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Photographic element and process

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US3457072A
US3457072A US3457072DA US3457072A US 3457072 A US3457072 A US 3457072A US 3457072D A US3457072D A US 3457072DA US 3457072 A US3457072 A US 3457072A
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silver
halide
out
photographic
layer
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Joseph R Ditzer Jr
Fred W Spangler
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Eastman Kodak Co
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/005Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/46Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein having more than one photosensitive layer
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/005Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/49Print-out and photodevelopable emulsions

Description

y 1969 J. R. DITZER, JR.. ETAL 3,457,072

PHOTOGRAPHIC ELEMENT AND PROCESS Filed Oct. 22, 1965 SILVER HAL/0E PRINT-OUT EMULSION m m TRANSPARENT su 097 mm SILVER HAL/0E DEVELOPl/YG-OUT NEGATIVE EMULS/ON PR/NF- 00 T DEVELOP/N6 00 7' E M UL .5 ION NEG'A T/ 5 EMULSION SUPPO/i T JOSEPH R. D/TZER,JR.

FRED W SPANGLER INVENTORS BY fiMM gWQ- QQ/ A TTOR/VEYS 3,457,072 PHOTOGRAPHIC ELEMENT AND PROCESS Joseph R. Ditzer, Jr., and Fred=W. Spangler, Rochester,

N.Y., assignors to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey Filed Oct. 22, 1965, Ser. No. 500,989 Int. Cl. G03c 1 78, 5/04 U.S. Cl. 96--27 14 Claims ABSTRACT OF THE DISCLOSURE This invention relates to novel photographic elements and methods for processing such elements.

Automatic photomechanical drafting equipment can be utilized to prepare a plurality of images on a photographic support. Such equipment provide for mechanical and optical means which allow an operator to position an image on the surface of a light-sensitive element. With such equipment, exposure is made in a particular area of the light-sensitive element, and thereafter, a second image is positioned in a dilferent area and a second exposure made, and so on for third, fourth or fifth exposures, if desired. In the operation of devices of this type, it is essential that each subsequent exposure be positioned accurately in relation to prior exposures. It would be highly desirable for the more accurate positioning of each exposure it the operator could immediately see a visible image in each exposed area before positioning the image for a second exposure.

It is an object of the invention to provide novel photographic elements suitable for use in automatic photomechanical drafting equipment.

It is another object of this invention to provide novel photographic elements which will produce a visible image immediately upon exposure to light, and which upon subsequent chemical processing, will'produce a high density silver image with low background density.

It is likewise an object of this invention toprovide a new process for preparing a plurality of images on a photographic element in a predetermined relationship to each other utilizing a plurality of image exposures, the image positioning for each exposure being determined from visible images resulting from any previous image exposures.

These and other objectsof the invention are accomplished with a photographic element comprising a substantially transparent support having coated thereon a printout silver halide layer that does not chemically develop to substantial density in low silver halide solvent-action "United States Patent 0 developing compositions and a high contrast fine-grain developing-out negative silver'halide layer that is chemically developable in low silver halide solvent-action developing compositions. A print-out image forming in the print-out silver halide layer of such photographic element is visible from both sides of the photographic element, and the silver halide layers of the photographic element are capable of being fixed with silver halide solvent such as alkali metal thiosulfates'The print-out silver halide layer and the developing-out negative silver halide ice layer are more generally positioned on opposite sides of the support although such silver halide layers can be positioned on the same side of the support.

In utilizing the photographic elements of the invention, the photographic element is positioned so that the print-out silver halide layer is closest to the exposing light source. The photographic element is exposed in a predetermined position with a suitable light source to produce a discernible print-out image when viewed through the photographic element. The exposure to produce the print-out image in the print-out silver halide layer also produces a corresponding latent image in the developing-out negative silver halide layer. The print-out image is used by the operator to position subsequent exposures. The operator is able to detect positional errors of earlier exposures as visible records of such earlier exposures occur in the print-out silver halide layer. After completion of the exposures, the photographic element is processed in a low silver halide solvent-action developing compositon, and thereafter fixed, washed and dried in the usual manner. Unexposed and undeveloped silver halide in both the print-out silver halide layer and the developing-out negative silver halide layer is removed during processing to leave high contrast fine-grain silver images in the areas of exposure in the developing-out negative silver halide layer.

The drawings illustrate diagrammatically in section and in an elevation typical embodiments of the inven tion, FIG. 1 illustrating a typical photographic element of the invention and FIG. 2 illustrating the typical exposure means for the photographic elements of the invention.

With respect to the photographic element of FIG. 1, on one side of transparent support 11 is positioned silver halide print-out emulsion layer 10 and on the other side silver halide developing-out negative emulsion layer 12.

FIG. 2 illustrates a typical exposure means for exposing a photographic element of the type described in FIG. 1. From light source 13, light passes through condenser lens system 14. Thereafter, the exposure light passes through image negative 15 which is focused by lens system 16 on the photographic element comprising transparent support 18 having coated thereon silver halide print-out emulsion layer 17 and silver halide developingout negative emulsion layer 19. A visible silver print-out image is formed in print-out emulsion layer 17, and which print-out image is visible through the photographic element to operator 20. A latent image is formed in the developing-out emulsion layer 19. The exposure apparatus illustrated by FIG. 2 is typically in a light-proof enclosure to prevent fogging of the light-sensitive element of the invention, although safelights can be used in the absence of such an enclosure.

Any print-out silver halide that does not chemically develop to substantial density in low silver halide solvent acting development compositions can be utilized for the light-sensitive layer used to form the print-out image of the present photographic elements. Such print-out silver halide systems can be prepared in the absence of a hinder or dispersing agent such as by vacuum deposition of the silver halide, although We prefer to utilize print-out silver halide emulsion systems for forming the print-out image in the present photoelements. Typical print-out silver halide systems are the so-called internal image-forming systems, such having silver halide grains wherein a pre dominant amount of the sensitivity is internal to the grains. Such internal image-forming systems are those which, when measured according to normal photographic techniques by coating a test portion of the emulsion on a transparent support, exposing to a light intensity scale having a fixed time between 1X10 and 1 second,

bleaching 5 minutes in a 0.3% potassium ferricyanide solution at 65 F. and developing for about 5 minutes at 65 F. in Developer B below (an internal-type developer), have a sensitivity, measured at a density of above fog, greater than the sensitivity of an identical test portion which has been exposed in the same way and developed for 6 minutes at 68 (a surface-type developer).

Sodium thiosulfate Water to make 1 liter.

The preparation of such internal image-forming silver halide systems are disclosed in: Davey et al., US. Patent 2,592,250, issued Apr. 8, 1952; Glafkides, Photographic Chemistry, vol. 1, pp. 31-2, Fountain Press, London; and copending McBride application, U.S. Serial No. 45 2,009 filed Apr. 29, 1965, now Patent 3,271,157 wherein 1s d 1sclosed the preparation of silver halide emulsions with organic thioether silver halide solvents present during the grain growth of the silver halide. In the above-mentioned copending application is taught the addition of the thioether silver halide solvent to the colloidal material in which the silver halide is precipitated, during the precipitation of the silver halide, or to the silver halide prior to F. in Developer A below least..two .,n.itrogenatoms.and at leastone divalentradical having the formula,

wherein X can; be,asulfur,atom,,an oxygenatom, a selenium atom or an .imino radical (:NH). When a nitrogen atom comprising D or R is attached directly to the nitrogen at oms of the above formulas, at least one hydrogen atom is attached to at least one of such nitrogen atoms of the halogen acceptor. The amino radical for sub'stitutent R can be represented by the formula,

wherein'R and R can each typically be such substitu- I cuts as hydrogen atoms, alkyl radicals, aryl radicals or acyl radicals as described above for R1 and R The thiocarbamylradical for substitutent R can be represented by the formula,

s R1 {|E .N/

wherein R and R can be the same substitutents as R and R or amino radicals.

or during the ripening of the silver halide. Typical of such thioethers are 3,6-dithia 1,8 octanediol, 1,10 dithia- 4,7,13,16-tetraoxacyclooctadecane, 7,10-diazo-1,16 dicarboxamido-3,l4-dithiahexadecane-6,1l-dione, and 1,17-di- (N-ethylcarbamyl)-6,12-dithia 9 oxaheptadecane. The amount of thioether utilized to prepare such silver halide emulsions can be widely varied although about .1 to 25 g. of thioether per mole of silver halide is generally utilized. The halide of the print-out silver halide is preferably at least 50 mole percent bromide, and the silver halide grains generally have an average grain size of about .1 to 10 microns, and more generaly about .5 to 1 micron.

Print-out silver halide systems typically contain halogen acceptors, such addenda being preferably utilized in the present invention. Preferred halogen acceptors are nitrogen-containing halogen acceptors, particularly those having the formulas l l 1 and R -NR wherein: R, R and R can each be hydrogen atoms, alkyl radicals, aryl radicals, including substituted alkyl and aryl radicals, or acyl radicals (e.g.,

0 ll C R4 wherein R is a hydrogen atom, an alkyl radical or an aryl radical); R can be a nitrogen-containing radical such as an amino radical or a thiocarbamyl radical, in-

eluding substituted amino and thiocarbamyl radicals; and

D represents the necessary atoms to complete a heterocyclic nucleus generally having 5 or 6 atoms including at Particularly useful nitrogen-containing halogen acceptors used in the emulsions of the'invention can be further represented by the following subgeneric formulas:

'azine-thiol, a thiobarbituric acid, a thiouracil, a urazole including'a thiourazole and'the like heterocyclic moieties. With respect to the above formulas of nitrogen-containing halogen acceptors: the aryl radical substitutents are those of the naphthyl and phenyl series; and include such common substitutents "as alkyl groups, halogen atoms, acyl radicals and the like; the alkyl radical substit uents typically can contain 1 to 20 carbon atoms and more generally 1 0 8 carbon atoms, and can be substituted with such radicals as aryl radicals, halogen atoms, acyl radicals and the like. 7

Typical useful halogen acceptors of the thiourea type represented by Formula A and Formula B are disclosed in copending Kitze application, US. ,Ser. No. 303,146, filed Aug. 19, 1963, now Patent 3,241,971; andin copendmg Fix applicatiOnQUS. Ser.' N o. 338,605, filed Jan. 20, 1964,"n'ow Patent 3,326,689. Typical halogen acceptors of the'lhydrazine type represented by Formula'C are disclosed in Ives, U,S. Patent"2,588,982. issued Marfll, 1952. Typical halogen acceptors of the type represented by Formula D are the urazole and thiourazole halogen acce'ptors disclosed in"Bacon 'and lllingsworth application,

U.S. Ser. No. 406,186, filed Oct. 23, 1964, now Patent 3,396,017.

Examples of specific nitrogen-containing halogen acceptors are set out below.

1,3-dimethyl-2-imidazolidinethione 2-imidazolidinethione 1-phenyl-5mercaptotetrazole Thiosemicarbazide Tetramethylthiourea p-Dimethylaminobenzaldehyde-thiosemicarbazone 1-isopentyl-2-thiourea 1-(Z-diethylarninoethyD-1,2,5,6-tetrahydro-1,3,5-

triazine-4-thiol 1,2-bis( 1,2,5,6-tetrahydro-1,3,5-triazine-4-thiol) ethane l-phenyl-Z-thiourea 1,3-diphenyl-2-thiourea 4-thiobarbituric acid 2-thiouracil l-acetyl-Z-thiourea 1,3-dibenzyl-2-thiourea 1,1-diphenyl-2-thiourea l-ethyl-1-(u-naphthyl)-2-thiourea Z-mercaptoimidazole 1-phenyl-2-imidazolidinethione 4,5-dipheny1-4imidazolidine-2thione 1-methyl-2-mercaptoimidazole l-n-butyl-1,2,5,6-tetrahydro-1,3,5-triazine-4-thiol Thiourea l-methyl-Z-imidazolidinethione D-mannose thiosemicarbazone Morpholino-Z-propane thiosemicarbazone D-galactose thiosemicarbazone Urazole 3-thiourazole 3,5-dithiourazole 3,5-dithiourazole hydrazine salt 4-aminourazole hydrazine salt Urazole sodium salt 4- l-naphthyl urazole 4-ethylurazole l-phenylurazole 4-phenylurazole l-butylurazole l-octylurazole 4-butyl-3,5-dithiourazole 1,4-diphenylurazole 1,4-dibutylurazole 1,4-dibutyl-3,S-dithiourazole 1,4-diphenyl-3,5-dithiourazole 1-ethyl-4-phenylurazole 1-ethyl-4-phenyl-3,S-dithiourazole 3-thio-5-iminourazole 5-selenourazole Hydrazine Phenylhydrazine hydrochloride 2,5-dichlorophenyl hydrazine p-Tolylhydrazine hydrochloride a-Naphthylhydrazine oa-Benzyl-a-phenylhydrazine p-Toluene sulfonyl hydrazine Hexylhydrazine Other typical halogen acceptors that can be used in the invention include aromatic mercaptans such as thiosalicylic acid; hydroquinones such as hydroquinone, chlorohydroquinone, gentisic acid and t-butylhydroquinone; catechols such as phenyl catechol and t-butylcatechol; paminophenols such as N-methyl-p-aminophenol.sulfate; 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, 4-methyl-1-phenyl-3-pyrazo1idone and 1-phenyl-4,4-dimethyl-3- pyrazolidone; phenylenediamines; nitriles; phenols; glycine; alkaline materials such as borax, alkali metal hydroxide, etc.; and the like halogen acceptors well known to those skilled in the art.

The concentration of halogen acceptors utilized in the print-out silver halide layer of the invention can be widely varied in accordance with usual practice. Usually, about .01 to mole percent, and more generally about .1 to 25 mole percent, based on the silver halide is utilized.

Silver halide print-out systems particularly useful in preparing the photographic elements of the invention are prepared with silver halide that has been precipitated or formed in the presence of lead ions. Water-soluble lead salts are suitably added with the water-soluble silver salt to an appropriate water-soluble halide to precipitate the lead-silver halide of the present emulsions. Typical suitable water-soluble lead or plumbous salts include lead acetate, lead nitrate, lead cyanide, and the like. The amount of lead utilized in the silver halide of the emulsions of the invention suitably ranges from about .01 to 5 mole percent based on the silver halide. The presence of a water-soluble lead salt during the silver halide formation or grain growth when preparing the light-developable, direct-print emulsions of the invention is to be distinguished from the addition of a water-soluble lead salt shortly prior to coating and after the silver halide grains have been formed.

The developing-out negative silver halide layer of the present photographic elements is a high contrast, finegrain silver halide which typically has a gamma of at least about 3. Typically, such a silver halide layer has an average particle size less than about one micron and more generally less than about .5 micron. High contrast or high gamma emulsions are well known in the graphic arts field and can be prepared by techniques well known in the art. Fine-grain Lippmann emulsions such as those referred to by Mees, The Theory of the Photographic Process, the MacMillan Company, New York, 1942 edition, page 34, can be utilized for the present developingout negative silver halide layer. Suitable developing-out negative silver halide is that which is chemically developable in conventional developing compositions having low silver halide solvent-action and which has silver halide that forms latent images predominantly on the surface. The halide of the developing-out negative silver halide is preferably at least 50 mole percent chloride. Such developing-out negative silver halide systems can be prepared in the absence of a binder or dispersing agent such as by vacuum deposition of the silver halide, although we prefer to utilize developing-out silver halide emulsion systems.

The silver halide in the layers comprising the photographic elements of the invention are preferably coated on the support as emulsions of hydrophilic water-permeable organic colloids wherein the silver halide is dispersed therein. Gelatin is more generally utilized although other colloidal material such as colloidal albumin, cellulose derivatives, synthetic resins or the like are useful. Suitable colloids that can be used are polyvinyl alcohol or a hydrolyzed polyvinyl acetate as described in Lowe. U.S. Patent 2,286,215, issued June 16, 1942; a far hydrolyzed cellulose ester such as cellulose acetate hydrolyzed to an acetyl content of 1-9 to 26% as described in U.S. Patent 2,327,808 of Lowe and Clark, issued Aug. 24, 1943; a Water-soluble ethanolamine cellulose acetate as described in Yutzy, U.S. Patent 2,322,085, issued June 15, 1943; a polyacrylamide having a combined acrylamide content of 30 to 60% and a specific viscosity of 0.25 to 1.5 on an imidized polyacrylamide of like acrylamide content and viscosity as described in Lowe, Minsk and Kenyon, U.S. Patent 2,541,474, issued Feb. 13, 1951; zein as described in Lowe, U.S. Patent 2,563,791, issued Aug. 7, 1951; a vinyl alcohol polymer containing urethane carboxylic acid groups of the type described in Unruh and Smith, U.S. Patent 2,768,154, issued Oct. 23,1956; or containing cyano-acetyl groups such as the vinyl alcohol-vinyl cyanoacetate copolymer as described in Unruh, Smith and Priest, U.S. Patent 2,808,331, issued Oct. 1, 1957; or a polymeric material which results from polymerizing a protein or a saturated acylated protein with a monomer having a vinyl group as described in Illingsworth, Dann and Gates, US. Patent 2,852,382, issued Sept. 19, 1958. Mixtures of such organic colloids can also be used. I

The light-sensitive silver halide layers utilized in preparing the photographic elements of the invention can contain or have associated therewith the addenda generally utilized in such products including antifoggants, hardeners, plasticizers, coating aids and the like. The light-sensitive silver halide layers of the subject photographic elements are characterized as having high sensitivity to light having shorter wavelengths, particularly to light in the ultraviolet region of the spectrum, and low sensitivity in the green and red regions of the spectrum. Hence, the subject silver halide systems are free of spectral sensitization for the longer wavelengths. Preferably, yellow filter dyes or pigments are utilized in the silver halide layers, particularly in the silver halide printout layer as a blue light filter and to avoid blue light scatter to produce a sharper image in the developingout negative silver halide layer. Such filter materials are removed during processing. The developing-out negative silver halide layer preferably contains a photographic desensitizing compound to reduce its sensitivity and to prevent overexposure of this layer when the print-out silver halide layer is suitably exposed to produce a printout image therein. Silver halide desensitizing data are well known to those skilled in the present art, suitable desensitizers include heterocyclic compounds containing at least one hetero atom such as sulfur or nitrogen, anthraquinone dyes and the like.

Any of the conventional transparent photographic sup ports can be utilized in preparing the photographic elements of the invention. Typical of such supports include glass, cellulose nitrate film, cellulose acetate film, polyethylene terephthalate film, polystyrene film, polycarbonate film, and related transparent materials.

In utilizing the photographic elements of the invention, a light source that is rich in ultraviolet light is typically utilized. In utilizing an exposure apparatus illustrated by FIG. 2 of the drawing, the print-out silver halide layer of the photographic element is faced toward the light source with the developing-out negative silver halide layer facing the operator. Typically, a suitable safelight filter (Kodagraph orange sheeting) is placed between the operator and the photographic element to prevent fogging and to facilitate viewing in roomlight. A red filter (e.g., No. 25 Wratten filter) is typically positioned in the image beam to prevent a premature exposure While the image is being visually positioned on the photographic element by the operator. For the exposure step, the red light filter is removed from the light path and an immediate print-out image is discernible to the operator, this printout image typically having a density of the magnitude of about .05 to .1. The subject photographic elements are of such thickness and composition that such a printout image can be observed through the photographic element. Simultaneously, the developing-out negative silver halide layer is exposed and a latent image formed therein. The visible print-out image is used by the operator to position subsequent exposures and to detect positional errors of earlier exposures.

After the sequential image exposures of a photographic element of the invention are complete, the exposed element is chemically developed in a conventional low silver halide solvent-action or surface latent image silver halide developing composition. Such processing develops to metallic silver the latent images in the developing-out negative silver halide layer. Suitable developing compositions are aqueous alkaline compositions containing a silver halide developer such as a 3-pyrazolidone, hydroquinone, hydroquinone derivatives such as N-methyl-p-aminophenol, or the like, and which developing compositions are free of substantial amounts of such silver halide solvents as thiosulfates and thiocyanides (i.e., insufiicient to develop internal latent image-forming silver halide grains of the type used in the print-out silver halide layer).

The invention is further illustrated by the following example of a preferred embodiment thereof.

EXAMPLE A light-sensitive, large-grain, direct-print, gelatino silver chlorobromide emulsion (about mole percent bromide and about 5 mole percent chloride) having silver halide grains of high internal sensitivity Was prepared by slowly adding an aqueous solution of silver nitrate containing .85 gram of lead nitrate per mole of silver to an agitated gelatin solution of potassium bromide and potassium chloride at 71 C. To the resulting emulsion was added five grams of tartrazine yellow, seven grams of the tetrahydro-1,3,5-triazine-4-thiol as a halogen acceptor, 0.5 gram of Z-anthraquinone sulfonic acid sodium salt and two grams of formaldehyde, such emulsion addenda being added in the amounts indicated per each mole of silver halide. The resulting print-out emulsion was coated on a polyethylene terephthalate film support at a coverage of 200 mg. of silver per square foot. On the opposite side of the support was coated a developing-out negative silver chloride emulsion layer at a coverage of 200 mg. per square foot, the silver chloride having an average particle size less than 0.5 micron. This developing-out negative silver halide emulsion also contained one gram of the S-nitroindazole as a desensitizer, 5 grams of tartrazine yellow as a filter dye, 8 grams of 4- hydroxy-6-methyl-l,3,3a,7-tetrazaindene as an antifog gant, and one gram of formaldehyde per mole of silver halide. The resulting film was successively exposed with a high intensity ultraviolet light (220-watt mercury arc lamp) to a plurality of images in a photomechanical drafting device of the type described hereinabove with reference to FIG. 2 of the drawing. The print-out emulsion layer of the photographic element was positioned, facing the image light source, and the developing-out negative emulsion layer of the photographic element was positioned facing the operator in the manner illustrated by FIG. 2 of the drawing. A Kodagraph orange sheeting was placed between the operator and the developing-out negative silver halide emulsion layer to prevent fogging when viewing in room-light. The print-out silver halide emulsion layer was exposed for a sufficient length of time to produce a print-out image which was visible to the operator through the photographic element. A plurality of such exposures were made in different areas of the photographic element, each exposure producing a print-out image visible through the photographic element, and a corresponding latent image in the developing-out negative silver halide emulsion layer. After completion of the exposures, the photographic element was processed by developing for three minutes at 68 F. in Kodak Dl9 developer, and thereafter fixed in hypo, washed and dried in the usual manner. After processing, sharp, high contrast silver images resulted in the areas of exposure of the developing-out negative silver halide emulsion layer.

The invention has been described in considerable 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 as described hereinabove and as defined in the appended claims.

We claim:

1. A photographic element comprising a substantially transparent support having coated thereon an internalimage print-out silver halide layer comprising gelatin and at least one other compound which is a halogen acceptor wherein said print-out silver halide layer does not chemically develop to substantial density in low silver halide solvent-action developing compositions, and a highcontrast fine-grain developing-out negative silver halide layer that is chemically developable in said low silver halide solvent-action developing compositions whereby a print-out image in said print-out silver halide layer will be visible from both sides of said photographic element.

2. A photographic element comprising a substantially transparent support having coated on opposite sides thereof a print-out silver halide emulsion layer comprising silver halide grains that form latent images predominant- 1y internal to said grains, gelatin, and at least one other organic compound which is a halogen acceptor and a high-contrast fine-grain developing-out negative silver halide emulsion layer having silver halide grains that from latent images predominantly on the surface of said grams whereby a print-out image in said print-out silver halide emulsion layer will be visible from said developing-out negative silver halide emulsion layer side of said photographic element.

3. A photographic element as described in claim 2 wherein the silver halide emulsion layers are gelatino silver halide emulsion layers.

4. A photographic element as described in claim 2 wherein the print-out silver halide emulsion layer contains a nitrogen-containing halogen acceptor.

5. A photographic element as described in claim 2 wherein the silver halide of the print-out silver halide emulsion layer was formed in the presence of lead ions.

6. A photographic element as described in claim 2 wherein at least one of the silver halide emulsion layers contains yellow filter dye.

7. A photographic element as described in claim 2 wherein the support is polyethylene terephthalate film.

8. A photographic element as described in claim 2 wherein the halide of the print-out silver halide is at least 50 mole percent bromide, and wherein the halide of the developing-out negative silver halide is at least 50 mole percent chloride.

9. A photographic element as described in claim 2 wherein an image in the developing-out layer will be visible from either side of the element after said element is processed in a low silver halide solvent-action developing composition.

10. A photographic element according to claim 1 wherein said print-out silver halide layer comprises from about .01 to 100 mole percent, based on the silver halide of a halogen acceptor.

11. A photographic element according to claim wherein said halogen acceptor is a nitrogen-containing halogen acceptor.

12. A photographic element according to claim 2 wherein said print-out, silver halide layer contains from .1 to 25 mole percent, based on said silver halide, of a halogen acceptor.

13. A photographic element according to claim 12 wherein said halogen acceptor is tetrahydro-1,3,5-triazine- 4-thiol.

14. In a process for preparing a plurality of silver images with a photographic element comprising a substantially transparent support having coated thereon an internal-image print-out silver halide layer that does not chemically develop to substantial density in low silver halide solvent-action developing compositions, and a high-contrast fine-grain developing-out negative silver halide layer that is chemically developable in said low silver halide solvent-action developing compositions whereby a print-out image in said print-out silver halide layer will be visible from both sides of said photographic element, wherein said process comprises imagewise exposing said photographic element to a light source rich in ultraviolet light with the print-out silver halide layer more proximate to the said exposing light source than the developing-out negative silver halide layer, forming a print-out image in the print-out silver halide layer and a corresponding latent image in the developing-out negative silver halide layer, sequentially repeating the imagewise exposure utilizing the print-out image to position each exposure, and thereafter chemically developing to silver the latent images in the developing-out negative silver halide layer with a low silver halide solvent-action developing composition.

References Cited UNITED STATES PATENTS 2,036,369 4/1936 Simsian 9668 3,178,282 4/ 1965 Luckey et a1 96-68 3,253,918 5/ 1966 Condax 96-44 .NO'RMAN G. TORCHIN, Primary Examiner J. R. EVERETT, Assistant Examiner US. Cl. X.R.

22 33 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3, L457, 072 Dated uly 22, 4 1 9 9 In ntoflsdjos enh R. Ditzer. Jr, and Fred W. Spengler- It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 2, line 20, "compositon" should read ---oompositio Column 3, line hit, "7,10diazo-1 ,16" should read 7,10- diaza-1 ,16 line 53, "generaly" should read ---generally-. Column line 11 line 21 line 27, line 57, line 59, "substitutents' should read ---substituents---. Column 9, line 12, "from" should read ---form---; line 13, "grams" should read grains---. Column 1 0, line 38, "Simsian" should read Simjian---.

SIGNED AND SEALED MAR 3 511970

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DE (2) DE1547741A1 (en)
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Cited By (7)

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US3511658A (en) * 1966-09-28 1970-05-12 Keuffel & Esser Co Photographic reproduction materials
US3547647A (en) * 1967-10-02 1970-12-15 Eastman Kodak Co Photographic systems comprising silver halide particles with occluded metal ions therein,a halogen acceptor,and an organic aldehyde
US3647463A (en) * 1969-08-14 1972-03-07 Eastman Kodak Co Direct-positive photographic elements containing multiple layers
US3784375A (en) * 1969-12-22 1974-01-08 Eastman Kodak Co Ectrostatic image forms a developable image in a silver salt
US3844789A (en) * 1967-03-06 1974-10-29 Gaf Corp Composite film elements
US3864134A (en) * 1971-10-28 1975-02-04 Fuji Photo Film Co Ltd Silver bromoiodide photographic emulsion with improved green sensitivity
US4373022A (en) * 1978-12-28 1983-02-08 Arnold Hoffman Method and apparatus for producing a high speed high resolution radiation sensitive article and a high speed high resolution radiation sensitive article

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US3503746A (en) * 1967-05-03 1970-03-31 Eastman Kodak Co Use of an enzyme inhibitor to retard the degradation of gelatin
US3647459A (en) * 1967-06-28 1972-03-07 Eastman Kodak Co Novel photographic elements and means for rapid processing of photographic elements
US3652287A (en) * 1969-10-10 1972-03-28 Du Pont Direct-writing emulsions prepared by adding after silver halide precipitation in the presence of lead, insolubilizing acid anions, and heterocyclic nitrogen compounds
US3708303A (en) * 1971-01-12 1973-01-02 Eastman Kodak Co Photographic elements and processes lithographic silver halide element containing a 1-(amidophenyl)-5-mercaptotetrazole sensitizing agent and development process of using same

Citations (3)

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US2036369A (en) * 1931-10-30 1936-04-07 Noel Associates Inc Quickproof process film
US3178282A (en) * 1959-01-12 1965-04-13 Eastman Kodak Co Photographic elements containing surface image and fogged internal image silver halide grains
US3253918A (en) * 1962-06-01 1966-05-31 Eastman Kodak Co Print-out element

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DE1303059B (en) * 1964-03-11
US3295976A (en) * 1964-09-01 1967-01-03 Eastman Kodak Co Novel inhibitors for use in the black and white development of color reversal film

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
US2036369A (en) * 1931-10-30 1936-04-07 Noel Associates Inc Quickproof process film
US3178282A (en) * 1959-01-12 1965-04-13 Eastman Kodak Co Photographic elements containing surface image and fogged internal image silver halide grains
US3253918A (en) * 1962-06-01 1966-05-31 Eastman Kodak Co Print-out element

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3511658A (en) * 1966-09-28 1970-05-12 Keuffel & Esser Co Photographic reproduction materials
US3844789A (en) * 1967-03-06 1974-10-29 Gaf Corp Composite film elements
US3547647A (en) * 1967-10-02 1970-12-15 Eastman Kodak Co Photographic systems comprising silver halide particles with occluded metal ions therein,a halogen acceptor,and an organic aldehyde
US3647463A (en) * 1969-08-14 1972-03-07 Eastman Kodak Co Direct-positive photographic elements containing multiple layers
US3784375A (en) * 1969-12-22 1974-01-08 Eastman Kodak Co Ectrostatic image forms a developable image in a silver salt
US3864134A (en) * 1971-10-28 1975-02-04 Fuji Photo Film Co Ltd Silver bromoiodide photographic emulsion with improved green sensitivity
US4373022A (en) * 1978-12-28 1983-02-08 Arnold Hoffman Method and apparatus for producing a high speed high resolution radiation sensitive article and a high speed high resolution radiation sensitive article

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Publication number Publication date Type
BE713273A (en) 1968-08-16 grant
GB1227621A (en) 1971-04-07 application
FR1574754A (en) 1969-07-18 grant
US3458317A (en) 1969-07-29 grant
GB1159856A (en) 1969-07-30 application
DE1772134A1 (en) 1970-12-03 application
DE1547741A1 (en) 1970-01-02 application

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