EP0183528A2 - Farbphotographisches Element - Google Patents

Farbphotographisches Element Download PDF

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Publication number
EP0183528A2
EP0183528A2 EP85308585A EP85308585A EP0183528A2 EP 0183528 A2 EP0183528 A2 EP 0183528A2 EP 85308585 A EP85308585 A EP 85308585A EP 85308585 A EP85308585 A EP 85308585A EP 0183528 A2 EP0183528 A2 EP 0183528A2
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EP
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Prior art keywords
emulsion
layers
layer
sensitized
silver halide
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French (fr)
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EP0183528A3 (en
EP0183528B1 (de
EP0183528B2 (de
Inventor
Sharon M. C/O Minnesota Mining And Simpson
John R. C/O Minnesota Mining And Boon
John M. C/O Minnesota Mining And Mcquade
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3M Co
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Minnesota Mining and Manufacturing 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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • 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
    • G03C5/16—X-ray, infrared, or ultraviolet ray processes
    • G03C5/164—Infra-red processes
    • 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
    • G03C7/3041—Materials with specific sensitometric characteristics, e.g. gamma, density

Definitions

  • This invention relates to color photographic elements and in particular. to color photographic elements capable of providing full color images with exposure of at least two silver halide emulsion layers to radiation outside the visible region of the electromagnetic spectrum.
  • the present invention relates to a color photographic element having at least three emulsion layers associated with color image providing materials, each emulsion layer being sensitized to a different region of the electromagnetic spectrum and at least two layers being sensitized to radiation within the infrared region of the. electromagnetic spectrum.
  • Dyes which have been capable of sensitizing silver halide emulsions to infrared regions of the electromagnetic spectrum have been known for many years.
  • Merocyanine dyes and cyanine dyes, particularly those with longer bridging groups between cyclic moieties have been used for many years to sensitize silver halide to the infrared.
  • U.S. Patent Nos. 3,619,154, 3,682,630); 2,395,955: 3,482,978; 3,758,461 and 2,734,900: and U.K. Patent Nos. 1,192,234 and 1,188,784 disclose well-known classes of dyes which sensitize silver halide to portions of the infrared region of the electromagnetic spectrum.
  • U.S. Patent 4,362,800 discloses dyes used to sensitize inorganic photoconductors to the infrared, and these dyes are also effective sensitizers for silver halide.
  • U.S. Patent No. 4,416,522 proposes daylight photoplotting apparatus for the infrared exposure of film.
  • This. patent also generally proposes a film comprising three emulsion layers sensitized to different portions of non-visible portions of the electromagnetic spectrum, including the infrared.
  • the film description is quite qeneral and the concentration of imagewise exposure on each layer appears to be dependent upon filtering of radiation by the apparatus prior to its striking the film surface.
  • a photographic element which is capable of providing full color images without exposure to corresponding visible radiation.
  • the element comprises at least three silver halide emulsion layers on a substrate.
  • the at least three emulsion layers are each associated with different photographic color image forming materials, such as color couplers capable of forming dyes of different colors upon reaction with an oxidized color photographic developer, diffusing dyes, bleachable dyes, or oxidizable leuco dyes.
  • the three emulsion layers are sensitized to three different portions of the electromagnetic spectrum with at least two layers sensitized to different regions of the infrared region of the electromagnetic spectrum.
  • the layers must be in a construction that prevents or reduces the exposure of layers by radiation intended to expose only one other layer. This is done by providing differences in speed of emulsions sensitive to different wavelengths of the infrared.
  • Figure 1 shows the D vs logE curve for the photographic element of Example 1 when exposed to 780nm radiation.
  • Curve (a) shows the density of the yellow-forming layer which is sensitized to 780nm.
  • Curve (b) shows the density of the magenta-forming layer which is sensitized to 830nm.
  • Curve (c) shows the density of the cyan-forming layer which is sensitized to 880nm.
  • a photographic element is herein described which photographic element is capable of providing a full color image or three color images with exposure of at least two silver halide emulsion layers to radiation outside the visible region of the electromagnetic spectrum comprising
  • said three silver halide emulsion layers comprising in any order a first emulsion sensitized to a first portion of the infrared region of the electromagnetic spectrum, a second silver halide emulsion sensitized to a second portion of the infrared region of the electromagnetic spectrum, the wavelength of maximum spectral sensitivity of which second emulsion differs by at least 15 nm from the wavelength of maximum spectral sensitivity to which said first emulsion is sensititized, and a third silver halide emulsion sensitized to a third portion of the electromagnetic spectrum, the wavelength of maximum spectral sensitivity of which portion differs by at least 15 nm from each the the wavelengths of maximum sensitivity to which said first and second emulsions are sensititized, the sensitivities of each of said three emulsion layers being such that between any two emulsion layers which are sensitized to portions of the infrared region of the electromagnetic spectrum, the emulsion having a wavelength of maximum spect
  • the difference between any two layers sensitive to the infrared be at least 20 nm, more preferred that the difference be at least 35 nm, and most preferred that the difference in wavelengths of maximum spectral sensitivity be at least 50 nm between any two layers sensitized to the infrared.
  • filter layers between emulsion layers can help reduce the needed levels of sensitivity differences between layers.
  • a filter dye between layers which absorbs strongly at the wavelengths of maximum spectral sensitivity of the uppermost emulsion layer (with respect to the direction from which exposure occurs) the needed difference in sensitivity of the lower layer can be somewhat reduced.
  • the preferred arrangement of layers has the wavelengths of maximum spectral sensitivity in the respective layers getting longer as one moves away from the direction (or surface) from which the exposure is to be made. That is, using for example, color paper or print as a reference, the infrared sensitive layer furthest from the paper base has a wavelength of maximum spectral sensitivity which is shorter than the wavelength of maximum spectral sensitivity of any other emulsion layer closer to the base. This preference is because sensitization peaks of dyes tend to fall off more quickly towards longer wavelengths making sensitivity separation more easily effected and filter dyes more easily chosen.
  • any two layers when all three emulsion layers are within the infrared region of the electromagnetic spectrum, any two layers must have wavelengths of maximum spectral sensitivity differing by at least 15 nm and speed differences of at least 0.2 logE units.
  • Spectral sensitizing dyes are available across the entire visible spectrum and even in to the ultraviolet. One of ordinary skill in the art could thus easily sensitize the third emulsion layer to a wavelength outside the infrared where there would be practically no overlap in spectral sensitization effected by the various sensitizing dyes.
  • the third emulsion layer could be sensitized more than 100 nm below the infrared (beginning approximately at about 750-780 nm) to the blue, green or yellow portions of the electromagnetic spectrum. If for any reason it were desired to have the third emulsion layer sensitized to a portion of the spectrum less than 100 nm from the shortest wavelength within the infrared to which an emulsion is sensitized, it would be desirable to give consideration to adjusting the speed of the emulsion sensitized to the visible in a manner similar to that done for shorter wavelengths within the infrared. If the emulsion layer sensitized to the visible portion of the electromagnetic spectrum is near to the infrared (e.g.
  • the speed of the emulsion sensitized to the visible should also be at least 0.2 or at least 0.5 logE units faster than the speed of the emulsion sensitized to a wavelength within the infrared nearest the visible portion of the spectrum.
  • the use of spectral sensitizing dyes within the visible portion of the electromagnetic spectrum which form J-bands will effectively reduce the impact of this consideration.
  • the speed of the emulsion layers is to be determined, at all times, at the wavelength of maximum sprestral sensitivity for the emulsion layer.
  • the term wavelength of maximum sensitivity should be read as wavelength of maximum spectral sensitivity in the practice of the present invention, that is, the wavelength of maximum sensitivity effected by the addition of spectral sensitizing dyes.
  • the broadest range of contrasts for use in construction of emulsions within the present invention is about 0.5 to 12.
  • the lower limit is essentially a function of the power available from lasers in imaging apparatus.
  • the upper limit tends to be a function of the type of use to which the film or paper is to be used.
  • a range of 1 to 11 for contrast is preferred; a contrast of 2 to 8 is more preferred.
  • a photographic element is further herein described, which photographic element is capable of providing a full color image with exposure of at least two silver halide emulsion layers to radiation outside the visible region of the electromagnetic spectrum comprising
  • the relative order in the relationship of the emulsion layers of the present invention is important in obtaining benefits from the technology.
  • the first layer as described above, must be the emulsion layer farthest from the imaging radiation. Thus, where exposure would be through a transparent base, the first layer would he the emulsion layer farthest from the base, the top emulsion layer from a conventional perspective. Normally, photographic elements are not exposed through the base, and the first layer would normally be the infrared sensitized emulsion layer closest to the base.
  • all of the silver halide emulsion layers are sensitized to different infrared regions of the electromagnetic spectrum. It is essential that at least two layers be sensitized to different infrared regions of the electromagnetic spectrum. The order of those at least two layers must still be that the emulsion layer sensitized to the longer wavelength is closest to the side of the photographic element first struck by the exposing radiation. There is more flexibility with respect to the placement of other silver halide emulsion layers which are sensitized to visible portions of the electromagnetic spectrum.
  • filter layers and reduced sensitivity of the emulsion layers would not be essential between the yellow layer and either of the infrared sensitive layers.
  • the differential in sensitivity and/or filter layers would still have to exist between any two infrared sensitive layers.
  • the filter layer (if any), would have to be placed between layers 2) and 3) or the emulsion sensitivities must differ, as required in the practice of the present invention, only as between layers 2) and 3).
  • Layer 1) would merely be constructed as a conventional yellow forming silver halide emulsion layer (or negative dye forming layer).
  • any filter layers must be between layers 1) and 3) and could be placed between layers 1) and 2) or between layers 2) and 3).
  • the difference in emulsion sensitivity, if used, according to the practice of the present invention would he between layers 1) and 3).
  • the sensitivity of layer 2) would be selected only on the basis of the activity desired to produce an effective yellow color. There are no significant considerations of guarding against exposure of layer 2 by radiation used to expose layers 1) or 3). Filters could be used if the dyes in layer 2) had a long tail on its absorption curve, hut that would occur only with less than skillful selection of the yellow sensitizing dye.
  • the visible light sensitive emulsion layer is used as the emulsion layer farthest from the base, similar considerations must he made.
  • the filter layer would still have to be between the two infrared sensitive layers, if a filter layer is used.
  • the difference in emulsion sensitivity must also be present between the two infrared sensitized layers if that method, according to the teachings of the present invention, is used.
  • the infrared portion of the electromagnetic spectrum is given various ranges, but is generally considered to he between 750 to 1500nm which overlaps a small portion of the visible regions of the electromagnetic spectrum (e.g., about 750-780nm).
  • a large number of dyes are known to sensitize silver halide emulsions to various portions of the infrared region of the spectrum.
  • cyanines and merocyanines are well documented as infrared sensitizers for various types of imaging systems including silver halide emulsions.
  • the sensitizing dyes chosen are extremely important to the construction of the color multilayer material.
  • these dye structures are usually symmetrical or unsymmetrically substituted dicarbocyanines 1 and tricarbocyanines 2 with the auxochromic portions of the dyes being lepidine 3, quinoline 4, naphthothiazole 5, benzothiazole 6, and so forth.
  • Heterocyclics may also be introduced into the methine chain to increase rigidity and stability of the dye molecule.
  • JR-sensitizing dyes 7 - 9 are shown in the following formulae. Each of these dyes was added to a silver chlorobromide emulsion coated and subsequently were exposed at various times with the emission from a tungsten-lamp source on a wedge spectrograph. The characteristic shape of their curves is a broad tail of sensitization stretching 150 to 300nm from the peak of maximum sensitization to the shorter wavelength side of the spectrum, but a narrow tail of sensitization approximately 50 to 70nm wide on the longer wavelength side.
  • Other cyanine-type dyes 10 - 20 with various auxochromic end groups also exhibited similar sensitization curves on the emulsion.
  • the wavelength of the peak of maximum sensitization (Peak) and the wavelength of the point at which minimum sensitization at longer wavelengths occur (Minimum) are shown. Any of the known useful anions may be associated with these compounds, but I-, Br-, tosylate, and para-toluene sulfonate are preferred.
  • infrared sensitizing dyes like most other sensitizing dyes do not have monochromatic absorption curves, but absorb, and thus sensitize to, a range of radiation wavelengths
  • J-banding dyes which tend to have a narrower range of absorption for each dye, absorb over a range of the electromagnetic spectrum. This range can extend from a few nanometers up to a few hundred nanometers.
  • exposing radiation sources from lasers can he essentially monochromatic, the spectral sensitivities of even single layer emulsions may have maximum sensitivities at the wavelength of the exposing radiation, but still bracket that wavelength with a range of sensitivity.
  • infrared laser diodes tend to emit radiation between wavelengths of 750-950nm. This tends to be too narrow a range to allow for multiple layer photos oaphic emulsions with different regions of sensitivity.
  • Sensitizing dyes selected to sensitize at about 780, 830, and 880, for example, would have sensitizing effects that could overlap the other wavelengths. Particularly in a photographic element intended to provide a full color image, an overlap in sensitizing ranges would cause poor faithfulness in color rendition because of the spurious imaging of multiple layers by the same wavelength of radiation.
  • the constructions of the present invention enable manufacture of high quality color photographic images, even where the various emulsion layers are sensitized to maximize sensitivity at peaks within fifty nanometers of each other.
  • any of the various types of photographic silver halide emulsions may be used in the practice of the present invention.
  • Silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chlorobromoiodide, and mixtures thereof may be used, for example.
  • Any configuration of grains, cubic orthorhombic, hexagonal, epitaxial, or tabular (high aspect ratio) grains may be used.
  • the couplers may he present either directly bound by a hydrophilic colloid or carried in a high temperature boiling organic solvent which is then dispersed within a hydrophilic colloid.
  • the colloid may be partially hardened or fully hardened by any of the variously known photographic hardeners. Such hardeners are free aldehydes (U.S. Pat.
  • the silver halide photographic elements can be used to form dye images therein through the selective formation of dyes.
  • the photographic elements described above for forming silver images can be used to form dye images by employing developers containing dye image formers, such as color couplers, as illustrated by U.K. Pat. No. 478,984, Yager et al. U.S. Pat. No. 3,113,864, Vittum et al,. U.S. Pat Nos. 3,002,03.6, 2,271,238 and 2,362,598. Schwan et al. U.S. Pat. No. 2,950,970, Carroll et al. U.S. Pat. No. 2,592,243, Porter et al. U.S. Pat. Nos.
  • the developer contains a color-developing aqent (e.g., a primary aromatic amine which in its oxidized form is capable of reacting with the coupler (coupling) to form the image dye.
  • a color-developing aqent e.g., a primary aromatic amine which in its oxidized form is capable of reacting with the coupler (coupling) to form the image dye.
  • instant self-developing diffusion transfer film can be used as well as photothermographic color film or paper using silver halide in catalytic proximity to reducable silver sources and leuco dyes.
  • the dye-forming couplers can be Incorporated in the photographic elements, as illustrated by Schneider et al. Die Chemie, Vol. 57, 1944, p. 113, Mannes et al. U.S. Pat. No. 2,304,940, Martinez U.S. Pat. No. 2,269,158, Jelley et al. U.S. Pat. No. 2,322,027, Frolich et al. U.S. Pat. No. 2,376,679, Fierke et al. U.S. Pat. No. 2,801,171, Smith U.S. Pat. No. 3,748,141, Tong U.S. Pat. No. 2,772,163, Thirtle et al. U.S. Pat. No.
  • the dye-forming couplers are commonly chosen to form subtractive primary (i.e., yellow, magenta and cyan) image dyes and are nondiffusible, colorless couplers, such as two and four equivalent couplers of the open chain ketomethylene, pyrazolone, pyrazolotriazole, pyrazolobenzimidazole, phenol and naphthol type hydrophobically ballasted for incorporation in high-boiling organic (coupler) solvents.
  • Such couplers are illustrated by Salminen et al. U.S. Pat. Nos. 2,423,730, 2,772,162, 2,895,826, 2,710,803, 2,407,207, 3,737,316 and 2,367,531, Loria et al.
  • the dye-forming couplers upon coupling can release photographically useful fragments, such as development inhibitors or accelerators, bleach accelerators, developing agents, silver halide solvents, toners, hardeners, fogging agents, antifoggants, competing couplers, chemical or spectral sensitizers and desensitizers.
  • Development inhibitor-releasing (DIP) couplers are illustrated by Whitmore et al. U.S. Pat. No. 3,148,062, Barr et al. U.S. Pat. No. 3,227,554, Barr U.S. Pat. No. 3,733,201, Sawdey U.S. Pat. No. 3,617,291, Groet et al. U.S. Pat. No.
  • Silver halide emulsions which are relatively light insensitive such as Lipmann emulsions, having been utilized as interlayers and overcoat layers to prevent or control the migration of development inhibitor fragments as described in Shiba et al. U.S. Pat. No. 3,892,572.
  • the photographic elements can incorporate colored dye-forming couplers, such as those employed to form integral masks for negative color images, as illustrated by Hanson U.S. Pat. No. 2,449,966, Glass et al. U.S. Pat. No. 2,521,908, Gledhill et al. U.S. Pat. No. 3,034,892, Loria U.S. Pat. No. 3,476,563, Lestina U.S. Pat. No. 3,519,429, Friedman U.S. Pat. No. 2,543,691, Puschel et al. U.S. Pat. No. 3,028,238, Men d el et al . U .S. Pat . No. 3,061,432 and Greenhalgh U.K.
  • Particularly useful color couplers include the materials shown in the list of compounds as numbers 21-24.
  • the color provided in the image produced by exposure of each of the differently sensitized silver halide emulsion layers does not have to be produced by color coupler reaction with oxidized color developers.
  • a number of other color image forming mechanisms well known in the art can also be used.
  • the commercially available color image forming mechanisms are the diffusion transfer of dyes, dye-bleaching, and leuco dye oxidation. Each of these procedures is used in commercial products, is well understood by the ordinarily skilled photographic artisan, and is used with silver halide emulsions. Multicolor elements using these different technologies are also commercially available.
  • these existing color forming systems may be modified by the ordinarily skilled artisan according to the teachings of the present invention.
  • the following steps would be taken to convert the element to the practice of the present invention.
  • the sensitizing dye used to spectrally sensitize the first silver halide photothermographic emulsion would be replaced with the sensitizing dye used to sensitize the first emulsion layer of Example 1 of the present application.
  • the filter layer described in Example 2 of the present application would be placed over all the coatings essential to the formation of color in the first deposited series of layers in Example 1 of U.S. Patent 4,460,681.
  • That filter layer could also function as the barrier layer required in the practice of that invention.
  • the second series of layers essential for the formation of the next color according to U.S. Patent 4,460,681 would then be deposited, the spectral sensitizing dye of that example being replaced by the spectral sensitizing dye of Rxample 1 of the present application.
  • the remaining layers in the photothermographic element could then be the same as those described in the patent if light-sensitivity of the element (due to the light-sensitivity of the layers forming the third color) could be tolerated.
  • the second filter layer of Example 2 of the present application could be placed over the second color-forming layer of the photothermographic element.
  • Patent 4,460,681 would then be applied over the filter layer, and the sensitizing dye in that silver halide emulsion layer replaced with the spectral sensitizing dye of the top emulsion layer of Example 1 of the present application.
  • Analogous substitution of sensitizing dyes, addition of filter layers, and/or modification of the relative sensitivities of silver halide layers in any of the other known color imaging processes could also be readily performed given the teachings of the present invention.
  • Diffusion photothermographic color image forming systems such as those disclosed in U.K. Patent 3,100,458A are also useful in the practice of the present invention.
  • the photographic elements can include image dye stabilizers.
  • image dye stabilizers are illustrated by U.K. Pat. No. 1,326,809, Lestina et al. U.S. Pat. Nos. 3,432,300 and 3,698,909, Stern et al. U.S. Pat. No. 3,574,627, B rannock et al. U.S. Pat. No. 3,573,050, Arai et al. U.S. Pat. No. 3,764,337 and Smith et al. U.S. Pat. No. 4,042,394 .
  • Filter dyes are materials well known to the photographic chemist. The dyes where used, must be selected on the basis of their radiation filtering characteristics to insure that they filter the appropriate wavelengths. Filter dyes and their methods of incorporation into photographic elements are well documented in the literature such as U.S. Patent Nos. 4,440,852; 3,671,648; 3,423,207; and 2,895,955; U.K. Patent No.485,624, and Research Disclosure, Vol. 176, December 1978, Item 17643. Filter dyes can be used in the practice of the present invention to provide room-light handleability to the elements.
  • Dyes which will not allow transmission of radiation having wavelengths shorter than the shortest wavelength to which one of the emulsion layers has been sensitized can be used in a layer above one or more (preferably all) of the emulsion layers.
  • the cut-off filter dye preferably does not transmit light more than approximately 50nm less than the shortest wavelength to which any of the emulsion layers have been sensitized.
  • Filter dyes should also be provided with non-fugitive (i.e., non-migratory) characteristics and should he decolorizable (by bleaching in developer or heat, for example) or leachable (e.g., removed by solvent action of any baths).
  • photographic addenda such as coating aids, antistatic agents, acutance dyes, antihalation dyes and layers, antifoggants, latent image stabilizers, antikinking agents, and the like may also be present.
  • HIRF high intensity reciprocity failure
  • stabilizers for this purpose are chloropalladites and chloroplati- nates (U.S. Pat. No. 2,566,263), iridium and/or rhodium salts (U.S. Pat. No. 2,566,263; 3,901,713), and cyanor- hodates (Beck et al., J. Signaletzorulsmaterialen, 1976, 4, 131).
  • a multi-layered IR-sensitive photographic color material was prepared by coating in order on resin-coated paper base the following layers:
  • the second layer A gelatin interlayer containing gel hardener, U.V. absorber, and antioxidant was coated so that the gelatin coating weights are 823 mg per m 2 .
  • the third layer as in the first layer, the same silver chlorobromide emulsion containing a magenta color-forming coupler 22 was sensitized to the 830nm region of the spectrum with dye 8 in the quantity of 1.6 x 10- 4 mol per mol of silver and was coated so that the coating silver and magenta coupler weights are 402 mg per m 2 and 915 mg per m 2 , respectively.
  • the fourth layer a gelatin interlayer containing hardener, U.V. absorber, and antioxidant was coated so that the gelatin coating weight are 1.19 gram per m 2.
  • the fifth layer the same gelatin silver chlorobromide emulsion as in the first layer containing a yellow color-forming coupler 21 was dye sensitized to the 780nm region of the spectrum with 7 in the quantity of 5.9 x 10- 4 mol per mol of silver and was coated so that the coating silver and yellow coupler weights are 346 mg per m 2 and 474 mg per m 2 , respectively.
  • the sixth layer a gelatin interlayer containing hardener, U.V. absorber and antioxidant was coated so that the gelatin coating weight is 873 mg per m 2 .
  • the seventh layer a protective gelatin topcoat containing a hardener and surfactant was coated so that the gelatin coating weight is 1.03 g/m 2 . ⁇
  • a three-color IR-sensitive material may be prepared in the following manner by coating on a resin-coated paper substrate:
  • the above described construction when exposed with a tungsten lamp sensitometer giving 2400 mc illuminance at the filter plane for 0.1 sec. through a 20 cm continuous wedge (gradient: 0.20 density/cm), a Wratten red selective filter, and a 780nm near infrared glass bandpass filter may have D logE curves similar to those shown in Figure 2. There is some overlap of D logE curves for layer 5 and layer 3 when no filter dye is present in layer 4 (shown with solid line) and therefore, no pure color separation would be observed after exposure.
  • the need for the 830nm absorbing filter dye in layer 2 may become unnecessary if the speed of the emulsion layers 1 and 3 are manipulated properly as described below:
  • overlap of D logE curves for Layer 5 and Layer 3 occurs without a filter dye present in Layer 4 (solid lines) and after the incorporation of the dye in Layer 4, pure color separation with the 780nm exposure is achieved as shown by the dashed line for Layer 3.
  • the 830nm filter full density of color for Layer 3 is achieved before any exposure of Layer 1 negates the need for a filter dye in Layer 2. Good color separation was achieved because of the accurate speed manipulation of both these layers.
  • a photographic element was prepared by coating sequentially the following three layers onto a subbed polyester film support.
  • Coating 2 was identical with Coating 1 except that a magenta dye developer of structure C replaced the yellow dye developer in the first layer and the silver halide emulsion was sensitized not to 780 nm but to 830 nm radiation by the addition of a sensitizing dye of structure D (5 x 10- 5 moles dye per mole silver).
  • the samples were laminated to Agfa-Gervaert "Copycolor CCF” dye receptor sheets using an Agfa-Gevaert "CP 380" color diffusion transfer processing machine containing 2% aqueous potassium hydroxide as processing solution.
  • the receptor sheets were separated after one minute.
  • Coating 1 showed a maximum sensitivity at 760 nm resulting in a positive yellow image on the receptor sheet. Coating 1 exhibited no measurable sensitivity at 820 nm or longer wavelengths.
  • Coating 2 was 0.57 reciprocal Log exposure units less sensitive at 760 nm than at 820 nm and 1.70 reciprocal Log exposure,units less sensitive at 880 nm than at 820 nm.
  • a single-color Infrared-sensitive photographic material was prepared by coating in order on resin-coated paper base the following layers:
  • a single-color Infrared-sensitive material was prepared as described in Example 5; however, dye was added as a filter dye and coated so that the filter dye coating weight was 15.1 mg/m 2 in the second layer.
  • a single-color Infrared-sensitive material was prepared as described in Example 5; however, no filter dye was incorporated into the second layer (control).
  • the materials were exposed with a tungsten lamp sensitometer giving 2400 mc illuminance at the filter plane for 0.1 seconds through a 20 cm continuous wedge (gradient: 0.20 density per cm), a Wratten red selective filter and a 830 nm near infrared, glass, bandpass filter. After exposure, these samples were processed in standard Kodak EP-2 processing color chemistry with conditions similar to those stated in U.S. Patent 4,363,873.
  • Relative speed measured at an absolute density of 0.75. 2 The slope of the line joining the density points of 0.50 and 1.30 above base + fog.
  • a full-color Infrared-sensitive material was prepared by coating in order on resin-coated paper base the following layers:
  • the second layer a gelatin interlayer containing gel hardener, U.V. absorber, and antioxidant was coated so that the gelatin coating weight was 828 mg/m2 .
  • the third layer a gelatin chemically sensitized silver chlorobromide emulsion (6.6% Ag) containing anti-foggants, speed enhancers, and magenta color-forming coupler 2 2 was sensitized to the 830 nm region of the spectrum with dye 8 in the quantity of 8.9 x 10- 5 mol per mol of silver and was coated so that the silver and magenta coupler coating weights were 492 mg/m 2 and 1.12 g/m 2 , respectively.
  • the fourth layer a gelatin interlayer containing hardener, U.V. absorber, antioxidant and the filter dye 29, which has been dissolved in methanol and added to the gelatin mixture, was coated such that the filter dye and gelatin coating weights were 8.3 mg/m 2 and 0.65 g/m 2 , respectively.
  • the fifth layer a gelatin chemically sensitized silver chlorobromide emulsion (6.7% Ag) containing antif ggants, speed enhancers, and yellow color-forming coupler 21 was dye sensitized to the 780 nm region of the spectrum with dye 7 in the quantity of 3.4 x 10- 4 mol per mol of silver and was coated so that the coating silver and yellow coupler weights were 497 mg/m 2 and 679 mg/m 2 , respectively.
  • the sixth layer a gelatin interlayer containing hardener, U.V. absorber, and antioxidant was coated so that the gelatin coating weight was 876 mg/m 2 .
  • the seventh layer a protective gelatin top-coat containing a hardener and surfactant was coated so that the gelatin coating weight was 1.04 g/m 2 .
  • a multi-color Infrared-sensitive material was prepared as described in Example 8; however, dye 8 was added as a filter dye and coated so that the filter dye coating weight was 8.3 mg/m 2 in the fourth layer.
  • a multi-color Infrared-sensitive material was prepared as descrihed in Example 8; however, no filter dye was incorporated into the fourth layer (control) and the gel coating weight was 1.20 g/m 2 .
  • the sensitometric results are shown in Table 2.
  • the filter dye gel interlayer (layer 4) from examples 8 and 9 were hand-spread onto polyethylene terephthalate as desribed above.
  • the absorption curves suggest that absorption of 780 nm and 830 nm light would be similar for the dye interlayer of example 8 and that less absorption of the 830 nm light vs. 780 nm light would be observed for the dye interlayer of example 9.
  • the sensitometric results for the multi-layer material of these examples also suggests this observation.
  • the loss in speed for layer 3 magenta color
  • the control is approximately .25 loqR and .36 logE for example 9 and 8, respectively.
  • the loss in speed for layer 3 vs. the control was minimal for example 9 (less dye interlayer filtering) vs. example 8 (0.9 logE vs..27 logE).
  • the first pass of 780 nm light through the multilayer materials of example 8 and 9 is non-filtered for layer 5 (780 nm sensitized) so that the first exposure occurs, then as the residual 780 nm light passes through layer 4, some of the light is absorbed. After this filtration, the remaining 780 nm light then continues through the layers, reaches the base, and is reflected back through the layers until more of this light is absorbed or filtered again (effective double filtration) while passing through layer 4 (filter layer) to reexpose the 780 nm layer (layer 5).
  • the total amount of effective 780 nm exposure will be less for multilayer materials containing the filter dye interlayers vs. non-filter dye interlayer constructions and therefore, the observed speed of the 780 nm sensitized (layer 5) will be less because of this total lower amount of exposure.
  • a multi-layered IR-sensitive photographic olor material was prepared by coating in order on resin-coated paper base the following layers:
  • the second layer A gelatin interlayer containing gelatin hardener, U.V. absorber, and antioxidant was coated so that the gelatin coating weight was 828 mg per m 2 .
  • the third layer A gelatin/chemically sensitized silver chlorobromide emulsion (88 mol %Br, 6.7% Ag, and approximately 0.5 micron grain size) containing. anti-foggants, speed enhancers, and the magenta color-forming coupler 22 was sensitized to the 830 nm region of the spectrum with dye 8 in the quantity of 8.8 x 10 -5 mol per mol silver. This was coated so that the silver and coupler coating weights were 492 mg per m 2 and 1.12 g per m 2 , respectively.
  • the fourth layer A gelatin interlayer containing hardener, U.V. absorber, and antioxidant was coated so that the gelatin coating weight was 1.20 g per m 2 .
  • the fifth layer The same gelatin silver chlorobromide emulsion as in the first layer, containing the yellow color-forming coupler 21, was dye sensitized to the 780 nm region of the spectrum with dye 7 in the quantity of 3.4 x 10- 4 mol per mol silver. This was coated so that the silver and coupler coating weights were 542 mg per m 2 and 748 mg per m 2 , respectively.
  • the sixth layer A gelatin interlayer containing hardener, U.V. absorber and antioxidant was coated so that the gelatin coating weight was 876 mg per m 2 .
  • the seventh layer A protective gelatin topcoat containing a hardener and surfactant was coated so that the gelatin coating weight was 1.04 g per m 2 .
  • a multi-layered IR-sensitive photographic material was prepared as described in Example 11, except that the 780 nm sensitized layer (fifth layer) was coated as the third layer and the 830 nm sensitized layer (third layer) was coated as the fifth layer.
  • a mnlti layered IR-sensitive photographic material was prepared as described in Example 11, except that the 700 nm sensitized layer (fifth layer) was coated as the first layer and the 880 nm sensitized layer (first layer) was coated as the fifth layer.
  • the constructions described above were first exposed with the output from a 780 nm 2 mw laser diode sensitometer.
  • the sensitometer is capable of writing laser raster exposures onto film strips through a circular wedge, neutral-density filter (metal vacuum-deposited, 0-4 neutral density). Separate samples were then similarly exposed using a 820 nm or a 880 nm laser diode source in the sensitometer. After exposure, these samples were processed in standard Kodak EP-2 processing color chemistry.
EP85308585A 1984-11-26 1985-11-26 Farbphotographisches Element Expired - Lifetime EP0183528B2 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US67458384A 1984-11-26 1984-11-26
US674583 1984-11-26
US70956185A 1985-03-08 1985-03-08
US709561 1985-03-08

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EP0183528A2 true EP0183528A2 (de) 1986-06-04
EP0183528A3 EP0183528A3 (en) 1987-11-19
EP0183528B1 EP0183528B1 (de) 1990-01-31
EP0183528B2 EP0183528B2 (de) 1999-02-03

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EP85308585A Expired - Lifetime EP0183528B2 (de) 1984-11-26 1985-11-26 Farbphotographisches Element

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EP (1) EP0183528B2 (de)
JP (1) JPH0690462B2 (de)
KR (1) KR940009426B1 (de)
AR (1) AR242306A1 (de)
AU (1) AU583323B2 (de)
BR (1) BR8505901A (de)
CA (1) CA1263051A (de)
DE (1) DE3575795D1 (de)
MX (1) MX162217A (de)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0385496A2 (de) * 1989-03-03 1990-09-05 Fuji Photo Film Co., Ltd. Lichtempfindliches Farbmaterial
EP0420012A1 (de) * 1989-09-26 1991-04-03 Eastman Kodak Company Infrarotempfindliches photographisches Element
EP0420011A1 (de) * 1989-09-26 1991-04-03 Eastman Kodak Company Infrarotempfindliches fotografisches Element mit mindestens zwei fotoempfindlichen Schichten
EP0421464A1 (de) * 1989-10-06 1991-04-10 Fuji Photo Film Co., Ltd. Verfahren zur Lagerung von infrarotempfindlichem fotografischem Silberhalogenidmaterial und fotografische Zusammensetzung enthaltend infrarotempfindliches fotografisches Silberhalogenidmaterial und dessen Verpackung
WO1991006038A1 (en) * 1989-10-20 1991-05-02 Eastman Kodak Company Color imaging process and apparatus
EP0479167A1 (de) * 1990-09-28 1992-04-08 Fuji Photo Film Co., Ltd. Wärmeentwickelbares lichtempfindliches Farbmaterial vom Farbdiffusionübertragungstyp

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JPH02157749A (ja) * 1988-12-09 1990-06-18 Fuji Photo Film Co Ltd フルカラー記録材料およびカラー画像形成法
JP2670876B2 (ja) * 1989-02-14 1997-10-29 富士写真フイルム株式会社 カラー画像形成方法
JPH0320730A (ja) * 1989-03-22 1991-01-29 Fuji Photo Film Co Ltd フルカラー記録材料およびカラー画像形成法
JPH02248945A (ja) * 1989-03-22 1990-10-04 Fuji Photo Film Co Ltd フルカラー高塩化銀写真感光材料およびこれを用いたカラー画像形成法
JP2896439B2 (ja) * 1989-04-04 1999-05-31 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料およびカラー画像形成方法
JPH02285345A (ja) * 1989-04-27 1990-11-22 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料
JPH0368938A (ja) * 1989-08-08 1991-03-25 Fuji Photo Film Co Ltd 反射カラー感光材料及びカラー画像形成法
JPH0384545A (ja) * 1989-08-29 1991-04-10 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料およびカラー画像形成方法
JPH0431854A (ja) * 1990-05-28 1992-02-04 Fuji Photo Film Co Ltd 熱現像カラー感光材料
JP2699008B2 (ja) * 1990-04-16 1998-01-19 富士写真フイルム株式会社 熱現像感光材料
JPH044161A (ja) * 1990-04-20 1992-01-08 Fuji Photo Film Co Ltd ハードコピー作成方法
DE69229515T2 (de) 1991-03-05 1999-10-28 Fuji Photo Film Co Ltd Farbphotographisches Diffusionsübertragungsmaterial und farbphotographisches hitzeentwickelbares Material
JPH08146577A (ja) 1994-11-25 1996-06-07 Fuji Photo Film Co Ltd 熱現像カラー感光材料
DE60120079T8 (de) 2000-10-31 2007-06-28 Dainippon Screen Mfg. Co., Ltd. Laserbestrahlungsgerät und Bildaufzeichnungsgerät
DE102006043216A1 (de) * 2006-06-02 2007-12-06 Inoviscoat Gmbh Verbundmaterial und Verfahren zum Herstellen eines derartigen Verbundmaterials

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US2403722A (en) * 1942-10-24 1946-07-09 Eastman Kodak Co Camouflage detection
US3663228A (en) * 1961-03-24 1972-05-16 Applied Photo Sciences Color photographic film having extended exposure-response characteristics
GB2114311A (en) * 1982-01-25 1983-08-17 Gerber Scient Inc Daylight photoplotting and film therefor
US4469779A (en) * 1983-03-16 1984-09-04 Environmental Research Institute Of Michigan Infrared color photographic film

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GB114311A (en) * 1917-02-24 1919-03-06 Herman Jansen Improvements in Letter Paper.
BE548641A (de) * 1955-06-15
JPS519436A (ja) * 1974-07-15 1976-01-26 Yoshino Zenzaburo Sekigaibunrisatsueihoho
JPS5910947A (ja) * 1982-07-10 1984-01-20 Konishiroku Photo Ind Co Ltd ハロゲン化銀カラ−写真感光材料
JPS5922049A (ja) * 1982-07-28 1984-02-04 Konishiroku Photo Ind Co Ltd 熱現像性カラ−写真感光材料及び画像形成方法
JPS5990848A (ja) * 1982-11-16 1984-05-25 Konishiroku Photo Ind Co Ltd ハロゲン化銀写真感光材料

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US2403722A (en) * 1942-10-24 1946-07-09 Eastman Kodak Co Camouflage detection
US3663228A (en) * 1961-03-24 1972-05-16 Applied Photo Sciences Color photographic film having extended exposure-response characteristics
GB2114311A (en) * 1982-01-25 1983-08-17 Gerber Scient Inc Daylight photoplotting and film therefor
US4469779A (en) * 1983-03-16 1984-09-04 Environmental Research Institute Of Michigan Infrared color photographic film

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0385496A2 (de) * 1989-03-03 1990-09-05 Fuji Photo Film Co., Ltd. Lichtempfindliches Farbmaterial
EP0385496A3 (de) * 1989-03-03 1991-09-25 Fuji Photo Film Co., Ltd. Lichtempfindliches Farbmaterial
US5413902A (en) * 1989-03-03 1995-05-09 Fuji Photo Film Co., Ltd. Color light-sensitive material
EP0420012A1 (de) * 1989-09-26 1991-04-03 Eastman Kodak Company Infrarotempfindliches photographisches Element
EP0420011A1 (de) * 1989-09-26 1991-04-03 Eastman Kodak Company Infrarotempfindliches fotografisches Element mit mindestens zwei fotoempfindlichen Schichten
EP0421464A1 (de) * 1989-10-06 1991-04-10 Fuji Photo Film Co., Ltd. Verfahren zur Lagerung von infrarotempfindlichem fotografischem Silberhalogenidmaterial und fotografische Zusammensetzung enthaltend infrarotempfindliches fotografisches Silberhalogenidmaterial und dessen Verpackung
WO1991006038A1 (en) * 1989-10-20 1991-05-02 Eastman Kodak Company Color imaging process and apparatus
EP0479167A1 (de) * 1990-09-28 1992-04-08 Fuji Photo Film Co., Ltd. Wärmeentwickelbares lichtempfindliches Farbmaterial vom Farbdiffusionübertragungstyp
US5270155A (en) * 1990-09-28 1993-12-14 Fuji Photo Film Co. Ltd. Dye diffusion transfer type heat developable color light-sensitive material

Also Published As

Publication number Publication date
AU5031585A (en) 1986-06-05
KR940009426B1 (ko) 1994-10-13
EP0183528A3 (en) 1987-11-19
CA1263051A (en) 1989-11-21
DE3575795D1 (de) 1990-03-08
JPH0690462B2 (ja) 1994-11-14
AU583323B2 (en) 1989-04-27
AR242306A1 (es) 1993-03-31
BR8505901A (pt) 1986-08-12
KR860004336A (ko) 1986-06-20
MX162217A (es) 1991-04-10
EP0183528B1 (de) 1990-01-31
EP0183528B2 (de) 1999-02-03
JPS61137149A (ja) 1986-06-24

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