Cl 559 8334 COOH OH H 556 79 (also has a 5-Cl on the pyridine ring)35 COOH OH ##STR21## 558 7836 COOH OH 5-SO.sub.2 CH.sub.3 563 8337 COOH OH 5-SO.sub.2 N(CH.sub.3).sub.2 562 8538 COOH OH 5-SO.sub.2 NHCH(CH.sub.3).sub.2 561 7839 COOH OH ##STR22## 559 83__________________________________________________________________________
EXAMPLE 2
Preparation of Compound 15 ##STR23##
2,3-Dihydroxypyridine (1.22 g, 11.0 mmoles) was dissolved in aqueous sodium hydroxide (15 ml, 10 percent) and chilled to 0.degree. C. Anthranilic acid (1.37 g, 10 mmoles) was dissolved in water (10 ml), diazotized with NaNO.sub.2 /HCl (5 ml 2 N NaNO.sub.2 /1.57 ml concentrated HCl) at 0.degree. C. and added to the dihydroxypyridine solution. The reaction mixture was stirred for 30 minutes and acidified with 1 N HCl to cause precipitation. The product was collected by filtration, washed with water and recrystallized from acetic acid/water (1:1); yield, 2.23 g (86.1 percent).
EXAMPLE 3
Preparation of Compound 31 ##STR24##
Methyl anthranilate (20.0 g, 0.13 mole) was dissolved in methanol (400 ml) containing dry HCl gas (approximately 10 g). After cooling in an ice bath, sodium nitrite (9.2 g) in water (25 ml) was slowly added. The reaction mixture was stirred for 30 minutes at 0.degree. C.
2,3-Dihydroxypyridine (14.5 g) was dissolved in methanol (300 ml) containing sodium acetate (25 g) and enough water to obtain a homogeneous solution. After cooling the dihydroxypyridine solution in an ice bath, the above-described diazonium salt solution was added slowly with rapid stirring. After the addition was completed, the mixture was stirred for 1 hour. The dye was collected by filtration and the filtrate was concentrated to yield an additional crop of dye; yield, 29.8 g (83 percent crude). The crude product was recrystallized from methanol containing 10 percent acetic acid; m.p. 190.degree. to 195.degree. C.
EXAMPLE 4
Preparation of Dye-Releasing Redox Compound No. 5
2,5-Bis[1-(p-t-butylphenyl)ethyl]-3,6-bis[N-(chloroformyl)-N-n-dodecylaminomethyl]benzoquinone (7.0 g, 7.4 mmoles) in dichloromethane (40 ml) was added to a solution of Compound 31 (6.0 g, 22.0 mmoles) in pyridine (50 ml) and diisopropylethylamine (1.9 g). After stirring overnight at room temperature under a nitrogen atmosphere, the reaction mixture was evaporated to dryness and the remainder triturated with cyclohexane/ethyl acetate (95:5) and filtered. The filtrate was evaporated to give crude product; yield, 11.2 g. The product was chromatographed on silica gel using cyclohexane/ethyl acetate (70:30) to obtain a pure sample; yield, 4.2 g (49.4 percent).
EXAMPLE 5
Preparation of Dye-Releasing Redox Compound 1
4-(3-Amino-4-methoxycarbonylbenzenesulfonamido)-N[4-(2,4-di-t-pentylphenoxy)butyl]-1-hydroxy-2-naphthamide (6.0 g, 8.5 mmoles) was dissolved in methanol (20 ml) saturated with HCl (g) and tetrahydrofuran (25 ml). The solution was cooled to -10.degree. C., combined with isopentyl nitrite (1.4 g) and stirred for 1 hour.
2,3-Dihydroxypyridine (1.4 g, 12.6 mmoles) was dissolved in pyridine (20 ml) and combined slowly with the above described diazonium solution at -10.degree. C. The reaction mixture was allowed to stand for 2 hours at room temperature, poured onto ice/HCl and filtered to obtain a crude product; yield, 6.5 g. The crude product was chromatographed on silica gel. The fractions containing the product were dissolved in dimethylformamide (25 ml) under nitrogen and treated with a 10 percent by weight potassium hydroxide solution (5 ml). After stirring for 2 hours, the solution was acidified and filtered; yield, 1.2 g (17.3 percent).
Intermediates
(A) Methyl-2-nitro-4-sulfobenzoate, potassium salt ##STR25##
2-Nitro-4-sulfobenzoic acid, potassium salt (20 g, 0.07 mole) was added to methanol (600 ml) saturated with HCl (g) and the mixture was refluxed for 3 days. The hot solution was filtered and the filtrate was evaporated to half volume. The concentrated filtrate was cooled and filtered; yield, 15.0 g (71.1 percent).
(B) Methyl-4-chlorosulfonyl-2-nitrobenzoate ##STR26##
Intermediate (A) (15.0 g, 0.05 mole) was added to thionyl chloride (80 ml). After adding dimethylformamide (3 ml), the mixture was stirred for 5 hours. The product was isolated by decomposing the excess thionyl chloride on ice with vigorous stirring and then filtering the mixture to obtain a solid which was dried in vacuo; yield, 12.0 g (90.2 percent).
(C) N-[4-(2,4-di-t-pentylphenoxy)butyl]-1-hydroxy-4-(4-methoxycarbonyl-3-nitrobenzenesulfonamido)-2-naphthamide ##STR27##
4-Amino-N-[4-(2,4-di-t-pentylphenoxy)butyl]-1-hydroxy-2-naphthamide (11.7 g, 23.8 mmoles) was dissolved in methylene chloride (300 ml) under nitrogen and reacted with intermediate (B) (6.7 g, 25.2 mmoles) in the presence of pyridine (2.0 g). After 5 hours of stirring at room temperature, acetic acid (2 ml) was added and the mixture was evaporated to dryness. Trituration of the residue gave a solid which was collected by filtration and recrystallized from ethanol; yield, 8.0 g (46.8 percent).
(D) 4-(3-Amino-4-methoxycarbonylbenzenesulfonamido)-N-[4-(2,4-di-t-pentylphenoxy)butyl]-1-hydroxy-2-naphthamide ##STR28##
Intermediate (C) (10.0 g, 13.9 mmoles) was reduced in tetrahydrofuran (100 ml) using Pd/C catalyst at 60 pounds pressure (H.sub.2 gas). The temperature rose to 30.degree. C. The catalyst was removed by filtration; the filtrate was concentrated to dryness. Trituration of the residue with methanol produced a solid; yield, 8.3 g (84.9 percent).
EXAMPLE 6
Compound 2 was synthesized by a procedure similar to that described for Compound 1, except that the ester hydrolysis was carried out before the coupling step. The dye releaser was recrystallized from isopropyl alcohol; m.p. 228.degree. C.
EXAMPLE 7
Comparative Test--Hues of Released Dyes
In U.S. Pat. No. 4,142,891 of Baigrie et al, the released dye from Compound 11 in that patent has the following structure: ##STR29##
In U.S. Pat. No. 4,207,104 of Chapman et al, Dye 26 in Table II of that patent has the following structure: ##STR30##
Compound 15 above has the following structure: ##STR31##
The spectra from the above three released dyes were compared using the same procedure as in Example 1.
The .lambda..sub.max at maximum density and the 1/2 BW were obtained as follows:
______________________________________ .lambda..sub.max 1/2 BWReleased Dye (nm) (nm)______________________________________Control Compound A 670 161Control Compound B 535 101Compound 15 550 77______________________________________
The above data indicate that the compound according to the invention has a much purer magenta hue, has a .lambda..sub.max of 550 which is optimum, and a narrower 1/2 bandwidth and less unwanted blue absorption than the other two control compounds.
EXAMPLE 8
Comparative Test--Hues of Released Dyes
Spectra from various compounds were obtained in order to determine the effect of various substituents on rings of the compounds according to the invention. The following compounds were tested: ##STR32##
The above compounds were tested in the same manner as in Example 1. They were metallized with nickel. The following results were obtained:
______________________________________ .lambda..sub.max 1/2 BWReleased Dye (nm) (nm)______________________________________Control Compound A 670 161Control Compound C 620 85Control Compound D 595 95Compound 15 550 77Compound 14 560 83______________________________________
The above results indicate that changing the "G" group from OH to COOH, yet retaining the nitro group on the phenyl group, improves the 1/2 BW and shifts the hue 50 nm (Control Compound A versus Control Compound C), yet the compound is still far away from being a magenta dye.
When the nitro group is removed from Control Compound C, however, to become Compound 14 of the invention, a very dramatic improvement occurs as the .lambda..sub.max shifts from 620 to 560, to become a very good magenta dye with very little unwanted absorption. Compound 15 is even better than Compound 14 with a narrow 1/2 BW and a .lambda..sub.max at the optimum 550 nm.
Control Compound D is the same as Compound 14 of the invention, except that G in Control Compound D is OH instead of COOH. It is seen that Compound 14 has an improvement in hue (595 to 560), as well as a decrease in the 1/2 BW. Compound 14 also exhibited less unwanted absorption than Control Compound D.
The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.

Number	Name	Date
4013633	Haase et al.	Mar 1977
4108850	Fields et al.	Aug 1978
4165987	Green et al.	Aug 1979
4183753	Baigre et al.	Jan 1980
4204870	Chapman et al.	May 1980
4228073	Chapman et al.	Oct 1980
4250238	Baigre et al.	Feb 1981
4272434	Baigre et al.	Jun 1981
4273706	Chapman et al.	Jun 1981
4278598	Hinshaw et al.	Jul 1981

Nondiffusible 6-arylazo-3-pyridinol

Information

Patent Number

Date Filed

Date Issued

Inventors

Original Assignees

Examiners

Agents

CPC

US Classifications

Field of Search

US

International Classifications

Abstract

Description

Claims

Parent Case Info

US Referenced Citations (10)

Foreign Referenced Citations (1)

Divisions (1)