US2452765A - Multilayer photographic element having a mixed grain emulsion and process employing it - Google Patents

Multilayer photographic element having a mixed grain emulsion and process employing it Download PDF

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Publication number
US2452765A
US2452765A US10186A US1018648A US2452765A US 2452765 A US2452765 A US 2452765A US 10186 A US10186 A US 10186A US 1018648 A US1018648 A US 1018648A US 2452765 A US2452765 A US 2452765A
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United States
Prior art keywords
emulsion
developer
type
silver
emulsions
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Expired - Lifetime
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US10186A
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English (en)
Inventor
Edward B Knott
Stevens Guy William Willis
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Eastman Kodak Co
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Eastman Kodak Co
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    • 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
    • G03C1/00—Photosensitive materials
    • G03C1/52—Compositions containing diazo compounds as photosensitive substances
    • G03C1/58—Coupling substances therefor
    • 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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • 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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/485—Direct positive emulsions
    • G03C1/48538—Direct positive emulsions non-prefogged, i.e. fogged after imagewise exposure
    • 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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/22—Subtractive cinematographic processes; Materials therefor; Preparing or processing such materials
    • G03C7/24—Subtractive cinematographic processes; Materials therefor; Preparing or processing such materials combined with sound-recording
    • 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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains
    • 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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • G03C2001/03564—Mixed grains or mixture of emulsions

Definitions

  • This invention relates to photographic processes and material therefor.
  • the latent photographic image formed by the action of light on a photographic silver halide emulsion is not confined to the surface of the silver halide grains but is also distributed internally throughout those grains. It is possible to develop only the so-called surface latent image by means of developers which have little solvent action for silver halide.
  • developers which have little solvent action for silver halide.
  • One of us has described in the literature given below that after removal of the surface latent image the internal latent image can be developed as simply and conveniently as can an ordinary surface latent image if this is done by employing adeveloper having a solvent action for silver halide;
  • this type of emulsion may be prepared in other known manners, for instance by taking an ordinary silver iodobromide emulsion containing between 0.5 and 5% silver iodide (based on the total silver halide), and coating it as a layer and then after drying,
  • the time of treatment must be suflicient to inhibit surface latent image formation as can easily be ascertained by exposing (after washing) and then treating with developers of Formulae I and III, given below.
  • Such an emulsion layer can then be used as it is or may be remelted and coated again as desired.
  • the Formula I developer is specified the developer of Formula III may be used in place thereof.
  • the emulsion need not conform to such a rigid requirement but it may be suflicient if in the above test the range of .3.0 is substituted by a'range giving densities of 0.1 to 0.501 of 0.1 to 1.0.
  • This emulsion is prepared by first forming in the absence of ammonia and in one or more stages silver salt grains consisting at least partly of a.
  • An internal latent image type of silver halide emulsion may also be defined as one which, when a'tes't portion is exposed to a light intensity scale for a fixed time between and 1 second, and developed for 4 minutes at 20 C. in the ordinary, surf-ace developer (Formula I), exhibits a maximum densitynot greater than .4 the ma imum density obtained when the same emulsion is equally exposed and developed for 3 minutes at 20 C. in an internal type developer (Formula Ila).
  • the maximum density obtained with the surface developer is not greater than the maximum density obtained when the same emulsion is developed in the internal type developer.
  • an internal latent image emulsion when developed in an internal type developer (Formula Ila) exhibits a maximum density at least 5, and preferably at least 10, times the maximum density obtained when the same'emulsion is exposed in the same way and developed in a surface developer (Formula I).
  • internal developer is necessarily capable of developing not only a latent image inside grains but also a latent on the surface of grains.
  • the present invention provides a useful sensitive photographic material comprising on a single support two sensitive silver salt emulsions one of which upon exposure forms the latent image mostly inside the grains and the other of which upon exposure forms a surface latent image on most of theexposed grains, the combination being such that either such emulsion can be exposed and. then simply developed by treating the whole with a developer without thereby causing a deleterious degree of development in the other.
  • a not specially colour sensitized emulsion of type I coated on a not specially colour sensitized emulsion of type II with a blue absorbing filter layer there-between, or the filtering material may be in one of the emulsions such as in the type I emulsion.
  • Such emulsions can be on the same side or opposite sides of the support.
  • Example I illustrates a material which can be employed in a two-colour process.
  • the two emulsions are then mixed at 30 C. and coated on a support such as paper, or they may be coated as superimposed layers.
  • this material can be processed to give a two-colour negative image by employing the procedure described below in Example II except omitting step (2) and using a coupler giving an orange image instead of the coupler giving a yellow image in step (3).
  • Selective developability depending on latent image distribution may also be usefully combined with known means (see for example United States Patent 2,231,684 dated Feb. 11, 1941) for obtaining selective developability.
  • silver bromide or iodo-bromide emulsion of type II may be mixed with a silver bromide or iodobromide emulsion of type I and a silver chloride emulsion of type II; alternatively these emulsions may be coated in three superimposed layers be selectively developed before the other emulsions are developed.
  • Example II --On a support, there is first coated a silver bromide or iodobromide emulsion of type II sensitized to the red with, for instance, 3:3 dimethyl-4 5 4 :5-dibenzthiacarbocyanine iodide. Over the layer so formed there is coated a mixture of a silver chloride emulsion (type II) sensitized to the green with a sensitizing dye hav ing little or no tendency to wander (e. g. the dye of Example III of United States Patent 2,282,116 dated May 5, 1942) and an emulsion of type I of silver iodobromide sensitive only to the blue.
  • a silver bromide or iodobromide emulsion of type II sensitized to the red with, for instance, 3:3 dimethyl-4 5 4 :5-dibenzthiacarbocyanine iodide.
  • This type I emulsion is one which absorbs blue light very strongly and this has the effect of reducing considerably the effective blue sensitivity of the red sensitive layer; alternatively this blue sensitivity can be effectively reduced in known manner by interposing a yellow filter layer between it and the other emulsions.
  • the blue sensitivity of the silver chloride emulsion is so low that there is practically no image formed therein when the blue sensitive emulsion mixed therewith is properly exposed.
  • This mixture may be made exactly as the mixture prescribed in Example I.
  • the two emulsions of the mixture may if desired be coated as superimposed layers.
  • Example III A film support is coated with a high contrast fine grain process type emulsion
  • This treatment converts, the process emulsion from type II to type I.
  • the other side of the film is then successively coated with a blue absorbing filter layer and then an emulsion of type II.
  • This material can be used for a two colour process as a printing material where it is desired to expose both emulsions prior to any processing step.
  • a support I is coated with a silver bromide or iodobromide emulsion I I, of type II containing red-sensitive silver'halide grains I2. Over this layer there is coated a single emulsion layer I 3 containing a mixture of green-sensitive silver chloride grains I4 and blue-sensitive silver iodobrornide grains I5 of type I. After ex posure of this material to a colored object or image, it is processed as shown in the remaining stages of the drawing.
  • the sensitive element after exposure is treated with a mildly acting developer containing a magenta coupler but no silver halide solvent to form a magenta dye image I6 in emulsion layer I3 leaving' a latent image I! of the red sensation in emulsion layer II and a latent image I8 of the blue sensation in emulsion layer I3.
  • the element is then subjected to the action of a color developer containing a cyan coupler but no silver halide solvent for a time sufilcient to develop a cyan dye image I9 in emulsion layer I I as shown in the third stage of the drawing.
  • the element is developed in a developing solution containing a yellow coupler and also containing a silver halide solvent, to form yellow dye image as shown in the fourth stage of the drawing. All silver and unused silver halide are then removed.
  • emulsions of difierent types on a single support are as follows, and in these examples the emulsions may be also differentially colour sensitized so that they can be exposed selectively by different coloured lights.
  • red and green spectacles may be processed in a simple manner by treatment of the whole film first with a developing solution for developing only one of the emulsions (and subsequently with a developing solution for developing the other emulsion).
  • a picture image and a sound track image can be developed separately without the trouble of applying the development solutions to the separate picture and sound areas of the cinematograph film (e. g. by applicator rollers) by employing (e. g. in admixture) an emulsion of one type for printing the sound track and an emulsion or emulsions of the other types for printing the picture.
  • the invention which has been described above requires that the emulsions of types I and II should be so arranged that either of them can be exposed and simply developed by treating the whole with a developer without thereby causing a deleterious degree of development in the other, it is possible to modify the above invention by dispensing with this requirement and making the emulsions so that they give widely differing gammas and then such a material, although less useful than those previously described, can be used for so-called multi-contrast purposes, such as for producing images of different contrasts from negatives of the same contrast or images of the same contrast from negatives of different contrasts.
  • a sensitive material for this purpose can be made by mixing in one layer or coating in superposed layers two emulsions giving widely differing gradations, one of the emulsions being of one of the above types and the other of another of the above types.
  • Such emulsions can be dye-sensitized or not.
  • we can employ an emulsion of type II giving a low gradation in Formula III and an emulsion of type I giving a high gradation in Formula II (b).
  • the threshold speed of type II emulsion when developed in developer Formula II or III should for example be higher than that of type I emulsion when developed in developer Formula II (b) preferably the characteristic curves under these conditions should cross at about a density of one.
  • the material so made can be printed with white light and then the contrast of the image controlled by choice of the developer.
  • the image will be of relatively low contrast if developed in a developer such as Formula III, or relatively medium contrast in a developer of Formula IIb, and of high contrast if then first treated in a mild silveroxidizing bath which destroys surface latent images in ordinary emulsions of type II and then developed in Formula IIb.
  • the threshold speed of the type II emulsion can be equal or lower than that of the type I emulsion.
  • Such a material gives low contrast mainly due to the type II emulsion on development in Formula III and a high con trast mainly due to the type I emulsion on development in Formula II(a) or 11(1)).
  • a sensitive photographic element comprising a support having thereon two superposed emulsion layers, one of which layers is a red sensitive silver halide emulsion (II) a test portion of which upon exposure to light and development for 4 minutes at 20 C1. in the following developer (11b);
  • a sensitive photographic element comprising a support having thereon two superposed emulsion layers, one of which layers is a red sensitive silver bromide emulsion (II) a test portion of which upon exposure to light and development for 4 minutes at 20 C. in the following developer (IIb) Grams Hydroquinone 12 N-methyl-p-aminophenol sulfate 3 Sodium sulfite, crystals 90 Potassium bromide 4 Sodium carbonate, crystals 150' Sodium thiosulfate, crystals 20 Water to 1000 ccs.
  • IIb red sensitive silver bromide emulsion
  • a sensitive photographic element comprising a suppor-t having on one side thereof two super posed emulsion layers, the layer adjacent the support being a red sensitive silver bromide emulsion (II) a test portion of which upon exposure to light and development for 4 minutes at 20C. in the following developer (IIb) Grams I-Iydroquinone 12 N methyl-p-aminophenol sulfate 3 Sodium sulfi-te, crystals 90 Potassium bromide 4 Sodium carbonate, crystals Sodium thiosulfate, crystals 20 Water to 1000 ccs.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Materials For Photolithography (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
US10186A 1942-09-02 1948-02-21 Multilayer photographic element having a mixed grain emulsion and process employing it Expired - Lifetime US2452765A (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB2452765X 1942-09-02
GB1242243 1943-10-04
GB10663/44A GB581790A (en) 1942-09-02 1944-06-02 Photographic processes and materials therefor
US14176A US2490751A (en) 1942-09-02 1948-03-11 Mixed grain multilayer photographic film and process

Publications (1)

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US2452765A true US2452765A (en) 1948-11-02

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US10186A Expired - Lifetime US2452765A (en) 1942-09-02 1948-02-21 Multilayer photographic element having a mixed grain emulsion and process employing it
US14176A Expired - Lifetime US2490751A (en) 1942-09-02 1948-03-11 Mixed grain multilayer photographic film and process

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Application Number Title Priority Date Filing Date
US14176A Expired - Lifetime US2490751A (en) 1942-09-02 1948-03-11 Mixed grain multilayer photographic film and process

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US (2) US2452765A (US07321065-20080122-C00020.png)
BE (1) BE468652A (US07321065-20080122-C00020.png)
CH (2) CH278966A (US07321065-20080122-C00020.png)
DE (2) DE854888C (US07321065-20080122-C00020.png)
FR (2) FR950279A (US07321065-20080122-C00020.png)
GB (4) GB581772A (US07321065-20080122-C00020.png)
NL (1) NL69459C (US07321065-20080122-C00020.png)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2581718A (en) * 1948-06-10 1952-01-08 Roland M Schaffert Method of preparing duplicate plastic-backed printing plates
US3404002A (en) * 1963-06-27 1968-10-01 Eastman Kodak Co Interimage characteristics of silver halide dye developer image transfer systems
US3607278A (en) * 1968-04-18 1971-09-21 Eastman Kodak Co Photographic elements containing fogged and unfogged silver halide grains and a slow silver halide emulsion layer
US5389507A (en) * 1992-12-31 1995-02-14 Eastman Kodak Company Reversal elements with internal latent image forming core-shell emulsions

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE491747A (US07321065-20080122-C00020.png) * 1948-10-22
US3000739A (en) * 1957-04-02 1961-09-19 Du Pont Process for preparing silver halide emulsions
US3152907A (en) * 1959-11-12 1964-10-13 Eastman Kodak Co Method for controlling speed and contrast of photographic emulsions
US3276877A (en) * 1964-07-17 1966-10-04 Eastman Kodak Co Method of preparing sensitized photographic emulsions
US3622318A (en) * 1970-03-20 1971-11-23 Eastman Kodak Co Photographic materials and processes
JPS5895345A (ja) * 1981-12-01 1983-06-06 Konishiroku Photo Ind Co Ltd 色素画像形成方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2197994A (en) * 1937-09-10 1940-04-23 Dufay Chromex Ltd Color photography

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2197994A (en) * 1937-09-10 1940-04-23 Dufay Chromex Ltd Color photography

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2581718A (en) * 1948-06-10 1952-01-08 Roland M Schaffert Method of preparing duplicate plastic-backed printing plates
US3404002A (en) * 1963-06-27 1968-10-01 Eastman Kodak Co Interimage characteristics of silver halide dye developer image transfer systems
US3607278A (en) * 1968-04-18 1971-09-21 Eastman Kodak Co Photographic elements containing fogged and unfogged silver halide grains and a slow silver halide emulsion layer
US5389507A (en) * 1992-12-31 1995-02-14 Eastman Kodak Company Reversal elements with internal latent image forming core-shell emulsions

Also Published As

Publication number Publication date
CH281462A (fr) 1952-03-15
DE848909C (de) 1952-09-08
FR61904E (fr) 1955-05-31
GB581790A (en) 1946-10-24
GB662360A (en) 1951-12-05
US2490751A (en) 1949-12-06
GB581772A (en) 1946-10-24
BE468652A (US07321065-20080122-C00020.png)
CH278966A (fr) 1951-11-15
FR950279A (fr) 1949-09-22
GB595419A (en) 1947-12-04
NL69459C (US07321065-20080122-C00020.png)
DE854888C (de) 1952-11-06

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