GB1601764A - Photosensitive photographic material - Google Patents

Description

PATENT SPECIFICATION

0 ( 21) Application No 22413/78 ( 22) Filed 25 May 1978 ( 31) Convention Application No 832 048 ( 32) Filed 9 Sept 1977 in c ( 33) United States of America (US) CI ( 44) Complete Specification published 4 Nov 1981 ( 51) INT CL 3 G 03 C 1/06, 5/54//C 07 C 103/76 ( 52) Index at acceptance G 2 C 20 X 212 221 223 242 27 Y 305 306 321 331 340 380 381 383 385 387 A 6 A C 19 Y C 21 C 2 C 222 227 22 Y 280 30 Y 321 32 Y 342 34 Y 365 36 Y 583 620 623 62 X 660 662 AA KH KP C 4 P 106 9 A 3 A 1 9 A 3 C 3 ( 72) Inventors JOSE MARTIN FERNANDEZ, MICHAEL DALE McCREARY, ROBERT EDWARD ROSS and JOHN TEWKSBURY STAPLES ( 11) 1 601764 ( 19) ( 54) PHOTOSENSITIVE PHOTOGRAPHIC MATERIAL ( 71) We, EASTMAN KODAK COMPANY, a Company organized under the laws of the State of New Jersey, United States of America, of 343 State Street, Rochester, New York 14650, United States of America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:-

This invention relates to photography In particular it relates to novel redox releasing compounds which can be used in photographic elements and processes to release dyes and other photographically useful groups as a function of silver halide development.

Published U S Patent Application B 351,673, dated January 28, 1975, discloses nondiffusible compounds which are alkali-cleavable upon oxidation to release a diffusible dye or dye precursor These compounds are known as redox releasing compounds One useful class of such compounds are ballasted dye-releasing sulphonamido compounds, including sulphonamidophenols and sulphonamidoanilines The ballast group which is attached to the sulphonamido compounds is an organic ballasting radical of such molecular size and configuration, including simple organic groups or polymeric groups, as to render the compounds non-diffusible during development in an alkaline processing composition A variety of specific individual ballast groups are suggested for use with the various sulphonamido compounds.

It has now been found that when the ballast group of a sulphonamido redox releasing compound is a N,N-disubstituted carbamoyl group, the compound exhibits an unexpectedly high degree of efficiency with respect to release of the photographically useful group.

In accordance with the present invention there is provided a photosensitive photographic material comprising a support bearing at least one photosensitive silver halide emulsion layer and contained therein or in an adjacent layer a nondiffusible redox releasing compound of the formula:

t CO-N NHSO 2 (I) wherein R' and R 2 are each an aliphatic, araliphatic or alicyclic group having 130 carbon atoms or an aromatic group having 6-30 carbon atoms, the groups R' and R 2 being of such size and configuration that the compound is rendered non-diffusible, G is -OR 5 or -NHIR 6 where R' is H or a hydrolysable group and R 6 is H, an alkyl of 1-22 carbon atoms or an -SO 2,-PUG group, Z represents the atoms necessary to complete a one-, two or three-ringed carbocyclic or heterocyclic group, which may be substituted, having 5-7 nuclear atoms in each ring, 5 PUG is the radical of a photographically useful compound and wherein the -NHSO 2 PUG group is joined to a position on Z so as to be conjugated to G.

The substituents R 1 and R 2 in the ballast group are of such size and configuration that the compound to which the ballast group is attached is rendered nondiffusible.

The term "non-diffusible" as used herein has its usual meaning in the art, viz, that 10 the compound will not, for all practical purposes, diffuse in the photographic material during processing with an alkaline processing solution Preferably R' and R 2 together contain a total of eight or more carbon atoms, e g, 8 to 50 carbon atoms.

Examples of cyclic groups completed by Z include benzene, naphthalene, anthracene, pyrazolone, pyridine, quinoline, pyrimidine, coumarin and indole 15 In a preferred embodiment Z completes a benzene or naphthalene ring, G is -OH or -NH 2 and the -NHSO 2-PUG group is meta to the ballasting carbamoyl group.

Examples of compounds from which PUG groups are derived include an imageforming dye or dye precursor, a development inhibitor, a development accelerator, a 20 bleach inhibitor, a bleach accelerator, a developing agent, a silver complexing agent, a fixing agent, a toner, a hardener, a fogging agent, and antifoggant, or a chemical or spectral sensitizer or a desensitizer.

Exemplary preferred R 1 and R 2 groups are alicyclic groups of 4 to 22 carbon atoms, e g cyclohexyl, cyclodecyl, or cyclooctadecyl, aliphatic groups such as straight 25 and branched chain alkyl groups of 1 to 22 carbon atoms, araliphatic groups such as aralkyl groups and aryloxyalkyl groups, e g methyl, butyl, dodecyl, benzyl, or phenoxypropyl, and aromatic groups such as aryl groups of 6 to 22 carbon atoms including alkaryl groups and alkoxyaryl groups (e g phenyl, naphthyl, methylphenyl or butoxyphenyl) 30 In a particularly preferred embodiment of this invention R 1 and R 2 are straight chain alkyl groups of 1 to 22 carbon atoms such as ethyl, pentyl, octyl, dodecyl, pentadecyl, octadecyl, or a 2,4-di-t-pentylphenoxybutyl group, and together R 1 and R 2 contain a total of eight or more carbon atoms In a highly preferred embodiment R 1 and R 2 each represent the same straight chain alkyl group containing 10 to 22 35 carbon atoms, such as decyl, dodecyl, pentadecyl or octadecyl.

In a particularly preferred embodiment of this invention G is -OH.

In a particular preferred embodiment of this invention PUG represents the radical of an image-forming dye or dye precursor Such dyes are well known to those skilled in the art and include azo, azomethine, azopyrazolone, indoaniline, indophenol, 40 anthraquinone, triarylmethane, alizarin, merocyanine, nitro, quinoline, cyanine, indigoide, phthalocyanine, metal complexed dyes, and dye precursors such as leuco dyes or shifed dyes.

These dye and dye precursor moieties may contain solubilizing groups, if desired, to aid in transfer of the dye Dye precursor moieties can be converted to dyes by 45 means well known to those skilled in the art, e g hydrolysis or oxidation, either in the photosensitive material, in a processing composition or in a dye imagereceiving layer to form the dye Preferred dyes and dye precursors are described in U S Patents 3,880,658, 3,931,144, 3,932,380, 3,932,381 and 3,942,987 As used hereinafter, unless the context indicates otherwise, the term "dye" includes dye precursors, it being 50 understood that the dye precursor is converted to the desired dye to form the final image.

Examples of ballasted redox dye releasing compounds which may be employed in the present invention include:

1,601,764 2 " 1 A Cyan Dye-Redox-Releasers :H 3 R 2 -( O C 2)4 o c 511 -t C 511 -t -C 12 H 25-n -C 8137-n -C 12 H 255-n -C 18 H 37-n O C 18 H 37 n ( 512)4 O CS H 11 -t c 5 H 11 -t XXXVIII -C 12 H 25-n VIII -C 8 Hl a-n cyclododecyl -C 18 H 37-n C 1 CH 3 -SO 2 N(CHCH 3)2 -502 N(CHCH 3 t) 2 (CH 14 s Hl 4 CM 11-t C 5 H 11 -t X -C 12 H 25-n Compound Number -C 2 H 5 -C,2 H 25-n -C 18 H 37-n -CUH 25-n -C 18 H 37-n -C 2 H 5 I II III IV V VI VII H H H Cl CI Cl Cl IX -C 4-IH 29-n Cl 1.601764 cyclododecyl H 1,601,764 B Magenta Dye-Redox-Releasers OH SO 2 z NHC(CH 3)3 CH 3502 NH Compound No.

(c 24 O c 5 C H 11 -t C 51 -t -C 12 H 25-n -C 8 H,-n O 18 C 8 H 37 n -(CH 2) 40 -C 5811 l -t Hll -t -C 8 H 37-n (CH 2) 4 O o-c 5 H 11 -t e 5 Hll O t -C 14 H 29,-n cyclododecyl XI XII XIII XIV XV XVI XVII XVIII XIX -C 2 Hb -CH, C 12 H 25-n -CH 3 -C 2 Hs -C 5 H,,n Cs Hli-n -C 8 H 37-n -C 14 H 29-n -C 4 HI 29-n -C 12 H 25-n c 7 1 -.

B Magenta Dye-Redox-Releasers ON 0 H 9 /el 2 \R NH Compound Number R Compound Number R.

XX -C 12 H 25-n o-0/ CH 3 502 N Hl' -C 12 H 25-n -C 12 H 255-n -CH 3 CH 2 CH 3 -CH 2 CH(CH 2) 3 CH 3 C 2 H s C Yellow-Dye-Redox-Releasers OCH 3 -C 2 H 25-n -C 1,H 3,-n CH 2 CH 3 i' -CH 2 CH(CH 2) 3 CH 3 14 H 29 n N Compound Number R 1 XXV -C 2 H 25-n XXVI -CH 3 R 2 -C 12 H 25-n -C 8 H-I 3,-n 0014 H 29 n -C 2 Hs XXI XXII XXIII XXIV XXVII 1.601764 Compound Number XXVIII XXVIX Compound Number XXX Rg -C 18 H 37-n -C 12 H 25-n OH R 1 -C.2 H 25-n OH COOH Compound Number R 1 XXXI -C 2 H 25-n 1,601,764 R 2 -C 18 H 37-n -C 112 H 25-n R 2 -C 2 H 25-n R 2 -C 12 H 25-n r, \R 2 7 1,601,764 7 D Cyan Dye-Redox-Releasers (Indophenol Dyes) OH O o, XXXII C:N(C 12 H 25)2 NH 2 (CH 2)3 COON O NC 0 CH 3 O N Ct OH OH O ii CN(C 18 H 37)2 XXXIII N 11502 CC NH6 ICNN N cl IH H 37)2 XXXIV 1,601,764 XXXV XXXVI CH 3 0 CN(C 12 H 25)2 Cl CH 3 i XXXVII R 9 1,601,764 9 E Leuco Cyan Dye-Redox-Releasers OH l BRAN (C 12 H 25) 2 xxxv"i NHSO 2 6-CON H XH NH Ct OH Photographic elements containing the redox releasing compounds employed in the present invention may be used in a variety of processes in which an imagewise distribution of the photographically useful compound is desired to aid in image 5 formation or enhancement The photographically useful compound may be released in an imagewise manner from the redox releasing compound by treating an imagewise exposed silver halide element containing a redox releasing compound with an alkaline processing composition (having a p H of e g 9-14) in the presence of a silver halide developing agent to effect development of the silver halide as a function of exposure 10 In developing silver halide, the developing agent is converted to its oxidized form, in which form it crossoxidizes (directly or indirectly) the redox releasing compound, which in its oxidized form cleaves thus releasing an imagewise distribution of the photographically useful compound This imagewise distribution can be used in a variety of ways to form or enhance a photographic image 15 The redox releasing compounds described herein have particular utility in diffusion transfer processes where it is desired to have a dye or dye precursor released imagewise However, in certain embodiments this invention relates to the release of an imagewise distribution of a diffusible photographically useful compound which is a photographic reagent Typical useful photographic reagents are known in the art, 20 such as in U S Patents 3,227,551, 3,698,898, 3,379,529 and 3,364,022, for example, a silver complexing agent, a toner, a hardener, an antifoggant, a fogging agent, a chemical or spectral sensitizer, a desensitizer, a developer, a development inhibitor, a development-accelerator, a bleach inhibitor or a bleach accelerator In other words, -NHSOPUG in the above formulae includes any moiety which, when combined 25 with a hydrogen atom, provides a photographic reagent upon cleavage.

The use of dye redox releasing compounds to form photographic colour images will be described in detail hereinafter as exemplary of the ways in which redox releasing compounds of this invention can be used.

Photographic colour images can be prepared with elements of this invention by 30 treating the element in the manner described above to form an imagewise distribution of diffusible dye or dye precursor as a function of the imagewise exposure of the silver halide emulsion Images can be formed employing the imagewise released diffusible dye, or the remaining imagewise distribution of unreacted dye redox releaser, or both The released diffusible dye or dye precursor can be allowed to diffuse to a 35 receiver sheet or layer to form a transfer image Alternatively, it can merely be removed from the element and not made further use of Whether the imagewise pattern of diffusible dye is used to form an image or not, the remaining dye redox releaser can be used as a retained image in the layer in which it was initially coated.

This mode of use could include removing residual silver and silver halide by any 40 conventional procedure known to those skilled in the art, such as a bleach bath followed by a fix bath or a bleach-fix bath In the event that the photographically useful group in the redox dye releaser is a dye precursor rather than a dye, the process for forming a retained image would include the step of converting the dye precursor lo 1.601,764 to the desired dye Alternatively, once the initially formed diffusible dye is removed from the element, the residual dye redox releaser can be employed to form a transfer image by oxidizing the dye redox releaser (e g by cross oxidation, or otherwise) to yield a second distribution of diffusible dye which can be transferred to a suitable receiver sheet or layer 5 A preferred process for producing a photographic transfer image in colour using compounds of our invention comprises the steps of:

1 treating an imagewise exposed photosensitive element of the invention with an alkaline processing composition in the presence of a silver halide developing agent to effect development of the silver halide emulsion layers as a 10 function of exposure, thereby oxidizing the developing agent and the oxidized developing agent in turn cross-oxidizing the dye redox releasing compound; 2 forming an imagewise distribution of diffusible released dye as a function of the development of the silver halide emulsion layers by cleaving, under alkaline conditions, cross-oxidized dye redox releasing compounds; and 15 3 diffusing out of the layer in which the dye redox releaser was coated at least a portion of the imagewise distributions of diffusible released dye.

The 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 compositions is by the use of a rupturable 20 container or pod which contains the composition In general, the processing composition contains the developing agent for development although the composition could just be an alkaline solution where the developer is incorporated in the photosensitive element, in which case the alkaline solution serves to activate the incorporated developer 25 A preferred photographic film unit according to our invention comprises:

1 a photographic element as described above; 2 an alkaline processing composition; and 3 means for discharging the alkaline processing composition within the film unit (such as a rupturable container which is adapted to be positioned during 30 processing of the film unit so that a compressive force applied to the container by 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 agent.

The film unit can include a dye image-receiving layer located on a separate 35 support adapted to be superposed on the photographic element after exposure thereof.

Such dye-image-receiving layers are generally disclosed, for example, in U S Patent No 3,362,819 When the means for discharging the processing composition is a rupturable container, typically it is positioned in relation to the photographic element and the image-receiving element so that a compressive force applied to the container 40 by pressure-applying members, such as found in a camera designed for incamera processing, will effect a discharge of the contents of the container between the dyeimage-receiving layer and the outermost layer of the photographic element After processing, the dye image-receiving element is separated from the photographic element 45 The film unit can include a dye image-receiving layer located integral with the photographic element Useful formats for integral receiver photographic elements is disclosed in Canadian Patents 928,559 and 928,560.

Still other useful integral formats in which the sulphonamido compounds can be employed are described in U S Patent Nos 3,415,644; 3,415,645; 3,415, 646; 50 3,647,437; and 3,635,707.

The photographic elements of the present invention can be used to produce positive images in single or multicolour In a three-colour system, the silver halide emulsion layers of the photographic element will have associated therewith a dyeimage-providing material, at least one of which is a dye redox releasing compound 55 of this invention, each dye-image-providing material possessing a predominant spectral absorption within the region of the visible spectrum to which said silver halide emulsion is sensitive, i e, the blue-sensitive silver halide emulsion layer will have a yellow dye-image-providing material associated therewith, the greensensitive silver halide emulsion layer will have a magenta dye-image-providing material associated 6 O therewith, and the red-sensitive silver halide emulsion layer will have a cyan dyeimage-providing material associated therewith Those silver halide emulsion layers that do not have associated therewith a dye redox releasing compound of this invention can have associated therewith another dye redox releasing compound or another dyeimage-providing material The dye redox releasing compound associated with the 5 silver halide emulsion layer can be contained either in the silver halide emulsion layer itself or in a layer adjacent to the silver halide emulsion layer.

The concentration of the dye re'dox releasing compounds 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, they may be 10 coated in layers as dispersions in a hydrophilic film-forming natural or synthetic polymer, such as gelatin or polyvinyl alcohol which is adapted to be permeated by aqueous alkaline processing composition Preferably, the ratio of dye redox releasing compound to polymer will be from 0 25 to 4 0 The compounds may then be incorporated in a gelatin by techniques known in the art (e g, use of a high boiling water 15 immiscible organic solvent or a low boiling or water miscible organic solvent) 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.

The silver halide emulsion layer(s) of the present photographic materials may 20 be negative or direct-positive emulsions.

Useful direct-positive emulsions are direct positive emulsions that form latent images predominantly inside the silver halide grains (as opposed to silver halide grains that form latent images predominantly on their surface) Such internal image emulsions are described in U S Patents 2,592,250, 3,761,276, 3,935,014 and 3,957,488 25 Such emulsions, when processed in the presence of fogging or nucleating agents provide direct positive silver images.

The solarizing direct-positive silver halide emulsions which may also be used are well-known silver halide emulsions which have been effectively fogged either chemically, such as by the use of reducing agents, or by radiation to a point which 30 corresponds approximately to the maximum density of the reversal curve as shown by Mees, Tlze Theory of the Photographic Process, published by the Macmillan Co, New York, New York, 1942, pages 261-297.

Negative silver halide emulsions useful in certain embodiments of this invention may comprise, for example, silver chloride, silver bromide, silver chlorobromide, silver 35 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.

Another embodiment of our invention uses the image-reversing technique disclosed in British Patent No 904,364, page 19, lines 1-41 In this system our redox dye-releasing compounds are used in combination with physical development nuclei -40 in a nuclei layer adjacent to the photosensitive silver halide negative emulsion layer.

The film unit contains a silver halide solvent, preferably in a rupturable container with the alkaline processing composition.

The silver halide emulsions useful in our invention are well known to those skilled in the art and are described in Product Licensing Index, (Research Disclosure), 45

Vol 92, December, 1971, publication 9232, p 107, paragraph I, "Emulsion types".

The following Examnles are provided for a further understanding of the invention.

Some results are illustrated in Figs 1-5 of the accompanying drawings.

Example 1.

Preparation of Compound XXV: 50 Step 1:

OH o OH 0 Co & CN(C 12 H 25)2 ch III 11 II= O NH(C 12 H 25)2 a To 26 5 g of the ester a were added 35 3 g of di-n-dodecylamine The mixture was heated at about 120 'C for 15 minutes The temperature of the oil bath was then 1 1 1.601764 14 -,_-,, v 12 increased to 180-190 C and the phenol sideproduct was removed under a vacuum aspirator The amber-coloured oil was then added while hot to 400 ml of nhexane.

No precipitation appeared on cooling and standing The solvent was removed in vacuo to yield an oil which gave a yellow precipitate on cooling in a dry iceacetone bath.

Crystallization from ethyl alcohol gave light-yellow crystals A second crystallization 5 from ethyl alcohol gave practically colorless crystals, m p 30-32 C.

Step 2:

OH O OH O o CN(C 12 125)2 CN(C 12 H 25)2 H 2 N-Q-(-OCH 3 N=NQO O CH 3 Ibc To 15 0 g of the naphthol b dissolved in methanol, sodium hydroxide and tetrahydrofuran, was added, at O C, a diazonium salt solution prepared from 3 7 g of p 10 anisidine, 30 ml of water, 9 0 ml concentrated hydrochloric acid and 2 1 g of sodium nitrite dissolved in 30 ml water The mixture was stirred for 30 minutes at 5 C A solution of 25 ml of glacial acetic acid in 300 ml of ice water was then added while stirring vigorously The bright orange precipitate turned a light brown The product was collected and was washed thoroughly with water 15 Step 3:

OH O OH o II If CN(C 125 H 2)2Na 2 52 04 C 2 H 2 N= N-Q-OCH 3 NH 2 c d To 9 2 g of the azonaphthol c dissolved in 200 ml of hot ethanol was added a solution of 6 0 g of sodium dithionite in 50 ml of water The reaction mixture was stirred vigorously while heating to reflux After 1/2 hour the dark solution had 20 become yellow in colour and an oil was visible on top of the solution The reaction mixture was stirred and heated for 1/2 hour followed by cooling in an ice bath with vigorous stirring At about 5 C the light oil solidified The off-white product was then collected and washed thoroughly with water Crystallization from n-hexane gave offwhite crystals; m p55-56 C 25 Step 4:

OH O 2 Cl Ig CN(C 12 M 25)2+ Compund f 1lll >Comoud M e d 1.601764 12) 13 1,601,764 13 To 4 0 g of the aminonaphthol d dissolved in 50 ml of dry pyridine were added 2.8 g of the sulphonyl chloride e at 12 C under nitrogen (temperature rose to about C) The reaction mixture was stirred at 15 C for 2 hours and at room temperature overnight The reaction mixture was then added to a mixture of 50 ml of concentrated hydrochloric acid and about 50 ml of ice water while stirring vigorously The product 5 was collected and washed thoroughly with water Crystallization from acetonitrile (twice) gave 2 5 g of yellow-orange crystals; m p 91-93 C.

Example 2.

Preparation of Compound XXI.

OH 502 Ct z C.N(C 12 H 2 5)2 9 pyridine Compound= o N=N 10 NH 2 N OH I OCH 3 d C:0 CN 3 f To 3 0 g of the aminonaphthol d (prepared according to Steps 1 through 3 of Example 1) dissolved in 50 ml of dry pyridine were added 2 6 g of the sulphonyl chloride f at 15 C under nitrogen The reaction mixture was stirred at 15 C for 2 hours and at room temperature overnight The reaction mixture was then added to a mixture of 50 ml of concentrated hydrochloric acid and 50 ml water with vigorous 15 stirring The magenta product was collected and washed thoroughly with water.

Crystallization from ethyl acetate gave 2 1 g of product; m p 185-188 C.

Example 3.

Retained Imaging By Solution Processing:

Colour photographic elements identified by the following schematic structure 20 were prepared The quantities of components are stated as grams/metre 2 in parenthesis.

Silver halide quantities are given in terms of silver.

Gelatin ( 1 08) Negative-working silver halide emulsion ( 1 35); Gelatin ( 2 70); Cyan, magenta 25 or yellow dye redox-releaser (see below) dissolved in half its weight of diethyl lauramide Cellulose acetate film support Separate elements contained a cyan, magenta or yellow dye redox releaser of 30 the invention, as compared to control elements containing dye redox releasers of the prior art having the same cyan, magenta and yellow dye moieties The incorporated dye redox releaser and its quantity in each element was as follows:

1,601,764 Element Cyan Dye Redox Releaser A (control) Compound 12 of U S 3,942,987 ( 0 92) Ri=H; R,= -(C 2) 4 o 9 C 5 H 11 -t C 5 H 1 l -t B (invention) Compound II ( 0 97) R 1 and R 2 =Ci 2 H 2,-n Magenta Dye Redox Releaser OH 502 NUC(CH 3).

v-OH CH 3 S Oz NH Element C (control) Com I Dound 6 of U S 3,932,380 ( 1 02) Ri=H; R= -(CH 2) 4 O C 5 H, -t C 5 H 11 -t D (invention) Compound XII ( 1 13) R 1 and R 2 =C, 2 H 2-n -NO 2 2 CH 3 Yellow Dye Redox Releaser OH CN \R 2 NH$ O N=N-1 ON Element E (control) Compound 1 of U S 3,923,510 ( 1 30) 5 Rc=,H; R 2 = (Co H 2)4 o c H 11 -t C 5 H 1 -t F (invention) Compound XXX ( 1 30) 10 R and Rd=C 2 H 25-n Samples of each element were exposed through a graduated density test object and processed by immersing the sample in a developer solution consisting of:

Na OH 2 2 g Nas PO 4 38 8 g 15 Na 2 S Oa 4 85 g K Br 10 0 g 5-Methylbenzotriazole 0 1 g 4-Hydroxymethyl-4-methyl 1phenyl-3-pyrazolidone 0 3 g 20 Water to 1 0 litre; p H adjusted to 11 5.

Elements A and B were developed for 8 minutes at 24 C, elements Q and D for 6 minutes at 24 C, and elements E and F for 3 minutes at 24 C All samples were then washed for 1 minute, bleach-fixed for 2 minutes, washed for 2 minutes and immersed in a p H 7 0 buffer solution for 1 minute There was obtained a graduated 25 density dye image.

The results were evaluated by generating from the dye images the density vs.

exposure curves shown in Figures 1, 2 and 3.

It is observed that the cyan, magenta and yellow dye images produced with the dye redox releasers of this invention demonstrate a substantial increase in photographic 30 speed and significant reduction in minimum densities Furthermore, to evaluate yellow stain, the density to blue light in the D>, areas of the dye images exhibited in Figures 1 and 2 were measured and showed 0 16 vs 0 09 for Element A vs B, and 0.21 vs 0 12 for Element C vs D.

Example 4 35

To compare the results at various processing p H's of dye-releasing-redox compounds of this invention relative to similar compounds of the prior art, two colour photographic elements, similar to Elements C and D of Example 3, were prepared according to the following schematic structures:

1,601,764 Element G (control) Gelatin ( 1 08) Negative-working silver halide emulsion ( 1 08); Gelatin ( 2 16) 5 Compound 6 of U S 3,932,380 ( 1.35) dissolved in diethyl lauramide ( 0 68) ///Cellulose acetate film support/// Element 10 H (invention) Gelatin ( 1 08) Negative-working silver halide emulsion ( 1 35); Gelatin ( 2 16) Compound XII ( 1 08) dissolved 15 in diethyl lauramide ( 0 54) /Cellulose acetate film support/ Samples of each element were exposed through a graduated-density test object and processed by immersing separate samples in portions of a developer solution differing only in p H for 1 5 and 6 minutes at 38 C The process was as follows: 20 Develop 1 5 or 6 minutes Wash 1 minute Bleach-fix 2 minutes Wash 1 minute Stabilize (p H 7 0 buffer) 1 minute 25 Developer Solution:

Potassium bromide 10 0 g 5-Methylbenzotriazole 0 1 g 4-Hydroxymethyl-4-methyl-1phenyl-3-pyrazolidone 0 3 g 30 Potassium phosphate 38 8 g Water to 1 0 litre; p H adjusted with KOH (see Table I)

The sensitometric results were measured by plotting the dye images as density 35 vs exposure curves and are tabulated in Table I.

1,601,764 1 K 17 1,601,764 17 TABLE I

1 5 Minute Development Blue D Green D Green D Max Dev Silver min mmin max Cmpd Cmpd Cmpd Cmpd.

p H Control XII Control XII Control XII Control XII 13.7 0 34 0 17 0 30 0 18 3 6 1 8 51 41 12.5 0 15 0 20 3 3 3712.0 0 33 0 13 0 87 0 26 3 9 3 2 48 33 11.5 0 39 0 18 1 33 0 63 4 0 3 4 44 32 11.0 0 53 0 32 2 32 1 52 4 0 3 4 30 24 10.5 0 71 0 47 3 28 2 26 3 9 3 5 14 22 10.0 0 91 0 59 4 20 2 74 4 2 3 5 05 18 The maximum developed silver is the analysed silver in g/m 2 obtained in areas of each sample.

the maximum exposed The reduced maximum dye density is the result of fog development, hence, the release of dye from unexposed areas.

TABLE I

6 0 Minute Development Blue Dmin Cmpd.

Control XII p H Green Dmin Cmpd.

Control XII Green Dmax Cmpd.

Control XII Max Dev Silver Cmpd.

Control XII 13.7 0 33 0 20 0 24 0 19 1 6 0 20 68 65 12.5 0 17 0 18 2 1 5712.0 0 28 0 15 0 64 0 18 3 7 3 1 69 52 11.5 0 30 0 14 0 82 0 22 3 8 3 3 69 53 11.0 0 34 0 17 1 28 0 50 3 9 3 4 60 50 10.5 0 56 0 43 2 32 1 45 4 0 3 4 37 38 10.0 0 85 0 49 3 83 2 40 4 4 3 5 18 31 The maximum developed silver is the analyzed silver in g/m 2 obtained in the maximum exposed areas of each sample.

The reduced maximum dye density is the result of fog development, hence, the release of dye from unexposed areas.

The data in Table I illustrates the following improvements with this invention:

( 1) lower green Dm, for the element of this invention compared with the control element This demonstrates a more effective release of dye per unit of developed 5 silver for the inventive element ( 2) lower blue D,, for the element of this invention compared with the control element This presumably is due to less yellow stain from the residual ballasted carrier moiety of the invention as well as less residual dye ( 3) Improved image discrimination for the inventive element, particularly under relatively low p H processing conditions is indicated by the larger difference between green D,; and green D ax for elements of this invention compared with the control element.

( 4) More rapid development This is suggested by the release of dye from unexposed areas at elevated p H conditions, which indicates that the development times employed 5 in this example were too long for the inventive element.

Example 5.

Colour Image Transfer.

A control element was prepared containing prior art sulphonamidonaphthol dye redox releasers The element was prepared by coating the following suitably hardened 10 layers in the order given on a transparent poly(ethylene terephthalate) film support.

The quantities of components are stated as grams/metre 2 in parenthesis unless specified otherwise Silver halide quantities are given in terms of silver.

Element I (control) ( 1) image-receiving layer of a polylstyrene-co-N-benzyl-N,N-dimethyl-Nvinyl 15 benzylammoniumsulphate-co-divinylbenzene) latex mordant ( 2 16) and gelatin ( 2 16); ( 2) reflecting layer of titanium dioxide ( 21 60) and gelatin ( 3 24); ( 3) opaque layer of carbon black ( 2 70) and gelatin ( 1 73); ( 4) cyan-dye-providing compound A ( 0 59) dissolved in diethyl lauramide 20 ( 0.30) and dispersed in gelatin ( 1 08); ( 5) red-sensitive, direct-positive silver bromide emulsion ( 1 35), gelatin ( 1 35), 5-sec-octadecylhydroquinone-2-sulphonic acid ( 16 g/mole silver), 1-l 4-( 2formylhydrazino)-phenyll-3-phenylthiourea (nucleating agent A) ( 3 5 mg/ mole silver), 1 acetyl 2 p l 5 amino 2 ( 2,4 di t pentyl 25 phenoxy)benzamidolphenyl hydrazine (nucleating agent B) ( 85 mg/mole silver); ( 6) interlayer of gelatin ( 1 62) and 2,5-di-sec-dodecylhydroquinone ( 1 30); ( 7) magenta-dye-providing compound B ( 0 54) dissolved in diethyllauramide ( 0 27) and dispersed in gelatin ( 1 22); 30 ( 8) green-sensitive, direct-positive silver bromide emulsion ( 1 35), gelatin ( 1.35), 5-sec-octadecyl-hydroquinone-2-sulphonic acid ( 16 g/mole silver) , 1 l 4 ( 2 formylhydrazino)phenyll 3 phenylthiourea ( 2 5 mg/ mole silver), 1 acetyl 2 p l 5 amino 2 ( 2,4 di t pentyl phenoxy)-benzamidol-phenyl}hydrazine ( 70 mg/mole silver); 35 ( 9) interlayer of gelatin ( 1 62) and 2,5-di-sec-dodecylhydroquinone ( 1 30); ( 10) yellow-dye-providing compound C ( 0 65) dissolved in diethyllauramide ( 0.32) and dispersed in gelatin ( 1 46); ( 11) blue-sensitive, direct-positive silver bromide emulsion ( 1 24), gelatin ( 1 24), 5-sec-octadecyl-hydroquinone-2-sulphonic acid ( 16 g/mole silver), 1 l 4 40 ( 2-formylhydrazino)phenyl-3-phenylthiourea ( 3 3 mg/mole silver), 1acetyl2 Up l 5 amino 2 ( 2,4 di t pentyl phenoxy)benzamidolphenyl hydrazine ( 80 mg/mole silver); ( 12) overcoat layer of gelatin ( O 89).

Compound A N 45 C 21 t CNHCH 2 C|HO C Ls XC 15 H 31 n O 902 CH 3 s,0 c 2 NO 2 1.601764 Compound B OH O a C C l HCC 2)40 C 5 ll-t C 5 H 1 l-t 502 NHC(CH 3)3 NH 50 H= OH CH 3 502 NH Compound C OH O CNH (CH 2)40 Co 9 C 5 H -t C 5 H 11-t H 502 9 Cl ON CN CN A second photographic element was prepared as above except that the cyan, S magenta and yellow dye redox releasing compounds were replaced with lesser amounts of dye redox releasing compounds according to this invention, which contained the same release dyes as the control Other variations included the use of less silver halide emulsion and gelatin and largely increased amounts of nucleating agents The element is described in terms of variation from the control as follows: 10 Element J (invention) ( 1-3) same as the control; ( 4) cyan dye redox compound IV ( 0 32) dissolved in diethyllauramide ( 0 16) and dispersed in gelatin ( 1 08); ( 5) red-sensitive, direct-positive silver bromide emulsion ( 0 92), gelatin ( 0 92), 15 nucleating agent A ( 4 5 mg/mole silver), nucleating agent B ( 125 mg/ mole silver) and other components similar to the control; ( 6) interlayer same as the control; ( 7) magenta dye redox releasing compound XII ( 0 32) dissolved in diethyllauramide ( 0 16) and dispersed in gelatin ( 1 22); 20 ( 8) green-sensitive, direct-positive silver bromide emulsion ( 0 92), gelatin ( 0.92), nucleating agent A ( 3 5 mg/mole silver), nucleating agent B ( 60 mg/mole silver) and other components similar to the control; ( 9) interlayer same as the control; ( 10) yellow dye redox releasing compound XXIX ( 0 43), dissolved in diethyl 25 lauramide ( 0 22) and dispersed in gelatin ( 1 46); ( 11) blue-sensitive, direct-positive silver bromide emulsion ( 0 92), gelatin ( 0 92), nucleating agent A ( 3 0 mg/mole silver), nucleating agent B ( 45 mg/mole silver) and other components similar to the control; ( 12) overcoat layer same as the control 30 Samples of the above-prepared photosensitive elements were exposed through a multicolour graduated density test object The exposed samples were then processed at 72 F ( 22 C) by rupturing a pod containing a viscous processing composition between the photosensitive element and a transparent cover sheet.

1,601,764 The processing composition was as follows:

Potassium hydroxide 46 8 g Sodium sulphite 1 0 g 5-Methylbenzotriazole 3 8 g 4-Hydroxymethyl-4-methyl-1 5 phenyl-3 pyrazolidone 12 0 g t-Butylhydroquinone 0 3 g Potassium fluoride 10 0 g Carbon dispersion (as carbon) 172 0 g Carboxymethyl cellulose 44 0 g 10 Water to 1 0 litre The cover sheet consisted of a transparent poly(ethylene terephthalate) film support having coated thereon:

( 1) a polyacrylic acid layer ( 189 meq/m 2) ( 2) a timing layer comprising 2 16 g/m 2 of a mixture of 89 % cellulose acetate 15 ( 40 % acetyl) and 11 % poly(styrene-co-maleic anhydride) (approximately % hydrolyzed) ( 3) a second timing layer comprising 2 16 g/m 2 of a latex dispersion of poly(acrylonitrile co-vinylidene chloride-co-acrylic acid.

Multicolour transferred images were produced in the receiving layer as viewed 20 through the transparent support The resulting images were evaluated by generating the characteristic curves (density vs exposure) shown in Figures 4 and 5.

It is observed from Figures 4 and 5 that substantially equal dye densities were produced with both elements, although significantly less material, e g silver halide, gelatin, and dye redox releasing compounds, were employed in the element of this 25 invention Additionally, a significant increase in speed, particularly in the green sensitive layer, was observed in the element according to this invention.

Example 6.

Photographic elements were prepared by coating a poly(ethylene terephthalate) film support with a light-sensitive layer comprising a negative-working silver halide 30 emulsion at 1 08 g/m 2, gelatin at 3 24 g/m 2, and one of a series of magenta redoxdye-releasing (RDR) compounds at 1 08 X 10-1 moles/m 2 dissolved in an equal weight of diethyl lauramide and dispersed in gelatin.

Separate samples of each element identified in the following Table were imagewise exposed through a graduated-density test object and processed at room tem 35 perature by laminating to a dye image receiving element and spreading a viscous processing composition therebetween.

The dye image receiving elements employed were comprised of a transparent poly(ethylene terephthalate) film support having coated thereon a layer comprising gelatin at 2 20 g/m 2 and poly(divinylbenzene-co-styrene-co-N-benzyl-N,Ndimethyl 40 N-vinylbenzyl ammonium chloride) at 2 29 g/m 2.

The processing composition consisted of a viscous solution containing:

Potassium hydroxide 60 g 4-Hydroxymethyl-4-methyl 1phenyl-3-pyrazolidone 2 0 g 45 Potassium bromide 20 g 5-Methylbenzotriazole 1 0 g Carboxymethyl cellulose 51 g Water to 1 0 litre After two minutes, the elements were separated The initiallyphotosensitive 50 samples were bleach-fixed, washed, treated in a p H 10 buffer solution and dried The receiver samples were washed and dried In each test, a well-defined negative dye image was transferred to the receiver and a positive dye image was retained in the samples of the initially-photosensitive elements.

The maximum and minimum transmission densities were measured for each 55 image and are recorded in the following table.

1,601,764 Compound Identification Magenta dye-releasers NH 502:02 NHC(CH 3)3 -OH CH 352 Compound XIV Compound XIX Compound XIII -C 2 H 5 -C 12 H 25 O C 18 H 37 n cyclododecyl -C 18 H 3,-n -CH 3 TABLE

Magenta-dye-releasers Retained Image Dmax Dmin Transferred Image Dmax Dmin Compound XIV 2 95 0 20 2 68 0 08 Compound XIII 3 02 0 25 3 00 0 12 Compound XIX 2 84 0 12 3 04 0 20 Identical dyes were released from all magenta dye releasers Example 7.

Photographic elements were prepared by coating a poly(ethylene terephthalate) film support with a light-sensitive layer comprising a negative-working silver halide emulsion at 1 08 g/m 2, gelatin at 3 24 g/m 2, and one of a series of cyan redox-dyereleasing (RDR) compounds at 7 56 X 10-4 moles/m 2 dissolved in an equal weight of 4-cyclohexanedimethanol-di( 2-ethylhexanoate) and dispersed in gelatin.

Separate samples of each element identified in the following table were imagewise exposed through a graduated-density test object and processed at room temperature by laminating to a dye image receiving element and spreading a viscous processing composition therebetween.

The dye image receiving elements employed were comprised of a transparent poly(ethylene terephthalate) film support having coated thereon a layer comprising gelatin at 2 29 g/m 2 and poly(divinylbenzene-co-styrene-co-N-benzyl-N,NdimethylN-vinvlbenzyl ammonium chloride) at 2 29 g Jm 2.

The processing composition consisted of a viscous solution containing:

1,601,764 1,601,764 Potassium hydroxide 4-Hydroxymethyl-4-methyl-1phenyl-3-pyrazolidone Potassium bromide 5-Methylbenzotriazole Carboxymethyl cellulose Water to g 2.0 g g 1.0 g 51 g 1.0 litre After two minutes, the elements were separated The initiallyphotosensitive samples were bleach-fixed, washed, treated in a p H 10 buffer solution and dried The receiver samples were washed and dried In each test, a well-defined negative dye image was transferred to the receiver and a positive dye image was retained in the samples of the initially-photosensitive elements.

The maximum and minimum transmission densities were measured for each image and are recorded in the following table.

Cyan dye-releasers OH NO 2 Compound VI Compound VII -C Hs O C 18 i H 37 n -(CH 2)4 O c 5 H ul -t C 5 H 11-t cyclododecyl -Cs H 11-n Compound XXXVIII -C 12 Hs-n TABLE

Cyan dye-releasers:

Retained image Dmax Dmin Transferred Image Dmax Dmin Compound VI 3 26 0 28 3 38 0 10 Compound VII 3 24 O 24 3 28 0 08 New Compound XXXVIII 3 04 0 30 2 86 0 15 Identical dyes were released from all cyan dye-releasers.

Claims (1)

1. WHAT WE CLAIM IS:-

   1 A photosensitive photographic material comprising a support bearing at least one photosensitive silver halide emulsion layer and contained therein or in an adjacent layer a non-diffusible redox releasing compound of the formula:

   IR z Co-N (I) " -5 \R 2 NN 502 wherein RI and R 2 are each an aliphatic, araliphatic or alicyclic group having 130 carbon atoms or an aromatic group having 6-30 carbon atoms, the groups R' and R 2 being of such size and configuration that the compound is rendered non-diffusible, 10 G is -OR 5 or -NHR 6 where R 5 is H or a hydrolysable group and R 6 is H, an alkyl of 1-22 carbon atoms or an -SO 2-PUG group, Z represents the atoms necessary to complete a one-, two or three-ringed carbocyclic or heterocyclic group, which may be substituted, having 5-7 nuclear atoms in each ring, 15 PUG is the radical of a photographically useful compound and wherein the NHSO 2 PUG group is joined to a position on Z so as to be conjugated to G.

   2 A photographic material as claimed in Claim 1 in which Z completes a benzene or naphthalene ring, G is -OH or -NH 2 and the -NHSO 2-PUG group 20 is meta to the ballasting carbamoyl group.

   3 A photographic material as claimed in Claim 1 or 2 in which PUG is the radical of a dye or dye precursor.

   4 A photographic material as claimed in any of Claims 1-3 in which R 1 and R 2 are both straight chain alkyl groups containing a total of 8-50 carbon atoms 25 A photographic material as claimed in any of Claims 1 -4 in which at least one silver halide emulsion layer comprises a direct-positive emulsion.

   6 A photosensitive photographic material according to Claim 1 substantially as described herein and with reference to the Examples.

   L A TRANGMAR, B Sc, C P A.

   Agent for the Applicants.

   Printed for Her Majesty's Stationery Office by the Courier Press, Leamington Spa, 1981.

   Published by the Patent Office, 25 Southampton Buildings, London, WC 2 A l AY, from which copies may be obtained.

   1,601,764