US3108001A - Novel photographic products, processes, and compositions - Google Patents

Novel photographic products, processes, and compositions Download PDF

Info

Publication number
US3108001A
US3108001A US834262A US83426259A US3108001A US 3108001 A US3108001 A US 3108001A US 834262 A US834262 A US 834262A US 83426259 A US83426259 A US 83426259A US 3108001 A US3108001 A US 3108001A
Authority
US
United States
Prior art keywords
exposure
emulsion
silver
silver halide
layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US834262A
Other languages
English (en)
Inventor
Green Milton
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Polaroid Corp
Original Assignee
Polaroid Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to BE594117D priority Critical patent/BE594117A/xx
Application filed by Polaroid Corp filed Critical Polaroid Corp
Priority to US834262A priority patent/US3108001A/en
Priority to GB26752/60A priority patent/GB902313A/en
Priority to FR835416A priority patent/FR1269416A/fr
Priority to DE1422442A priority patent/DE1422442C3/de
Application granted granted Critical
Publication of US3108001A publication Critical patent/US3108001A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/02—Photosensitive materials characterised by the image-forming section
    • G03C8/04—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of inorganic or organo-metallic compounds derived from photosensitive noble metals
    • G03C8/06—Silver salt diffusion transfer
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/29—Development processes or agents therefor
    • G03C5/30—Developers
    • G03C5/3021—Developers with oxydisable hydroxyl or amine groups linked to an aromatic ring

Definitions

  • the present invention relates to photography and more particularly to compositions, products, and processes useful in the development of selectively photoexposed photosensitive silver halide elements, and especially to compositions and products useful in difiusion transfer processes, particularly in high speed diffusion processes wherein a silver halide photosensitive emulsion has been underexposed in relation to its A.S.A. exposure index, that is, to processes for deriving useful photographic transfer prints from latent images formed at low exposure levels.
  • the photosensitive silver halide emulsion is developed with a processing composition in a viscous condition which is spread between the photosensitive element comprising the silver halide emulsion, and a print-receiving element comprising, preferably, a suitable silver precipitating layer.
  • the processing cornpos-i tion effects development of the latent image in the emulsion and substantially contemporaneous therewith forms a soluble silver complex, for example, a thiosulfate or thiocyanate complex, with undeveloped silver halide.
  • This soluble silver complex is, at least in part, transported in the direction of the print-receiving element and the silver thereof is largely precipitated in the silver precipitating layer of said element to form the desired positive image therein.
  • High speed dilfusion transfer processes are generally of the type in which, for example, a silver halide stratum containing a latent image formed at a low exposure level and an image-receiving stratum, in superposition, are subjected to a processing composition containing a highly energetic silver halide developing agent and a silver halide solvent in order to form a silver transfer print in and/ or on the image-receiving stratum.
  • the silver halide developing agent serves to reduce photoexposed silver halide to silver in the photosensitive emulsion stratum.
  • the silver halide solvent reacts with unreduced silver halide to form the aforementioned soluble silver complex which, in turn, is reduced in the presence of the image-receiving stratum to form the desired positive print.
  • the photo sensitive stratum may be subsequently dissociated from the image-receiving stratum.
  • the silver halide stratum may be underexposed in relation to its rated A.S.A. exposure index and the silver halide developing agent is specifically selected from the class hereinafter set forth.
  • the image-receiving strutum is in such condition as to cause silver reduced there, in comparison with silver reduced in the photosensitive silver halide stratum, to possess very high covering power, that is, opacity per iven mass of reduced silver.
  • This high covering power is achieved by accumulating the silver deposited in the silver-receptive stratum in unsually dense masses, for example, by minimizing the thickness of the stratum in which the silver-receptive material is contained.
  • the high speed diffusion transfer processes set forth herein provide readily available and uniquely simple proc- 3, l Patented Oct. 22, 1963 esses for producing satisfactory high quality of good resolution and trivial granularity at low illumination levels, for example, at overall exposures that are equivalent to A.S.A. exposure indices of 1,000 and up.
  • objects of the present invention are to provide: novel products, developer compositions, and processes employing such products and developer compositions, for the development of selectively photoexposed silver halide emulsions; novel products and developer compositions useful in high speed diffusion transfer processes wherein a selectively photoexposed silver halide emulsion has been substantially underexposed in relation to its A.S.A. exposure index; and to employ, in processes of the aforementioned type, a silver halide developing agent selected from the class hereinafter set forth.
  • the invention accordingly comprises the several steps and the relation and order of one or more of such steps with respect to each of the others, and the products and compositions possessing the features, properties and the relation of elements which are exemplified in the following detailed disclosure, and the scope of the application of which will be indicated in the claims.
  • FIGURE 1 is a diagrammatic enlarged cross-sectional view illustrating the association of elements during one stage of the performance of a diffusion transfer process
  • FIG. 2 is a view similar to that of FIGURE 1 illustrating the association of elements during one stage of the performance of another diffusion transfer process, for the production of positive silver prints.
  • R is an alkyl group comprising from 1 to 4 carbon atoms such as methyl, ethyl, isopropyl, etc., or an alkoxy group comprising from 1 to 5 carbon atoms such as methoxy, ethoxy, isopropoxy, etc.
  • R is an alkyl group comprising from 1 to 4 carbon atoms, an alkoxy group comprising from 1 to 4 carbon atoms, or where R is an alkoxy group, R may comprise hydrogen; and both R and R comprise not more than 5 carbon atoms.
  • the developing agents of the present invention may be employed in the form of their acid addition salts, such as the hydrochloride.
  • amino group may be substituted where desired, for example, by a lower alkyl group such as a methyl group.
  • the reduction mixture was acidified immediately on opening with 10 cc. of concentrated hydrochloric acid, and catalyst was filtered off. The filtrate was concentrated in vacumn to about /5 its original volume, at which point white crystals began to separate. 50 cc. of concentrated hydrochloric acid was added, and the mixture was then chilled and filtered. The precipitate was washed with acetone, then with ether. The product melted at 267 C. with decomposition. [Yield was 69%.]
  • indices and diffusion transfer exposure indices can be readily established by obtaining a standardized silver transfer positive and determining the illumination, by measuring with an exposure meter calibrated according to an A.S.A. standard which includes a computer in which has been entered the shutter duration and f-stop of the camera, found necessary to provide the standard transfer print.
  • ASA. exposure index is intended to signify the exposure index determined in accordance with the aforementioned Ameri can Standards Association specifications.
  • diffusion transfer exposure index is intended to signify, in reference to diffusion transfer processes, or the materials used therein, the exposure index as determined in the aforementioned manner. Both designations, in one sense, serve the same purpose.
  • the ASA. exposure index of the negative is based upon the exposure to which the negative must be subjected in order to obtain a good photograph. of a predetermined subject by conventional processing, whereas the diffusion transfer exposure index is based upon the exposure to which a negative for use in a silver diffusion transfer process must be subjected in order to obtain a good positive by that process.
  • This negative material may be employed, for example, in a silver diffusion transfer process of the present invention to effect a diffusion transfer exposure index vastly different from the A.S.A. exposure index of the negative material.
  • a positive print of satisfactory high quality is produced from a negative material subjected to exposures less, in some cases many times less, than recommended by its rated ASA. exposure index.
  • Such an exposure provides a latent image having a density gradient confined to the low exposure or toe region of the negative materials characteristic curve.
  • FIGURE 1 illustrates one assemblage and process of the present invention in the performance of a diffusion transfer process for the production of positive silver prints.
  • an aqueous alkaline fi-uid layer 12 of a silver halide developing agent chosen in accordance with the present invention and a suitable silver halide solvent are spread between photosensitive emulsion layer 11 which is superposed on support in and image-receiving layer 13 which is affixed to support lever 14.
  • l rnage receiving layer 13 preferably contains silver precipitating agents or nuclei such as the silver precipitating nuclei disclosed in U.S. Patent No. 2,698,237.
  • Support layer 14 may comprise an opaque material where a reflection print is desired or may comprise a transparent material where a transparency is desired.
  • Fluid layer 12 may be obtained by distribution of the processing composition in a substantially uniform manner between photosensitive emulsion layer l1 and imagereceiving layer 13 for example, in accordance with the procedures disclosed in U.S. Patent No. 2,543,181.
  • one or more rupturable containers may be attached to either photosensitive emulsion layer 11 and/or image-receiving layer 13 such that upon superposition of the respective layers Ill and 13 said container or containers are so positioned as to be capable, upon rupture, of releasing their contents in a substantially uniform layer between and in contact with the opposed surface of each of said layers.
  • Rupture of the container or containers and spreading of the contents thereof may be 8 accomplished, for example, by compression between a pair of opposed, suitably gapped, rollers.
  • the processing composition preferably comprises a film-forming transfer processing com-position. It may comprise, for example, one or more of the previously enumerated developing agents of the present invention, an alkali such as sodium hydroxide, a silver halide complexing agent such as sodium thiosulfate, and a high molecular weight film-forming thickening agent such as sodium carboxy-methyl cellulose. All these materials are preferably in aqueous solution.
  • photographic agents are preferably contained in solution in the processing composition prior to the spreading thereof as layer 12, but they may be in part or in whole added to the processing composition as it is spread between the photosensitive emulsion ll and image-receiving layer 13, said agents being so located on, in, or adjacent to a surface of one or both of said layers as to be dissolved by or otherwise interacted with the liquid agent when the latter wets said layers.
  • the photosensitive emulsion 11 is exposed to a predetermined subject matter to form therein a latent image of said subject matter.
  • the exposed emulsion is superposed on image-receiving layer 13 and the photographic processing composition 12 spread between the opposed surfaces of said emulsion 1i and said image-receiving layer 13.
  • Reagents permeate into the photosensitive emulsion ll, developing the latent image contained therein and forming a soluble silver complex of unexposed silver halide.
  • Soluble silver complex is transported from photosensitive emulsion layer 11, at least in part, by imbibition, to print-receiving stratum l3 and the silver of the complex is precipitated thereon and/or therein to provide the desired positive image formation.
  • the laminate formed by the spreading of the processing composition as layer 12 between photosensitive emulsion layer 11 and print-receiving layer 13 is kept intact for approximately 12 to 1 /2 minutes, preferably 1 minute, and at the termination of this time interval the print-receiving layer 13 is dissociated from photosensitive emulsion lll as, for example, by manual stripping.
  • FIG. 2 A further transfer process of the present invention for the production of positive silver prints is illustrated in FIG. 2 and comprises a spreader sheet 15, a layer of relatively viscous processin-s composition 1'2, a photosensitive gelatin emulsion layer 11 superposed on imagereceiving layer 13 which is, in turn, superposed on a support layer 14.
  • image-receiving layer 13 preferably contains silver precipitating nuclei and support layer l4 may comprise either an opaque or transparent material.
  • Fluid composition layer 12 may be obtained by spreading a photographic processing composition, for example, in a manner disclosed in U.S. Patent No. 2,698,244.
  • the liquid processing composition may be disposed in a r upturable container so positioned in regard to the appropriate surface of photosensitive emulsion layer 11 that, upon compression by spreader sheet 15, a substantially uniform layer 12 of processing composition is distributed over the external surface of said photosensitive emulsion 11, with respect to image-receiving layer 13.
  • the photosensitive emulsion ll. is exposed to a predetermined subject matter to form therein a latent image of said subject matter.
  • a substantially uniform distribution of processing composition 12 is distributed on the external surface of said emulsion ill, as for example, according to the previously described procedure. Processing composlowly. Stirring was continued for one hour. The oil that separated was extracted with ether and the ether extracts combined and extracted with dilute hydrochloric acid. The acid phase was neutralized with 3 N Na C0 and the oil taken up in ether. The ether extract was dried over MgSO the solvent removed, and the residue distilled. The product boiled at 102 to 105 C. at 0.25 mm. pressure. [Yield was 50 to 60%.]
  • EXAMPLE 3 Syntheses of 4-Amino-Z-Methoxy-Phenol, 4-Amz'no-2- Etlzoxy-Phenol, 4-Am1'lz0..-Propoxy-Phen0l, 4-Ali'lill0- Z-Butoxy-Phenol, 4-Amilz0-2,6-Dimethyl-Phenol, 4- Amin0-2-Methyl-6-Pr0pyl-Phen0I, zmd 4-Amz'n0-2,6- Dimetlzoxy-P/renol
  • the aforementioned compounds were synthesized by coupling sulfanilic acid into the appropriate phenol and reducing the resultant alkyl and/or alkoxy substituted 4-sulfopheny lazo-phenol with sodium hydrosulfite.
  • An alternative synthesis for the compounds of the present invention is to couple 2,5-dichioroaniline into the appropriate phenol, reduce the resultant product catalytically, and separate the desired product by the addition of one equivalent of hydrochloric acid followed by ether.
  • novel silver halide developing agents of the present invention are useful in conventional black-and-white development and in difiusion transfer processes, both dye and silver. Examples of such processes are disclosed in U.S. Patents Nos. 2,543,181 and 2,662,822 to Edwin H. Land.
  • novel silver halide developing agents of the present invention are highly useful in so-called high speed diffusion transfer processes wherein high quality silver transfer prints are obtained from a silver halide emulsion which has been substantially underexposed in relation to its A.S.A. rating.
  • Such an exposure provides a latent image having a density gradient confined to the low exposure or toe region of the ne ative maa terials characteristic curve.
  • Processes of this type are exhibited a meltinr t3 disclosed in the copending application of Edwin H. Land et a1., Serial No. 564,492, filed February 9, 1956.
  • the speed of a photosensitive material comprises generally an empirically derived relative measurement which may be defined as a value representing the reciprocal of the exposure required to produce a given result. Any precise definition of speed, therefore, is based upon the selection of a particular result as the standard reference point.
  • a precise quantitative measure of speed has been developed from the work of L. A. Jones et al., as reported in Mees, The Theory of the Photographic Process, The Macmillan Compan New York, 1944, chapters XIX and XXII. This work suggested a system in which negative sensitive materials are assigned a speed that is in 'erms of the exposure required to give a negative image from which a positive print of specified quality can be produced.
  • emulsion speed is considered as a value inversely proportional to the minimum exposure which must be incident upon the negative material, from the scene element of minimum brightness in which detail is visible, in order that a print of excellent quality can be made from the resultant negative.
  • H. & D. curve of a negative material that is, the curve relating the logarithm of the original exposure of the negative to density in said negative.
  • the value of speed derived from the standard characteristic curve so determined is specified as equal to the reciprocal of the exposure, E, on the characteristic curve at which the slope is 0.3 times the average slope for a log exposure range of 1.5 of which E is the minimum exposure.
  • E the reciprocal of the exposure
  • the precise method for determining speed in this manner is described in detail in the publication of The American Standards Association, Incorporated, PH 2.54954, and titled American Standard Method for Determining Photographic Speed and Exposure Index.
  • the A.S.A. speed rating is to be distinguished from hat is termed the A.S.A. exposure index, for use with exposure meters and calculators.
  • the exposure index so obtained indicates generally the correct exposure rating to which an A.S.A. calibrated exposure meter must be set in order that it give correct exposure data for producing pictures of satisfactory high quality.
  • the A.S.A. speed rating is to be further distinguished from what may be termed diifusion transfer process exposure index.
  • the exposure index may be based on a curve relating original exposure of the negative to the density in the resultant positive. It has been found experimentally that the diffusion transfer exposure index of a silver transfer process may be determined by plotting a characteristic curve of the reflection density of the positive as a function of the log exposure of the negative, determining the exposure in metercandle-seconds (m.c.s.) at the point on this curve corresponding to a density of 0.50, and dividing the constant, 4.0, by the exposure so determined.
  • the exposure index so obtained indicates generally the correct exposure rating of a silver transfer process to which an exposure meter, calibrated to the A.S.A. exposure index, must be set in order that it give correct exposure data for producing transfer prints of satisfactory high quality, and is sometimes referred to as the equivalent A.S.A. exposure index.
  • Both the A.S.A. exposure index fer exposure index can be judged or rated according to sensitometric criteria with exposure, that is the luminance flux reaching a unit area of the photosensitive surface, being measured in m.c.s.
  • sensitometric criteria that is the luminance flux reaching a unit area of the photosensitive surface, being measured in m.c.s.
  • an imagewise distribution of soluble silver complex is formed from unexposed and undeveloped silver halide within said emulsion.
  • At least part of said silver complex, solubilized, is transferred, by imbibition, to print-receiving stratum 13.
  • the transferred silver complexes are reacted therein to provide a positive, reversed image of the latent image.
  • dissociation of said layer from emulsion layer 11 may be effected.
  • the image-receiving layer 13 may be dissociated from emulsion layer 11 by stripping the emulsion from the surface thereof.
  • a conventional stripping layer may be provided to facilitate separation of emulsion layer 11 from image-receiving layer 13 subsequent to transfer processing.
  • Sufficient abrasion-resistant properties may be provided to image-receiving layer 13 as to alleviate any necessity of subsequently overcoating the external surface of said image-receiving layer 13 with a transparent abrasion-resistant water-soluble plastic to prevent subsequent laceration and resultant degradation of the positive image.
  • Image-receiving layer 13 may also comprise sufiicient integral dimensional stability as to alleviate the necessity of a separate support layer 14.
  • spreading of the liquid processing composition on the external surface of photosensitive emulsion layer 11 is preferably effected by rupture of a suitably positioned frangible container and distribution of its processing composition contents by means of a converted cellulose acetate spreader sheet, that is, a cellulose acetate sheet the surface of which has been converted to cellulose.
  • the converted cellulose acetate spreader sheet may exhibit an adhesive capacity for the processing composition in excess of the adhesive capacity exhibited by the photosensitive emulsion.
  • a means is thus provided for effecting dissociation of the processing composition from contact with the photosensitive emulsion, subsequent to image formation, by dissociating the spreader sheets from its proximate relationship to the external emulsion surface.
  • the facility with which the photosensitive emulsion layer is dissociated from contact with the print-receiving layer may be increased by pro viding a conventional stripping layer interposed between said emulsion and said print-receiving layer.
  • the stripping layer may be coated on the surface of thesetceiving element and a photosensitive emulsion thereafter coated on the external surface of said stripping layer.
  • a photosensitive element after exposing a suitable apparatus and while preventing further exposure thereafter to actinic radiation, may be removed from such apparatus and permeated with the liquid processing composition as, for example, by coating, spraying, flowing etc., the composition on said photosensitive element or otherwise wetting said element with a composition, following which the permeated, exposed, photosensitive element, still without additional exposure to actinic radiation, is brought into contact with the image-receiving element for image formation in the manner heretofore described.
  • the rupturable containers may be constructed in accordance with the disclosures set forth in U.S. Patent No. 2,634,886.
  • Containers of this type are generally constructed from a blank comprising a flexible, deformable,
  • the container blank is folded upon itself such as to provide a fluid-containing cavity and a container exhibiting a sealed passage adjacent to an edge thereof which may be substantially uniformly unsealed throughout a predetermined length of the seal passage upon application of stress to the container.
  • the passage may be formed by the utilization of differential adhesion.
  • the print-receiving stratum preferably contains silver precipitating agents or nuclei, whose presence during the transfer process has a desirable effect on the amount and character of the silver precipitated during positive print formation.
  • silver precipitating agents are the metallic sulfides and selenides, thiooxalates, and thioacetamides, and colloidal metals disclosed in U.S. Patent No. 2,698,237.
  • a suitable water-insoluble, inorganic, preferably siliceous, material such as silica aerogel.
  • Silver halide solvents suitable for incorporation in the processing composition include conventional fixing agents such as sodium thiosulfate, sodium thiocyanate, ammonium thiosulfate, or associations of cyclic imides and nitrogenous bases such as associations of barbiturates or uracils and ammonia or amines. Of these, the conventional fixing agents specified are preferred.
  • the solution also contains a film-forming material such as a water-soluble plastic, starch or gum imparting a viscosity of from 1000 to 200,000 centipoises at a temperature of 20 C. in order to permit the solution to be readily controlled during and after spreading.
  • the relative proportions of the agents of the developer composition set forth herein may be altered to suit the requirements of the operator.
  • modify the herein described developing compositions by the substitution of preservatives, alkalies, silver halide solvents, etc., other than those specifically mentioned.
  • components such as restrainers, accelerators, etc.
  • concentration of developing agent may be varied over a wide range and when desirable the developing agent may be disposed in the photosensitive element prior to the exposure of the emulsion.
  • the devevloping agent may be disposed in a separate permeable layer of the photosensitive element and/or in the photosensitive emulsion.
  • the emulsion support layer designated in the drawing as 10 may comprise any of the various types of conventional rigid or flexible supports, for example, glass, paper, metal, and polymeric films of both the synthetic types and those derived from naturally occurring products.
  • the photosensitive emulsion stratum may comprise a commercially available silver halide gelatin emulsion such as sold by Eastman Kodak Company under the trade names Microfile, Spectrum Analysis, Contrast Process, SXX Aero Recon, Verichrome, Royal Pan, Royal X Pan, or Tri X Pan, or sold by E. I. du Pont under the trade names Fine Grain Pan, High Speed Pan, Arrow Pan, or Superior 3, or sold by Ansco under the trade name Triple S Pan, or sold by Gevaert under the trade name Gevapan.
  • a commercially available silver halide gelatin emulsion such as sold by Eastman Kodak Company under the trade names Microfile, Spectrum Analysis, Contrast Process, SXX Aero Recon, Verichrome, Royal Pan, Royal X Pan, or Tri X Pan, or sold by E. I. du Pont under the trade names Fine Grain Pan, High Speed Pan, Arrow Pan, or Superior 3, or sold by Ansco under the trade name Triple S Pan, or sold by Gevaert under the trade name Gevapan
  • R and R are each alkoxy groups containing from 1 to 4 carbon atoms and compounds wherein R comprises an alkyl containing from 1 to 4 carbon and R comprises an alkoxy group containing from 1 to 4 carbon atoms and in each case wherein R and R together comprise not more than 5 carbon atoms.
  • R and R are characterized by unexpected and exceptional high process speeds when employed in diffusion transfer processes.
  • compuonds of the present invention may also be used in small quantities with other silver halide developers, for example, hydroquinone or one of its derivatives, to produce high speed prints of exceptional quality by diffusion transfer processes.
  • other silver halide developers for example, hydroquinone or one of its derivatives
  • a silver iodobromide emulsion having the designated A. S.A. exposure index is exposed to a predetermined subject through a stop which gives rise to the indicated diffusion transfer exposure index, advanced in superposed relationship with an image-receiving element, comprising a silver-receptive stratum containing silver precipitating nuclei dispersed in a matrix of colloidal silica coated on a water-impervious base according to the practice described in U.S. Patent 2,823,122, issued to Edwin H. Land on February 11, 1958, between a pair of pressure-applying rollers to spread a processing composition comp-rising:
  • the region of the ASA. characteristic curve of the negative used in accordance with the present invention lies at a relatively low exposure level and corresponds to an exposure gradient predominantly below approximately 0.015 mes.
  • the fog level in such a case is at a point on the characteristic curve that corresponds to an exposure gradient predominantly above approximately 0.005 m.c.s.
  • the shoulder speed is the minimum amount of exposure in metercandle-seconds which can be used to expose the negative emulsion and give a transfer image in which there is the minimum contrast which the eye can distinguish, i.e., there is visible detail in the shadow regions of the transfer image.
  • This exposure level is determined at the point on the shoulder portion of the previously described characteristic curve of the positive transfer image where the slope is 0.4.
  • the photosensitive emulsions of the present processes are underexposed in relation to their respective A. ⁇ S.A. exposure index to produce therein a weak latent image having an exposure gradient predominantly in the toe region of the A.S.A. density versus log exposure curve of the photosensitive emulsion.
  • the emulsion is therefore exposed to produce a latent image lying in the toe region of the A.S.A. characteristic curve for the negative emulsion such that, by the standard A.S.A. development method, it would be impractical to develop the emulsion such as to provide a useful conventional negative image.
  • compositions, products and processes of the present invention one may advantageously employ a photosensitive emulsion having a stated A.S.A. exposure inlex and provide said emuision with an effective exposure that ordinarily would require a photosensitive emulsion having a higher A..S.A. exposure index to provide an acceptable positive print resultant therefrom.
  • Concentration Diffusion Emulsion (grauis/ Imbibition Density Density Transfer 1.5.11. Shoulder Compound 10 cc. proe- Time (maximum) (minimum) Slope Exposure Exposure Speed ossing (minutes) Index index (n1.c.s.)
  • composition 0. 4 1 1. 40 O. 01 2. 02 2, 000 200 0.000 10 0. 4 1 0. 82 0.01 0. 00 9,000 0a. 300 0. 00022 0. 4 1 1. 07 0.01 1. 18 100 200 0. 00030 0. 4 1 1. 31 0. 03 0. 06 180 Ca. 800 0. 0024 0. 4 2 1.14 0.00 1. 54 12, 100 0:1..800 0. 00015 0. 4 1 1. 12 0.01 O. 79 3, $40 ca. 800 0. 00015 0. 2 2 1. 36 O. 00 1. 74 3, 000 200 0. 00016 0. 4 2 0. 99 0.00 1. 23 15, 100 ca. 800 0. 000074 0. 4 1 1. 23 0.10 O. 88 1,150 On. 800 0. 00051 0. 4 1 1.18 0. 02 0. 73 l, 900 ca. 800 0. 000077 0. 4 1 1. 30 0.
  • the present invention provides satisfactory positive images from both underexposed and adequately exposed conventional silver halide photosensitive emulsions.
  • a convenient measure of the amplification of image development, obtained according to the present disclosure, over the results obtained from conventional development prac- 13 tices, is in terms of increase in the speed or quantum excitation sensitivity of the emulsion as indicated by the results previously set forth, over the normal specified speed of the same emulsion as determined by the results of standard development practice.
  • a photographic process which comprises the steps of underexposing a photosensitive silver halide emulsion with respect to its A.S.A. exposure index to produce therein a latent image having an exposure gradient in the toe region of the A.S.A. density versus log exposure curve of said silver halide emulsion, developing said emulsion with an aqueous halide emulsion, developing said emulsion with an aqueous alkaline solution comprising a silver halide developing agent of the formula:
  • R is selected from the group consisting of alkyl and alkoxy groups comprising from 1 to .4 carbon atoms; R is an alkoxy group comprising from 1 to.4 carbon atoms; and both R and R taken together comprise not more than 5 carbon atoms; contacting unreduced and undeveloped silver halide therein with a silver halide solvent to form an imagewise distribution of soluble silver complex, transferring at'least part of said imagewi-se distribution, by im-bibition, to a contiguous image-receiving material containing silver precipitating agents, and thereby effecting precipitation of transferred soluble silver complex to provide a positive silver print of full pictorial density on said imagereceiving material.
  • the photographic process which comprises the steps of selectively exposing a photosensitive gelatino silver halide emulsion with a luminance flux incident thereon not substantially in excess of 0.015 meter-candle-seconds; developing exposed silver halide in said photosensitive emulsion with an aqueous alkaline solution containing a silver hailde developing agent of the formula:
  • R is selected from the group consisting of alkyl and alkoxy groups comprising from 1 to 4 carbon atoms; R is an alkoxy group comprising from 1 to 4 carbon atoms; and both R and R taken together comprise not more than 5 carbon atoms; and a silver halide solvent;
  • a photographic process which comprises the steps of exposing a photosensitive gelatino silver halide emulsion with a light flux incident thereon predominantly within the exposure range delineated by the toe region of said emulsions "characteristic H. and D. curve, determined according to A.S.A. Standard PH 2.5-1954; developing exposed silver halide in said photosensitive emulsion with an aqueous alkaline solution of a silver halide developing agent of the formula:
  • R is selected from the group consisting of alkyl and alkoxy groups comprising from 1 to 4 carbon atoms; R is an alkoxy group comprising from 1 to 4 carbon atoms; and both R and R taken together comp-rise not more than 5 carbon atoms; contacting undeveloped silver halide with a silver halide solvent and forming thereby an imagewise distribution of soluble silver complex in the unexposed areas of said emulsion; transferring from said emulsion, at least in part, said imagewise distribution of soluble silver complex to a print-receiving element, containing silver precipitating agents, in superposed relationship to said emulsion; and precipitating said silver complex to provide thereby a reversed, positive print possessing a characteristic curve with a slope greater than the slope of said H. and D. curve, said positive prints characteristic curve determined by plotting the reflection density of the positive print as a function of the log exposure of the negative.
  • Patent 2,823,122 read UOS, Patent No, 2,823,122 columns 11 and 12, in the table, ninth column, line 3 thereof, for "0.00030 read 0.0030 column 12, line 37, for "inlex” read index column 13, lines 18 and 19, strike out "developing said emulsion with an aqueous halide emulsion,"; line 55, for

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US834262A 1959-08-17 1959-08-17 Novel photographic products, processes, and compositions Expired - Lifetime US3108001A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
BE594117D BE594117A (de) 1959-08-17
US834262A US3108001A (en) 1959-08-17 1959-08-17 Novel photographic products, processes, and compositions
GB26752/60A GB902313A (en) 1959-08-17 1960-08-02 Novel photographic products, processes and compositions
FR835416A FR1269416A (fr) 1959-08-17 1960-08-09 Nouveaux produits, procédés et compositions photographiques
DE1422442A DE1422442C3 (de) 1959-08-17 1960-08-17 Entwickler für das Silbersalz diffusionsverfahren

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US834262A US3108001A (en) 1959-08-17 1959-08-17 Novel photographic products, processes, and compositions
DEJ0018588 1960-08-17

Publications (1)

Publication Number Publication Date
US3108001A true US3108001A (en) 1963-10-22

Family

ID=25982283

Family Applications (1)

Application Number Title Priority Date Filing Date
US834262A Expired - Lifetime US3108001A (en) 1959-08-17 1959-08-17 Novel photographic products, processes, and compositions

Country Status (4)

Country Link
US (1) US3108001A (de)
BE (1) BE594117A (de)
DE (1) DE1422442C3 (de)
GB (1) GB902313A (de)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3196015A (en) * 1962-01-31 1965-07-20 Polaroid Corp Diffusion transfer process
US3276873A (en) * 1963-08-30 1966-10-04 Polaroid Corp Photographic processes
US3325284A (en) * 1962-06-27 1967-06-13 Gevaert Photo Prod Nv Silver complex diffusion transfer process
US3647436A (en) * 1970-08-31 1972-03-07 Eastman Kodak Co Developers for diffusion transfer film units
US3790383A (en) * 1970-12-21 1974-02-05 Fuji Photo Film Co Ltd Infectious developer composition
US3804624A (en) * 1970-10-27 1974-04-16 Fuji Photo Film Co Ltd Method for developing silver halide photosensitive material
US3849133A (en) * 1970-04-20 1974-11-19 Fuji Photo Film Co Ltd Process for forming photographic images by high speed diffusion transfer process
US3873315A (en) * 1970-10-27 1975-03-25 Fuji Photo Film Co Ltd Method of developing silver halide photosensitive material

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2692830A (en) * 1944-11-03 1954-10-26 Polaroid Corp Photographic silver halide transfer process
US2740717A (en) * 1952-05-03 1956-04-03 Eastman Kodak Co Photographic transfer process
US2909430A (en) * 1958-10-08 1959-10-20 Polaroid Corp Photographic processes
US3039869A (en) * 1957-04-24 1962-06-19 Polaroid Corp Photographic color processes and compositions

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2692830A (en) * 1944-11-03 1954-10-26 Polaroid Corp Photographic silver halide transfer process
US2740717A (en) * 1952-05-03 1956-04-03 Eastman Kodak Co Photographic transfer process
US3039869A (en) * 1957-04-24 1962-06-19 Polaroid Corp Photographic color processes and compositions
US2909430A (en) * 1958-10-08 1959-10-20 Polaroid Corp Photographic processes

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3196015A (en) * 1962-01-31 1965-07-20 Polaroid Corp Diffusion transfer process
US3325284A (en) * 1962-06-27 1967-06-13 Gevaert Photo Prod Nv Silver complex diffusion transfer process
US3276873A (en) * 1963-08-30 1966-10-04 Polaroid Corp Photographic processes
US3849133A (en) * 1970-04-20 1974-11-19 Fuji Photo Film Co Ltd Process for forming photographic images by high speed diffusion transfer process
US3647436A (en) * 1970-08-31 1972-03-07 Eastman Kodak Co Developers for diffusion transfer film units
US3804624A (en) * 1970-10-27 1974-04-16 Fuji Photo Film Co Ltd Method for developing silver halide photosensitive material
US3873315A (en) * 1970-10-27 1975-03-25 Fuji Photo Film Co Ltd Method of developing silver halide photosensitive material
US3790383A (en) * 1970-12-21 1974-02-05 Fuji Photo Film Co Ltd Infectious developer composition

Also Published As

Publication number Publication date
BE594117A (de)
DE1422442C3 (de) 1973-11-22
DE1422442B2 (de) 1973-05-03
DE1422442A1 (de) 1968-11-28
GB902313A (en) 1962-08-01

Similar Documents

Publication Publication Date Title
US2726154A (en) Photographic product
US2944894A (en) Photographic processes utilizing screen members
US3702244A (en) Diffusion transfer photographic processes and elements utilizing ph-sensitive agents to prevent fogging by extraneous actinic radiation during development
US2699393A (en) Photographic process for the direct production of positive images
US3108001A (en) Novel photographic products, processes, and compositions
US3730716A (en) Silver image stabilization with noble metal compounds and alpha,beta-enediol developer
US3985561A (en) Diffusion transfer process using silver halide emulsions with 90% chloride and high binder to silver halide ratios
US3345166A (en) Photographic process whereby a fully developed and fixed negative is formed concurrently with a positive silver transfer image
US3740220A (en) Photographic material
US3091530A (en) Photographic products, processes and compositions
US3704126A (en) Silver image stabilization with noble metal compounds
US3666460A (en) Diffusion transfer article and process using humectant in emulsion layer
JPS60104942A (ja) 銀塩拡散転写用処理組成物
US3257207A (en) Photographic products, processes and compositions
US3235599A (en) Mono-n-benzyl-diamino-phenyl compounds
US3276873A (en) Photographic processes
US3694204A (en) Diffusion transfer product having heat activatable processing system and an opacity providing layer
US3196015A (en) Diffusion transfer process
US3256091A (en) Photographic processes
US2966408A (en) Photographic films
US3313625A (en) Novel photographic products and processes
US3326683A (en) Diffusion transfer photographic process using 4, 6-diamino-ortho cresol
US3620728A (en) Receiving sheet for diffusion transfer processes
US2939788A (en) Novel photographic developers
US2584029A (en) Photographic silver transfer product and process, including a lead salt