USH1515H - Silver halide photographic material - Google Patents

Silver halide photographic material Download PDF

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Publication number
USH1515H
USH1515H US08/113,755 US11375593A USH1515H US H1515 H USH1515 H US H1515H US 11375593 A US11375593 A US 11375593A US H1515 H USH1515 H US H1515H
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group
hydrogen atom
alkyl
alkyl group
aryl
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US08/113,755
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Yasushi Hattori
Yoshiharu Yabuki
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Assigned to FUJI PHOTO FILM CO., LTD. reassignment FUJI PHOTO FILM CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HATTORI, YASUSHI, YABUKI, YOSHIHARU
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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
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
    • G03C1/83—Organic dyestuffs 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
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/91—Photosensitive materials characterised by the base or auxiliary layers characterised by subbing layers or subbing means
    • 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
    • G03C2200/00—Details
    • G03C2200/47—Polymer

Definitions

  • This invention relates to a silver halide photographic material, and more particularly to a silver halide photographic material which is well adapted for rapid processing, and which provides an image of high quality and has high sensitivity.
  • Conventional methods for exposure of photographic materials to light include an image forming method using a scanner system. Therein, the original is scanned, and a silver halide photographic material is exposed to light based on the resulting image signals to form a negative image or a positive image corresponding to that of the original.
  • Many recording devices which practically use such a scanner system type image forming method are conventionally known.
  • Light sources which are conventionally used for the recording of the scanner system type recording devices include glow lamps, xenon lamps, mercury vapor lamps, tungsten lamps and light-emitting diodes. However, these light sources are disadvantageous in that their output is low and their working life is short.
  • Scanners and laser printers are known where exposure to light is conducted under high illumination conditions using coherent laser beams such as He-Ne laser beams, argon laser beams and He-Cd laser beams as light sources for the scanner system to remedy the above-described disadvantages.
  • coherent laser beams such as He-Ne laser beams, argon laser beams and He-Cd laser beams
  • these scanners and laser printers are disadvantageous in that the devices are large-sized and expensive and a modulator is required.
  • the illumination source for exposure emits visible light, there is a limit to safelight use for the photographic materials, and handleability is also poor.
  • semiconductor lasers are small-sized and inexpensive, modulation is easily conducted, and semiconductor lasers have a working life which is longer than that of the foregoing lasers.
  • a safelight is advantageously used with semiconductor lasers which emit light in the infrared region. Thus, handleability and workability are improved.
  • Dyes which absorb light in the infrared region are generally used to prevent halation, to thereby reduce blurring of the image due to exposure to infrared light.
  • the dyes can remain in the photographic material after processing, so long as the dyes do not absorb visible light.
  • the dyes usually absorb some visible light, and a residual color is formed when the dyes remain in the photographic material after processing. The formation of the residual color is practically not preferred. Accordingly, water-soluble dyes are used as the antihalation dyes.
  • dyes which absorb light in the visible wavelength region are mainly disclosed in the above patent specifications. Even where dyes which absorb light in the infrared region are disclosed, it has been found that the dyes specifically exemplified therein are not sufficiently fixed to a specific layer.
  • An object of the present invention is to provide a silver halide photographic material having high sensitivity and providing high image quality, and which photographic material is well adapted for rapid processing.
  • a silver halide photographic material comprising a transparent support having thereon a dye layer, a hydrophobic polymer layer and at least one light-sensitive silver halide emulsion layer, wherein the dye layer contains at least one dye represented by formulae (I) to (VIII) dispersed in the form of fine solid particles, the dye layer is disposed between the at least one light-sensitive silver halide emulsion layer and the support, the hydrophilic colloid coating weight of the dye layer is 0.5 g/m 2 or less, and the hydrophobic polymer layer is disposed between the dye layer and the support: ##STR1## wherein T 10 , T 11 and T 12 independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carboxyl group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio
  • examples of a substituent group for R 15 and R 16 include a hydrogen atom, an alkyl group, an alkoxy group and a halogen atom.
  • examples of a substituent group for R 75 and R 76 include an hydrogen atom, an alkyl group, an alkoxy group and a halogen atom.
  • an alkyl group has preferably 1 to 8 carbon atoms and more preferably 1 to 4 carbon atoms.
  • Examples of the alkyl group include methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, hexyl and octyl. Further, the alkyl group may be substituted.
  • substituents include an alkyl group, an aryl group, an alkoxy group, a halogen atom, a cyano group, a carboxyl group, a sulfonamido group, a sulfamoyl group, an acyl group, an alkoxycarbonyl group, an acylamino group, a carbamoyl group, a hydroxyl group and an alkylsulfonyl group.
  • the aryl group is preferably a phenyl group or a naphthyl group and more preferably a phenyl group.
  • the aryl group may be substituted.
  • substituents include the substituents for the alkyl group described above.
  • the alkoxy group has preferably 1 to 8 carbon atoms and more preferably 1 to 4 carbon atoms.
  • Examples of the alkoxy group include methoxy, ethoxy, n-propyloxy and n-butoxy.
  • the alkoxy group may be substituted.
  • Examples of the substituents include an alkyl group, an alkoxy group, an aryl group and a halogen atom.
  • the aryloxy group is preferably a phenoxy group or a naphthoxy group and more preferably a phenoxy group.
  • the aryloxy group may be substituted.
  • substituents include the substituents for the alkyl group described above.
  • examples of the heterocyclic group include a pyridyl group, a thienyl group, a furano group and an imidazolyl group.
  • examples of the halogen atom include fluorine, chlorine, bromine and iodine. Among these, fluorine, chlorine and bromine are preferred.
  • examples of X.sup. ⁇ include Cl.sup. ⁇ , Br.sup. ⁇ , CF 3 SO 3 .sup. ⁇ , ClO 4 .sup. ⁇ , PF 6 .sup. ⁇ , CH 3 SO 3 .sup. ⁇ and CH 3 CO 2 .sup. ⁇ .
  • the dyes for use in the present invention can be easily synthesized by the methods described in PCT-WO 88/04794, European Patent (Laid-Open) Nos. 0,274,723A1, 276,566 and 299,435, JP-A-52-92716, JP-A-55-155350, JP-A-55-155351, JP-A-61-205934, JP-A-48-68623, JP-A-3-167546, JP-A-3-7931, JP-A-2-282244, and U.S. Pat. Nos. 2,527,583, 3,486,897, 3,746,539, 3,933,798, 4,130,429 and 4,040,841 and referring to these methods.
  • dye dispersed in the form of fine solid particles refers to a dye contained in a dye layer, which dye has poor solubility in the dye (colored) layer so that the dye can not be present therein in the molecular state, but is present as a solid having a (large) particle size so that the dye substantially does not diffuse within the dye layer.
  • the dispersion can be prepared according to the method described in JP-A-63-197943.
  • the contents are added to 160 g of a 12.5 wt % aqueous solution of gelatin, and placed in a roll mill for 10 minutes to reduce bubbles.
  • the resulting mixture is filtered to remove the ZrO 2 beads.
  • the resulting solid as such is composed of fine particles having an average particle size of about 0.3 ⁇ m. Accordingly, the particles are classified by centrifugal separation into particles having a particle size of 1 ⁇ m or smaller.
  • the dye crystallites for use in the present invention have a particle size of preferably 1.0 ⁇ m or smaller, more preferably 0.5 ⁇ m or smaller and most preferably 0.01 to 0.5 ⁇ m.
  • the dyes are coated in an amount of preferably 5 to 300 mg/m 2 , particularly preferably 10 to 150 mg/m 2 .
  • the amount of gelatin used in preparation of the dispersion is that amount which provides a coating weight of gelatin (hydrophilic colloid) of 0.5 g/m 2 or less.
  • the gelatin (hydrophilic colloid) coating weight of the dye layer of the present invention is 0.5 g/m 2 or less, preferably 0.05 to 0.3 g/m 2 .
  • the total coating weight of hydrophilic colloid of the photographic material of the present invention is preferably not more than 3 g/m 2 , more preferably 1 to 2.5 g/m 2 per each side of the support.
  • the dye layer is preferably provided as a subbing layer.
  • the subbing layer contains a hydrophilic colloid to improve adhesion between the support and another hydrophilic colloid layer such as a silver halide emulsion layer. Accordingly, when the dye layer serves as the subbing layer (e.g. the second subbing layer as described below), the dye layer can be provided without increasing the total amount of hydrophilic colloid.
  • the coating weight of silver is preferably 3 g/m 2 or less, more preferably 2 g/m 2 or less, particularly preferably 0.5 to 3 g/m 2 .
  • Examples of the transparent support preferably used in the present invention include polyethylene terephthalate film and cellulose triacetate film.
  • the surface of the support is preferably subjected to a corona-discharging treatment, a glow-discharging treatment or an ultraviolet-irradiation treatment to improve the adhesion between the support and the hydrophilic colloid layer.
  • a first subbing layer comprising, for example, a styrene butadiene latex or a vinylidene chloride latex (hydrophobic polymer layer) is disposed between the dye layer and the support.
  • hydrophobic polymers for use in the first subbing layer include styrene-butadiene copolymers, vinylidene chloride copolymers, water-soluble polyesters and polyacrylic esters. Of these polymers, styrene-butadiene copolymers and vinylidene chloride copolymers are preferred. More preferred are the styrene-butadiene copolymers.
  • the styrene-butadiene copolymers may be copolymers of styrene and butadiene monomers in a weight ratio of from 9/1 to 1/9, and may optionally comprise a repeating unit derived from a third monomer such as acrylic acid.
  • the coating weight of the hydrophobic polymer in the first subbing layer is preferably 100 to 1,000 mg/m 2 .
  • the drying temperature of the subbing layer is preferably 80° to 200° C.
  • An aqueous dispersion (latex) of the hydrophobic polymer for use in the first subbing layer is preferably prepared as a coating solution, and further a crosslinking agent, a surfactant, a swelling agent, a matting agent, an antistatic agent, etc. are optionally added to the aqueous dispersion.
  • crosslinking agent examples include the triazine compounds described in U.S. Pat. Nos. 3,325,287, 3,288,775 and 3,549,377 and Belgian Patent 6,602,226; the dialdehyde compounds described in U.S. Pat. Nos. 3,291,624 and 3,232,764, French Patent 1,543,694 and U.K. Patent 1,270,578; the epoxy compounds described in U.S. Pat. No. 3,091,537 and JP-B-49-26580 (the term "JP-B” as used herein means an "examined Japanese patent publication”); the vinyl compounds described in U.S. Pat. No. 3,642,486; the aziridine compounds described in U.S. Pat. No. 3,392,024; the ethyleneimine compounds described in U.S. Pat. No. 3,549,379; and methylol compounds. Of these compounds, dichlorotriazine compounds are preferred.
  • a hydrophilic colloid layer as a second subbing layer is preferably provided on the first subbing layer (hydrophobic polymer layer) in the present invention.
  • the coating weight of hydrophilic colloid in the second subbing layer is preferably 20 mg/m 2 to 0.4 g/m 2 .
  • the drying temperature of the second hydrophilic colloid layer is preferably 80° C. or more to effect good adhesion of the second layer to the first subbing layer.
  • the drying temperature is 180° C. or lower.
  • the drying temperature is not higher than 160° C.
  • a back layer as described in Japanese Patent Application No. 3-145168 is used to balance the drying property with repsect to curling.
  • a light-insensitive hydrophilic colloid layer containing a hydrophilic colloid as a binder is provided on a second side of the support opposite the side having thereon at least one silver halide emulsion layer, and a hydrophobic polymer layer is provided on the second side of the support further away from the support than the light-insensitive hydrophilic colloid layer, and the light-insensitive hydrophilic colloid layer and the hydrophobic polymer layer are substantially not swollen when contacted with a processing solution (i.e., the thickness of their layers after the drying step is not more than 1.05 times that after completion of the water washing step in the development).
  • a biaxially stretched blue-colored polyethylene terephthalate film of 175 ⁇ m in thickness was subjected to corona discharging treatment.
  • the polyethylene terephthalate film contained 1,4-bis(2,6-diethylanilino) anthraquinone.
  • the following hydrophobic polymer layer was then coated on the film in such amount as to provide the following coating weights. The coating was carried out using a wire bar coater. The coated film was dried at 175° C. for one minute.
  • the latex solution contained 0.4% by weight of the following emulsifying dispersant (a) based on the amount, on a solid basis, of the latex.
  • Emulsifying Dispersant (a) ##STR10##
  • hydrophilic colloid layer was coated thereon in such amount as to provide the following coating weights.
  • the coating was carried out using a wire bar coater.
  • the coated film was dried at 150° C. for one minute.
  • Second Subbing Layer Hydrophilic Colloid Layer
  • the resulting emulsion was washed with water by conventional flocculation method, and 30 g of gelatin was added thereto.
  • the pH of the emulsion was adjusted to 5.2, and the pAg thereof was adjusted to 7.5.
  • 1 mg of sodium thiosulfate and 1.5 mg of the following compound (a) were added thereto, and chemical sensitization was carried out so as to provide the maximum sensitivity.
  • the resulting samples were exposed to light through an interference filter having a peak at 633 nm and a continuous wedge using a xenon flash lamp (emission time: 10 -6 sec), and processed under the following temperature and time conditions using an automatic processor FG-710NH (manufactured by Fuji Photo Film Co., Ltd.) to carry out sensitometry.
  • an automatic processor FG-710NH manufactured by Fuji Photo Film Co., Ltd.
  • the pH was adjusted with sodium hydroxide to 10.7.
  • the pH was adjusted with sodium hydroxide to 6.0.
  • the reciprocal of the exposure amount providing a density of 3.0 is referred to as the sensitivity.
  • the sensitivity is shown in Tables 1 and 2 below relative to the sensitivity of Photographic Material 4 taken as 100.
  • the incline of the straight line formed by joining the point of a density of 0.1 on the characteristic curve to the point of a density of 3.0 thereon is referred to as the gradation.
  • Films having a size of 24.5 ⁇ 30.5 cm were processed in an automatic processor.
  • the films which left the drying zone of the processor were immediately touched with the hand, and the dry state of the films was examined.
  • the criterion of evaluation is as follows:
  • the mark B The film leaving the drying zone was damp to touch and insufficiently dried.
  • a biaxially stretched blue-colored polyethylene terephthalate film of 175 ⁇ m in thickness was subjected to corona discharging treatment.
  • the polyethylene terephthalate film contained 1,4-bis(2,6-diethylanilino)anthraquinone.
  • the following hydrophobic polymer layer was coated on the film in such amount as to provide the following coating weights. The coating was carried out using a wire bar coater. The coated film was dried at 175° C. for one minute.
  • the latex solution contained 0.4 wt % of the following emulsifying dispersant (a) based on the amount, on a solid basis, of the latex.
  • Emulsifying Dispersant (a) ##STR18##
  • hydrophilic colloid layer was coated thereon in an amount to provide the following coating weight.
  • the coating was carried out using a wire bar coater.
  • the coated film was dried at 150° C. for one minute.
  • Second Subbing Layer Hydrophilic Colloid Layer
  • the pH of the emulsion was adjusted to 6.5, and the pAg thereof was adjusted to 8.1. Subsequently, 2.5 mg of sodium thiosulfate and 5 mg of chloroauric acid were added thereto, and chemical sensitization was carried out at 65° C. Further, 0.2 g of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene was added thereto, and the emulsion was quenched to solify the same (Emulsion A).
  • cubic monodisperse silver chlorobromide grains having a mean grain size of 0.3 ⁇ m were prepared in the same manner as Emulsion A, except that the gelatin solution was heated to 40° C. After desalting, 50 g of gelatin was added thereto. The pH of the emulsion was adjusted to 6.5, and the pAg thereof was adjusted to 8.1. Subsequently, 2.5 mg of sodium thiosulfate and 5 mg of chloroauric acid were added thereto, and chemical sensitization was carried out at 65° C. Further, 0.2 g of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene was added thereto, and the emulsion was quenched to solidify the same, thereby obtaining Emulsion B.
  • Emulsion A and Emulsion B in a ratio of 1:1 by weight were mixed, and the following additives were added to the emulsion mixture to obtain an emulsion coating solution, each amount being per mol of silver halide.
  • a container was heated to 40° C. and the following additives were added thereto to prepare the coating solution.
  • the above emulsion coating solution and the above coating solution for the surface protective layer were coated on each of Supports 9 and 10 in such amount as to provide a total silver coating weight (as Ag) of 2.3 g/m 2 to prepare each of Photographic Materials 10 and Ill.
  • the gelatin coating weight of the emulsion layer was 1.4 g/m 2
  • the gelatin coating weight of the surface protective layer was 1.0 g/m 2 .
  • the sensitivity of each emulsions was measured by the following sensitometry.
  • the sensitometry of the thus-prepared Photographic Materials 10 and 11 was carried out in the following manner to measure the sensitivity and the gamma (contrast) value.
  • Photographic Materials 10 and 11 were stored at 25° C. and 60% RH for 7 days after coating, and subjected to scanning exposure at room temperature using a semiconductor laser of 780 nm ("FCR Laser Image Printer type CR-LP414" manufactured by Fuji Photo Film Co., Ltd.).
  • the photographic materials were then processed using an automatic processor FCR (manufactured by Fuji Photo Film Co., Ltd.) under conditions of a development temperature of 35° C., and a Dry to Dry time of 67 seconds.
  • the conveying speed was mm/min.
  • the replenishment rate of the developing solution was 23 ml/m 2 of the photographic material, and that of the fixing solution was 23 ml/m 2 of the photographic material.
  • the reciprocal of the exposure amount providing an optical density of the density of the unexposed area +1.0 is referred to as the sensitivity.
  • the sensitivity is represented relative to the sensitivity of the Photographic Material 11 taken as 100.
  • the processing solutions had the following compositions.
  • subbing layers were provided on the side opposite to that on which the subbing layers were previously coated in preparation of Support 3 of Example 1.
  • the side on which the subbing layers were previously coated is referred to as the front side, and the side on which the following subbing layers are provided is referred to as the back side.
  • the following first subbing layer was coated on the back side in such amount as to provide the following coating weights.
  • the coating was carried out using a wire bar coater.
  • the coated support was dried at 185° C. for one minute.
  • the latex solution contained 0.4 wt % of the following emulsifying dispersant (a) based on the amount, on a solid basis, of the latex.
  • Emulsifying Dispersant (a) ##STR26##
  • the following second subbing layer was coated on both sides of the support in such amount as to provide the following coating weights.
  • the coating was carried out using a wire bar coater.
  • the coated support was dried at 150° C. for one minute.
  • the following insensitive hydrophilic colloid layer and the following polymer layer were coated (in this order) on the back side of Support 11 in such amount as to provide the following coating weights.
  • the coated support was dried at 50° C. for 5 minutes.
  • the emulsion layer and the surface protective layer were coated on the front side of Support 11 in the same manner as in preparation of Photographic Material 4 of Example 1.
  • the obtained Samples were cut into test pieces of 5 cm (long) by 1 cm (wide), stored at 25° C. and 60% RH for 3 days and then transferred to an atmosphere of 25° C. and 10% RH. After 2 hours, the extent of curling of the test pieces was measured.
  • the curling value is determined by the following formula.
  • the present invention provides silver halide photographic materials having high sensitivity and good image quality, which photographic materials are well adapted for rapid processing.

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Abstract

A silver halide photographic material is disclosed, which comprises a transparent support having thereon a dye layer, a hydrophobic polymer layer and at least one light-sensitive silver halide emulsion layer, wherein the dye layer containing one or more specified dyes dispersed in the form of fine solid particles is provided between the light-sensitive silver halide emulsion layer and the support, the hydrophilic colloid coating weight of the dye layer is 0.5 g/m2 or less, and a hydrophobic polymer layer is provided between the dye layer and the support.

Description

FIELD OF THE INVENTION
This invention relates to a silver halide photographic material, and more particularly to a silver halide photographic material which is well adapted for rapid processing, and which provides an image of high quality and has high sensitivity.
BACKGROUND OF THE INVENTION
Conventional methods for exposure of photographic materials to light include an image forming method using a scanner system. Therein, the original is scanned, and a silver halide photographic material is exposed to light based on the resulting image signals to form a negative image or a positive image corresponding to that of the original. Many recording devices which practically use such a scanner system type image forming method are conventionally known. Light sources which are conventionally used for the recording of the scanner system type recording devices include glow lamps, xenon lamps, mercury vapor lamps, tungsten lamps and light-emitting diodes. However, these light sources are disadvantageous in that their output is low and their working life is short. Scanners and laser printers are known where exposure to light is conducted under high illumination conditions using coherent laser beams such as He-Ne laser beams, argon laser beams and He-Cd laser beams as light sources for the scanner system to remedy the above-described disadvantages. However, although providing a high output, these scanners and laser printers are disadvantageous in that the devices are large-sized and expensive and a modulator is required. Additionally, because the illumination source for exposure emits visible light, there is a limit to safelight use for the photographic materials, and handleability is also poor.
On the other hand, semiconductor lasers are small-sized and inexpensive, modulation is easily conducted, and semiconductor lasers have a working life which is longer than that of the foregoing lasers. In addition, a safelight is advantageously used with semiconductor lasers which emit light in the infrared region. Thus, handleability and workability are improved.
Dyes which absorb light in the infrared region are generally used to prevent halation, to thereby reduce blurring of the image due to exposure to infrared light. Practically, the dyes can remain in the photographic material after processing, so long as the dyes do not absorb visible light. However, the dyes usually absorb some visible light, and a residual color is formed when the dyes remain in the photographic material after processing. The formation of the residual color is practically not preferred. Accordingly, water-soluble dyes are used as the antihalation dyes.
When water-soluble dyes are used in layers on the same side of the support as that coated with silver halide emulsions, the dyes diffuse into the silver halide emulsion layers. Consequently, sensitivity is greatly lowered.
To solve this problem, a method has recently been proposed wherein dyes which are decolorizable in the development processing stage are dispersed in the form of fine solid particles to fix the dyes to a specific layer [See, (PCT)WO 88/04794, European Patent (Laid-Open) Nos. 0,274,723A1, 276,566 and 299,435, JP-A-52-92716 (the term "JP-A" as used herein means an "unexamined published Japanese patent application"), JP-A-55-155350, JP-A-55-155351, JP-A-61-205934, JP-A-48-68623, U.S. Pat. Nos. 2,527,583, 3,486,897, 3,746,539, 3,933,798, 4,130,429 and 4,040,841, Japanese Patent Application No. 1-50874, JP-A-2-282244, JP-A-3-167546 and JP-A-4-180057].
However, dyes which absorb light in the visible wavelength region are mainly disclosed in the above patent specifications. Even where dyes which absorb light in the infrared region are disclosed, it has been found that the dyes specifically exemplified therein are not sufficiently fixed to a specific layer.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a silver halide photographic material having high sensitivity and providing high image quality, and which photographic material is well adapted for rapid processing.
The above-described object of the present invention has been achieved by providing a silver halide photographic material comprising a transparent support having thereon a dye layer, a hydrophobic polymer layer and at least one light-sensitive silver halide emulsion layer, wherein the dye layer contains at least one dye represented by formulae (I) to (VIII) dispersed in the form of fine solid particles, the dye layer is disposed between the at least one light-sensitive silver halide emulsion layer and the support, the hydrophilic colloid coating weight of the dye layer is 0.5 g/m2 or less, and the hydrophobic polymer layer is disposed between the dye layer and the support: ##STR1## wherein T10, T11 and T12 independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carboxyl group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, a carbamoyl group, an amino group, a sulfonamido group, a carbonamido group, a ureido group, a sulfamido group, a hydroxy group, a vinyl group or an acyl group; R13 and R14 independently represent a hydrogen atom, a halogen atom, an alkoxy group, an alkyl group, an alkenyl group, an aryloxy group or an aryl group; R15 and R16 independently represent a hydrogen atom or a substituent group; and R17 and R18 independently represent an alkyl group, an aryl group, a vinyl group, an acyl group, an alkyl group or an arylsulfonyl group; or T11 and T12, R13 and R15, R14 and R16 R17 and R18 R15 and R17 R16 and R18 may be combined together to form a ring; ##STR2## wherein R21 represents a hydrogen atom, an alkyl group, an aryl or a heterocyclic group; R22 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, COR24 or SO2 R24 ; R23 represents a hydrogen atom, a cyano group, a hydroxyl group, a carboxyl group, an alkyl group, an aryl group, COOR24, OR24, NR25 R26, CONR25 R26, NR25 COR24, NR25 SO2 R24 or NR25 CONR25 R26 ; R24 represents an alkyl group or an aryl group; R25 and R26 each represents a hydrogen atom, an alkyl group or an aryl group; L21, L22 and L23 each represents a methine group; and n21 represents 1 or 2; ##STR3## wherein X41 and X42 each represents a hydrogen atom, a hydroxyl group, a carboxyl group, --COOR41, --COR41, --CONH2, --CONR41 R4242, an alkyl group, an aryl group or a heterocyclic group; Y41 and Y42 each represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group; Z41 and Z42 each represents a hydrogen atom, --CN, a carboxyl group, --COOR43, --COR43, --CONH2, --CONR43 R44, --NHCOR43, --NHSO2 R43, --SO2 R43, an alkyl group, an aryl group or a heterocyclic group; R41 and R43 each represents an alkyl group or an aryl group; R42 and R44 each represents a hydrogen atom, an alkyl group or an aryl group; L41, L42, L43, L44 and L45 each represents a methine group; and m41 and n41 each represents an integer and the sum of m41 and n41 is 2; ##STR4## wherein R51 and R52 each represents an alkyl group, an alkenyl group or an aryl group; L51 represents a bonding group formed by bonding five or seven methine groups through conjugated double bonds; Z51 represents an atomic group required for completing an aromatic ring; and X.sup.⊖ represents an anion; ##STR5## wherein R61 represents a hydrogen atom, an alkyl group or an aryl group; R62, R63, R64 and R65 each represents a hydrogen atom, an alkyl group, a halogen atom, an alkoxy group, an alkoxycarbonyl group, a carboxyl group, a hydroxyl group or an amino group; L61, L62, L63, L64 and L65 each represents a methine group; and m61 and n61 each represents an integer and the sum of m61 and n61 is 2; ##STR6## wherein L71 represents nitrogen atom or a group formed by bonding five or seven unsubstituted or substituted methine groups through conjugated double bonds; E represents O, S or N--R79 ; R70 and R79 independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an amino group, a hydrazino group or a diazenyl group; R71 represents a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, an alkynyl group or a heterocyclic group; R72 represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, a carboxyl group, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amino group, an acyloxy group, a carbamoyl group, a sulfamoyl group, a alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group or an alkynyl group; R70 and R79 may be combined together to form a ring; R73 and R74 independently represent a hydrogen atom, a halogen atom, an alkoxy group, an alkyl group, an alkenyl group, an aryloxy group or an aryl group; R75 and R76 independently represent a hydrogen atom or a substituent group; and R77 and R78 independently represent an alkyl group, an aryl group, a vinyl group, an acyl group or an alkyl- or arylsulfonyl group; or R73 and R75, R74 and R76, R77 and R78, R75 and R77 or R76 and R78 may be combined together to form a ring; ##STR7## wherein X81 represents a hydrogen atom, a hydroxyl group, COOR87, CONR87 R88, an alkyl group or an aryl group; Y82 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group or NR87 R88 ; Z81 represents a hydrogen atom, an alkyl group, an aryl group, a cyano group, COOR89, CONR87 R88, COR89, SO2 R89, NR88 COR89, a nitro group or a pyridyl group; R81, R82, R83 and R84 each represents a hydrogen atom, an alkyl group, OR89, NR89 COR87, COOR89, CONR87 R88 or a halogen atom; R85 and R86 each represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group; and R87, R88 and R89 each represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group; or R81 and R82, R85 and R86, R82 and R85, R83 and R86, or R87 and R88 may be combined together to form a five-membered or six-membered ring; ##STR8## wherein R91, R92 and R93 each represents a hydrogen atom an alkyl group or an aryl group; Q1 represents an atomic group required for forming a basic heterocyclic ring; L91, L92, L93, L94, L95 and L96 each represents a methine group; p91, m91 and n91 each represents 0 or 1 provided that the sum total of p91 +m91 +n91 is an integer of 2 or more; and the compound of formula (VIII) has at least one member selected from the group consisting of a carboxyl group, a sulfonic acid arylamido group and a phenolic hydroxyl group contained in the molecular structure thereof.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is illustrated in greater detail below.
In formula (I), examples of a substituent group for R15 and R16 include a hydrogen atom, an alkyl group, an alkoxy group and a halogen atom.
In formula (VI), examples of a substituent group for R75 and R76 include an hydrogen atom, an alkyl group, an alkoxy group and a halogen atom.
In formulae (I) to (VIII), an alkyl group has preferably 1 to 8 carbon atoms and more preferably 1 to 4 carbon atoms. Examples of the alkyl group include methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, hexyl and octyl. Further, the alkyl group may be substituted. Examples of the substituents include an alkyl group, an aryl group, an alkoxy group, a halogen atom, a cyano group, a carboxyl group, a sulfonamido group, a sulfamoyl group, an acyl group, an alkoxycarbonyl group, an acylamino group, a carbamoyl group, a hydroxyl group and an alkylsulfonyl group.
In formulae (I) to (VIII), the aryl group is preferably a phenyl group or a naphthyl group and more preferably a phenyl group. The aryl group may be substituted. Examples of the substituents include the substituents for the alkyl group described above.
In formulae (I) to (VIII), the alkoxy group has preferably 1 to 8 carbon atoms and more preferably 1 to 4 carbon atoms. Examples of the alkoxy group include methoxy, ethoxy, n-propyloxy and n-butoxy. The alkoxy group may be substituted. Examples of the substituents include an alkyl group, an alkoxy group, an aryl group and a halogen atom.
In formulae (I) to (VIII), the aryloxy group is preferably a phenoxy group or a naphthoxy group and more preferably a phenoxy group. The aryloxy group may be substituted. Examples of substituents include the substituents for the alkyl group described above.
In formulae (I) to (VIII), examples of the heterocyclic group include a pyridyl group, a thienyl group, a furano group and an imidazolyl group.
In formulae (I) to (VIII), examples of the halogen atom include fluorine, chlorine, bromine and iodine. Among these, fluorine, chlorine and bromine are preferred.
In formulae (I) to (VIII), examples of X.sup.⊖ include Cl.sup.⊖, Br.sup.⊖, CF3 SO3.sup.⊖, ClO4.sup.⊖, PF6.sup.⊖, CH3 SO3.sup.⊖ and CH3 CO2.sup.⊖.
Specific examples of preferred compounds capable of forming a fine solid particle dispersion, represented by formulae (I) to (VII), for use in the present invention include, but are not limited to, the following compounds. ##STR9##
The dyes for use in the present invention can be easily synthesized by the methods described in PCT-WO 88/04794, European Patent (Laid-Open) Nos. 0,274,723A1, 276,566 and 299,435, JP-A-52-92716, JP-A-55-155350, JP-A-55-155351, JP-A-61-205934, JP-A-48-68623, JP-A-3-167546, JP-A-3-7931, JP-A-2-282244, and U.S. Pat. Nos. 2,527,583, 3,486,897, 3,746,539, 3,933,798, 4,130,429 and 4,040,841 and referring to these methods.
The term "dye dispersed in the form of fine solid particles" as used herein refers to a dye contained in a dye layer, which dye has poor solubility in the dye (colored) layer so that the dye can not be present therein in the molecular state, but is present as a solid having a (large) particle size so that the dye substantially does not diffuse within the dye layer.
Methods for preparing the fine solid particle dispersion are described in PCT-W088/04794, European Patent (Laid-Open) (EP) No. 0,276,566A1 and JP-A-63-197943. Generally, the dye is crushed in a ball mill and stabilized by using a surfactant and gelatin.
In the present invention, the dispersion can be prepared according to the method described in JP-A-63-197943.
Namely, 434 ml of water and a 6.7 wt % solution of 53 g of Triton X-200 surfactant ("TX-200" manufactured by Rohm & Haas Co.) are placed into a 1.5 l screw-cap bottle. To the bottle, there are added 20 g of the dye and 800 ml of zirconium oxide (ZrO2) beads (2 mm diameter). The cap of the bottle is tightly closed. The bottle is placed in a mill, and the contents are crushed for 4 days.
The contents are added to 160 g of a 12.5 wt % aqueous solution of gelatin, and placed in a roll mill for 10 minutes to reduce bubbles. The resulting mixture is filtered to remove the ZrO2 beads. The resulting solid as such is composed of fine particles having an average particle size of about 0.3 μm. Accordingly, the particles are classified by centrifugal separation into particles having a particle size of 1 μm or smaller.
The dye crystallites for use in the present invention have a particle size of preferably 1.0 μm or smaller, more preferably 0.5 μm or smaller and most preferably 0.01 to 0.5 μm.
The dyes are coated in an amount of preferably 5 to 300 mg/m2, particularly preferably 10 to 150 mg/m2.
The amount of gelatin used in preparation of the dispersion is that amount which provides a coating weight of gelatin (hydrophilic colloid) of 0.5 g/m2 or less.
The gelatin (hydrophilic colloid) coating weight of the dye layer of the present invention is 0.5 g/m2 or less, preferably 0.05 to 0.3 g/m2.
When the coating weight of the entire hydrophilic colloid of the photographic material is increased, the amount of water absorbed by the photographic material during processing is increased and the load applied to the drying stage is increased. Hence, an increase in the coating weight of the entire hydrophilic colloid is not preferred from the standpoint of rapid processing. Accordingly, the total coating weight of hydrophilic colloid of the photographic material of the present invention is preferably not more than 3 g/m2, more preferably 1 to 2.5 g/m2 per each side of the support. To reduce the total coating weight of the hydrophilic colloid, the dye layer is preferably provided as a subbing layer. The subbing layer contains a hydrophilic colloid to improve adhesion between the support and another hydrophilic colloid layer such as a silver halide emulsion layer. Accordingly, when the dye layer serves as the subbing layer (e.g. the second subbing layer as described below), the dye layer can be provided without increasing the total amount of hydrophilic colloid.
When the coating weight of silver is increased, processing dependence of photographic properties is increased. Accordingly, an increase in the coating weight of silver is not preferred from the standpoint of rapid processing and a reduction in the replenishment rate, both of which have been in demand in recent years. The coating weight of silver is preferably 3 g/m2 or less, more preferably 2 g/m2 or less, particularly preferably 0.5 to 3 g/m2.
Examples of the transparent support preferably used in the present invention include polyethylene terephthalate film and cellulose triacetate film.
The surface of the support is preferably subjected to a corona-discharging treatment, a glow-discharging treatment or an ultraviolet-irradiation treatment to improve the adhesion between the support and the hydrophilic colloid layer. A first subbing layer comprising, for example, a styrene butadiene latex or a vinylidene chloride latex (hydrophobic polymer layer) is disposed between the dye layer and the support.
Examples of hydrophobic polymers for use in the first subbing layer (hydrophobic polymer layer) include styrene-butadiene copolymers, vinylidene chloride copolymers, water-soluble polyesters and polyacrylic esters. Of these polymers, styrene-butadiene copolymers and vinylidene chloride copolymers are preferred. More preferred are the styrene-butadiene copolymers.
The styrene-butadiene copolymers may be copolymers of styrene and butadiene monomers in a weight ratio of from 9/1 to 1/9, and may optionally comprise a repeating unit derived from a third monomer such as acrylic acid.
The coating weight of the hydrophobic polymer in the first subbing layer is preferably 100 to 1,000 mg/m2. The drying temperature of the subbing layer is preferably 80° to 200° C.
An aqueous dispersion (latex) of the hydrophobic polymer for use in the first subbing layer is preferably prepared as a coating solution, and further a crosslinking agent, a surfactant, a swelling agent, a matting agent, an antistatic agent, etc. are optionally added to the aqueous dispersion.
Examples of the crosslinking agent include the triazine compounds described in U.S. Pat. Nos. 3,325,287, 3,288,775 and 3,549,377 and Belgian Patent 6,602,226; the dialdehyde compounds described in U.S. Pat. Nos. 3,291,624 and 3,232,764, French Patent 1,543,694 and U.K. Patent 1,270,578; the epoxy compounds described in U.S. Pat. No. 3,091,537 and JP-B-49-26580 (the term "JP-B" as used herein means an "examined Japanese patent publication"); the vinyl compounds described in U.S. Pat. No. 3,642,486; the aziridine compounds described in U.S. Pat. No. 3,392,024; the ethyleneimine compounds described in U.S. Pat. No. 3,549,379; and methylol compounds. Of these compounds, dichlorotriazine compounds are preferred.
A hydrophilic colloid layer as a second subbing layer is preferably provided on the first subbing layer (hydrophobic polymer layer) in the present invention.
The coating weight of hydrophilic colloid in the second subbing layer is preferably 20 mg/m2 to 0.4 g/m2. The drying temperature of the second hydrophilic colloid layer is preferably 80° C. or more to effect good adhesion of the second layer to the first subbing layer. The drying temperature is 180° C. or lower. When the drying temperature is too high, the amount of the dye from the dye layer taken up by the first subbing layer is increased, and a residual color is formed. More preferably, the drying temperature is not higher than 160° C.
Preferably, a back layer as described in Japanese Patent Application No. 3-145168 is used to balance the drying property with repsect to curling.
That is, a light-insensitive hydrophilic colloid layer containing a hydrophilic colloid as a binder is provided on a second side of the support opposite the side having thereon at least one silver halide emulsion layer, and a hydrophobic polymer layer is provided on the second side of the support further away from the support than the light-insensitive hydrophilic colloid layer, and the light-insensitive hydrophilic colloid layer and the hydrophobic polymer layer are substantially not swollen when contacted with a processing solution (i.e., the thickness of their layers after the drying step is not more than 1.05 times that after completion of the water washing step in the development).
Various additives and methods described in the following patent specifications can be used to prepare the photographic material of the present invention without particular limitation. These additives and methods are described in the cited portions of the patent specifications as follows.
______________________________________                                    
Item         Patent Specification Citations                               
______________________________________                                    
(1)  Silver halide                                                        
                 JP-A-2-68539 (the 6th line from the                      
     emulsion and                                                         
                 bottom of right lower column of page                     
     preparation 8 to the 12th line of right upper                        
     thereof     column of page 10); JP-A-3-24537                         
                 (the 10th line of right lower column                     
                 of page 2 to the first line of right                     
                 upper column of page 6, and the 16th                     
                 line of left upper column of page 10                     
                 to the 19th line of left lower                           
                 column of page 11); JP-A-4-107442;                       
                 JP-A-2-97937 (the 12th line of right                     
                 lower column of page 20 to the 14th                      
                 line of left lower column of page                        
                 21); JP-A-2-12236 (the 19th line of                      
                 right upper column of page 7 to the                      
                 12th line of left lower column of                        
                 page 8); and JP-A-4-33043.                               
(2)  Chemical    JP-A-2-68539 (the 13th line of right                     
     sensitization                                                        
                 upper column of page 10 to the 16th                      
     method      line of left upper column of page                        
                 10); Japanese Patent Application No.                     
                 3-105035; and selenium sensitization                     
                 method described in Japanese Patent                      
                 Application No. 3-189532.                                
(3)  Anti-fogging                                                         
                 JP-A-2-68539 (the 17th line of left                      
     agent,      lower column of page 10 to the 7th                       
     stabilizer  line of left upper column of page                        
                 11, and the second line of left                          
                 lower column of page 3 to left lower                     
                 column of page 4);-JP-A-2-103526                         
                 (the 19th line of right lower column                     
                 of page 17 to the 4th line of right                      
                 upper column of page 18, and the                         
                 first line to the 5th line of right                      
                 lower column of page 18); and thio-                      
                 sulfinic acid compounds described                        
                 in JP-A-1-237538.                                        
(4)  Color tone  JP-A-62-276539 (the 7th line of left                     
     improver    lower column of page 2 to the 20th                       
                 line of left lower column of page                        
                 10); and JP-A-3-94249 (the 15th line                     
                 of left lower column of page 6 to                        
                 the 19th line of right upper column                      
                 of page 11).                                             
(5)  Spectral    JP-B-46-10473 (the 18th line of                          
     sensitizing right column of page 1 to the 24th                       
     dye         line of left column of page 2, and                       
                 the 23rd line of right column of                         
                 page 2 to the 22nd line of left                          
                 column of page 6); U.S. Patent                           
                 3,482,973 (the 22nd line of the                          
                 second column to the 59th line of                        
                 the 4th column); U.S. Patent                             
                 3,623,881 (the 34th line of the                          
                 second column of the 53rd line of                        
                 the 7th column); JP-A-59-191032 (the                     
                 8th line of right of right upper                         
                 column of page 3 to the 9th line of                      
                 left lower column of page 3, and the                     
                 12th line of right lower column of                       
                 page 3 to the bottom of page 7); JP-                     
                 A-60-80841 (the 18th line of right                       
                 lower column of page 4 to the 6th                        
                 line of right lower column of page                       
                 12); and JP-A-1-97947 (the first                         
                 line of left upper column of page 4                      
                 to the 11th line of right upper                          
                 column of page 4, and the 11th line                      
                 of right lower column of page 4 to                       
                 the 6th line of right upper column                       
                 of page 8, and the 9th line of left                      
                 lower column of page 10 to the                           
                 second line of left lower column of                      
                 page 11).                                                
(6)  Super-      JP-A-59-192242 (the 19th line of                         
     sensitizing left lower column of page 10 to the                      
     dye         15th lone of left lower column of                        
                 page 12); and JP-A-60-80841 (the                         
                 10th line of right upper column of                       
                 page 13 to the first line of left                        
                 upper column of page 16).                                
(7)  Surfactant, JP-A-2-68539 (the 14th line of left                      
     antistatic  upper column of page 11 to the 9th                       
     agent       line of left upper column of page                        
                 12); JP-A-2-12236 (the 7th line of                       
                 right upper column of page 9 to the                      
                 7th line of right lower column of                        
                 page 9); and JP-A-2-18542 (the 13th                      
                 line of left lower column of page 2                      
                 to the 18th line of right lower                          
                 column of page 4).                                       
(8)  Matting agent,                                                       
                 JP-A-2-68539 (the 10th line of left                      
     lubricant   upper column of page 12 to the 10th                      
     (i.e., sliding                                                       
                 line of right upper column of page                       
     agent)      12, and the 10th line of left lower                      
     plasticizer column of page 14 to the first line                      
                 of right lower column of page 14);                       
                 and JP-A-2-103526 (the 15th line of                      
                 left upper column of page 19 to the                      
                 15th line of right upper column of                       
                 page 19).                                                
(9)  Hydrophilic JP-A-2-68539 (the 11th line of left                      
     colloid     lower column of page 12 to the 16th                      
                 line of left lower column of page                        
                 12).                                                     
(10) Hardening   JP-A-2-68539 (the 17th line of left                      
     agent       lower column of page 12 of the 6th                       
                 line of right upper column of page                       
                 13); and JP-A-2-103526 (the 5th line                     
                 to the 17th line of right upper                          
                 column of page 18).                                      
(11) Dye         JP-A-63-49752 (the 4th line of left                      
                 lower column of page 18 to the                           
                 second line of left upper column of                      
                 page 19).                                                
(12) Binder      JP-A-2-18542 (the first line to the                      
                 20th line of right lower column of                       
                 page 3).                                                 
(13) Polyhydroxy-                                                         
                 JP-A-3-39948 (left upper column of                       
     benzenes    page 11 to left lower column of page                     
                 12); EP 452,7-72A; and JP-A-2-55349                      
                 (the 9th line of left upper column                       
                 of page 11 to the 17th line of right                     
                 lower column of page 11).                                
(14) Polymer latex                                                        
                 JP-A-2-103526 (the 12th line to the                      
                 20th line of left lower column of                        
                 page 18).                                                
(15) Compound    JP-A-2-103526 (the 6th line of right                     
     having an   lower column of page 18 to the first                     
     acid group  line of left upper column of page                        
                 19); and JP-A-2-55349 (the 13th line                     
                 of right lower column of page 8 to                       
                 the 8th line of left upper column of                     
                 page 11).                                                
(16) Hydrazine   JP-A-2-12236 (the 19th line of right                     
     nucleating  upper column of page 2 to the third                      
     agent       line of right upper column of page                       
                 7); and compounds of formula (II)                        
                 and compounds II-1 to II-54                              
                 described in JP-A-3-174143 (the                          
                 first line of right lower column of                      
                 page 20 to the 20th line of right                        
                 upper column of page 27).                                
(17) Nucleation  Compounds of formulas (II-m) to                          
     accelerator (II-p) and compounds II-1 to II-22                       
                 described in JP-A-2-103536 (the 13th                     
                 line of right upper column of page 9                     
                 to the 10th line of left upper                           
                 column of page 16); and compounds                        
                 described in JP-A-1-179939                               
(18) Black pepper                                                         
                 Compounds described in U.S. Patent                       
     inhibitor   4,956,257 and JP-A-1-118832                              
(19) Redox       Compounds of formula (I) (particu-                       
     compound    larly compounds 1 to 50) described                       
                 in JP-A-2-301743; compounds of                           
                 formulas (R-1), (R-2) and (R-3) and                      
                 compounds 1 to 75 described in JP-A-                     
                 3-174143 (pages 3 to 20); and                            
                 compounds described in Japanese                          
                 Patent Application Nos. 3-69466 and                      
                 3-15648.                                                 
(20) Monomethine Compounds of formula (II) (particu-                      
     compound    larly compounds II-1 to II-26)                           
                 described in JP-A-2-287532                               
(21) Layer       JP-A-3-198041                                            
     structure                                                            
(22) Processing  JP-A-2-103037 (the 7th line of right                     
     method      upper column of page 16 to the 15th                      
                 line of left lower column of page                        
                 19); JP-A-2-115837 (the 5th line of                      
                 right lower column of page 3 to the                      
                 10th line of right upper column of                       
                 page 6); and JP-A-2-55349 (the first                     
                 line of right lower column of page                       
                 13 to the 10th line of left upper                        
                 column of page 16                                        
______________________________________
The present invention is now illustrated in greater detail by reference to the following Examples which, however, are not to be construed as limiting the invention in any way.
EXAMPLE 1
Preparation of Supports 1 to 8
A biaxially stretched blue-colored polyethylene terephthalate film of 175 μm in thickness was subjected to corona discharging treatment. The polyethylene terephthalate film contained 1,4-bis(2,6-diethylanilino) anthraquinone. The following hydrophobic polymer layer was then coated on the film in such amount as to provide the following coating weights. The coating was carried out using a wire bar coater. The coated film was dried at 175° C. for one minute.
Hydrophobic Polymer Layer
______________________________________                                    
Hydrophobic Polymer Layer                                                 
______________________________________                                    
Polymer (compound shown in Table                                          
                        0.322  g/m.sup.2                                  
1 below)                                                                  
Sodium Salt of 2,4-Dichloro-6-                                            
                        8.4    mg/m.sup.2                                 
hydroxy-s-triazine                                                        
______________________________________
The latex solution contained 0.4% by weight of the following emulsifying dispersant (a) based on the amount, on a solid basis, of the latex.
Emulsifying Dispersant (a) ##STR10##
Subsequently, the following hydrophilic colloid layer was coated thereon in such amount as to provide the following coating weights. The coating was carried out using a wire bar coater. The coated film was dried at 150° C. for one minute.
Second Subbing Layer (Hydrophilic Colloid Layer)
______________________________________                                    
Gelatin          amount shown in                                          
                 Table 1 below                                            
Polyethyl Acrylate                                                        
                   20 mg/m.sup.2                                          
C.sub.12 H.sub.25 O(CH.sub.2 CH.sub.2 O).sub.10 H                         
                   4 mg/m.sup.2                                           
 ##STR11##       0.27 mg/m.sup.2                                          
Dye              compound and                                             
                 amount shown in                                          
                 Table 1 below                                            
______________________________________
Preparation of Silver Halide Emulsion
To the following solution 1 kept at 38° C. and a pH of 4.5 with stirring, there were simultaneouly added the following solutions 2-a and 2-b over a period of 16 minutes to form a core. Subsequently, the following solutions 3-a and 3-b were added thereto over a period of 16 minutes to form an intermediate phase. Further, the following solutions 4-a and 4-b were added thereto over a period of 5 minutes to form the outermost phase, and 0.15 g of potassium iodide was added thereto to thereby complete the formation of grains.
The resulting emulsion was washed with water by conventional flocculation method, and 30 g of gelatin was added thereto. The pH of the emulsion was adjusted to 5.2, and the pAg thereof was adjusted to 7.5. Subsequently, 1 mg of sodium thiosulfate and 1.5 mg of the following compound (a) were added thereto, and chemical sensitization was carried out so as to provide the maximum sensitivity.
______________________________________                                    
Solution 1                                                                
Water                   one    liter                                      
Gelatin                 20     g                                          
Sodium Chloride         2      g                                          
1,3-Dimethylimidazolidine-                                                
                        20     mg                                         
2-thione                                                                  
Sodium Benzenethiosulfonate                                               
                        6      mg                                         
Solution 2-a                                                              
Water                   300    ml                                         
Silver Nitrate          75     g                                          
Solution 2-b                                                              
Water                   300    ml                                         
Sodium Chloride         23     g                                          
Potassium Bromide       10     g                                          
Potassium Hexachloroiridate (III)                                         
                        15     ml                                         
(0.001 wt %)                                                              
K.sub.3 RhCl.sub.6 (0.001 wt %)                                           
                        0.67   ml                                         
Solution 3-a                                                              
Water                   300    ml                                         
Silver nitrate          75     g                                          
Solution 3-b                                                              
Water                   300    ml                                         
Sodium Chloride         23     g                                          
Potassium Bromide       10     g                                          
Solution 4-a                                                              
Water                   100    ml                                         
Silver Nitrate          25     g                                          
Solution 4-b                                                              
Water                   100    ml                                         
Sodum Chloride          7.6    g                                          
Potassium Bromide       3.3    g                                          
K.sub.3 RhCl.sub.6 (0.001 wt %)                                           
                        0.22   ml                                         
Compound (a)                                                              
 ##STR12##                                                                
______________________________________
Further, 50 mg of 4-hydroxy-6-methyl-l,3,3a,7-tetrazaindene as a stabilizer and 100 ppm of phenoxyethanol as the antiseptic were added thereto to finally obtain a cubic silver iodochlorobromide emulsion having a silver chloride content of 80 mol% and a mean grain size of 0.20 μm (coefficient of variation: 9%).
Preparation of Coated Sample
Further, 100 mg of the following compound (b) as a spectral sensitizing dye and 100 mg of the following compound (c) as the supersensitizing agent were added to the emulsion, each amount being per mol of silver. Furthermore, 2.5 g of hydroquinone per mol of silver, 50 mg of 1-phenyl-5-mercaptotetrazole per mol of silver as anti-fogging agents, 0.4 g/m2 of colloidal silica having a particle size of 10 μm, a polyethyl acrylate latex, as a plasticizer, in an amount of 25 wt % based on the amount of the gelatin binder and 2-bis(vinylsulfonylacetamido)ethane as the hardening agent were added thereto, and the resulting emulsion was coated on each of Supports 1 to 8 in an amount to provide a coating weight of 3.4 g/m2 in terms of silver. The coating weight of gelation was 1.4 g/m2. ##STR13##
The following lower and upper protective layers having the following compositions were simultaneously coated on the emulsion layer.
______________________________________                                    
Lower Protective Layer                                                    
Gelatin                0.25   g/m.sup.2                                   
Dye (d) described below                                                   
                       250    mg/m.sup.2                                  
Sodium Benzenethiosulfonate                                               
                       2      mg/m.sup.2                                  
1,5-Dihydroxy-2-benzaldoxime                                              
                       25     mg/m.sup.2                                  
5-Chloro-8-hydroxyquinoline                                               
                       5      mg/m.sup.2                                  
Polyethyl Acrylate Latex                                                  
                       160    mg/m.sup.2                                  
Upper Protective Layer                                                    
Gelatin                0.25   g/m.sup.2                                   
Silica having an average particle                                         
                       30     mg/m.sup.2                                  
size of 2.5 μm (matting agent)                                         
Silicon Oil            100    mg/m.sup.2                                  
Colloidal silica having a                                                 
                       30     mg/m.sup.2                                  
particle size of 10 μm                                                 
Compound (e) described below                                              
                       5      mg/m.sup.2                                  
Sodium Dodecylbenzenesulfonate                                            
                       22     mg/m.sup.2                                  
Dye (d)                                                                   
 ##STR14##                                                                
Compound (e)                                                              
 ##STR15##                                                                
______________________________________
Evaluation of Photographic Performance
The resulting samples were exposed to light through an interference filter having a peak at 633 nm and a continuous wedge using a xenon flash lamp (emission time: 10-6 sec), and processed under the following temperature and time conditions using an automatic processor FG-710NH (manufactured by Fuji Photo Film Co., Ltd.) to carry out sensitometry.
The following developing solution and the following fixing solution were used.
______________________________________                                    
Developing Solution                                                       
______________________________________                                    
Sodium 1,2-Dihydroxybenzene-                                              
                         0.5    g                                         
3,5-disulfonate                                                           
Diethylenetriaminepentaacetic Acid                                        
                         2.0    g                                         
Sodium Carbonate         5.0    g                                         
Boric Acid               10.0   g                                         
Potassium Sulfite        85.0   g                                         
Sodium Bromide           6.0    g                                         
Diethylene Glycol        40.0   g                                         
5-Methylbenzotriazole    0.2    g                                         
Hydroquinone             30.0   g                                         
3-Hydroxymethyl-4-methyl-1-phenyl-3-                                      
                         1.6    g                                         
pyrazolidone                                                              
2,3,5,6,7,8-Hexahydro-2-thioxo-4-                                         
                         0.05   g                                         
(1H)-qunazolinone                                                         
Sodium 2-Mercaptobenzimidazole-5-                                         
                         0.3    g                                         
sulfonate                                                                 
Water to make            one liter                                        
______________________________________
The pH was adjusted with sodium hydroxide to 10.7.
______________________________________                                    
Fixing Solution                                                           
______________________________________                                    
Sodium Thiosulfate (Anhydrous)                                            
                        150    g                                          
Compound h described below                                                
                        0.1    mol                                        
Sodium Bisulfate        30     g                                          
Disodium Ethylenediamine-                                                 
                        25     g                                          
tetraacetate Dehydrate                                                    
Water to make           one liter                                         
______________________________________
The pH was adjusted with sodium hydroxide to 6.0.
______________________________________                                    
Compound h                                                                
 ##STR16##                                                                
Processing Stage                                                          
Development  38° C.  14     sec                                    
Fixing       37° C.  9.7    sec                                    
Rinse        26° C.  9      sec                                    
Squeeze                     2.4    sec                                    
Drying       55° C.  8.3    sec                                    
Total                       43.4   sec                                    
______________________________________
The reciprocal of the exposure amount providing a density of 3.0 is referred to as the sensitivity. The sensitivity is shown in Tables 1 and 2 below relative to the sensitivity of Photographic Material 4 taken as 100. The incline of the straight line formed by joining the point of a density of 0.1 on the characteristic curve to the point of a density of 3.0 thereon is referred to as the gradation.
                                  TABLE 1                                 
__________________________________________________________________________
                              Amount of                                   
                                      Amount of                           
Photographic         Dye in   Gelatin in                                  
                                      Gelatin per                         
Material                                                                  
        Polymer in   Subbing Layer                                        
                              Subbing Layer                               
                                      One Side                            
                                            Sensi-                        
                                                Residual                  
                                                     Drying               
                                                          Support         
No.     Subbing Layer                                                     
                     (Amount) (mg/m.sup.2)                                
                                      (g/m.sup.2)                         
                                            tivity                        
                                                Color                     
                                                     Property             
                                                          No.             
__________________________________________________________________________
1 (Comp. Ex.)                                                             
        butadiene-sytrene                                                 
                     Comparative                                          
                              160     2.4   85  G    G    1               
        copolymer latex                                                   
                     compound (a)                                         
        (butadiene/styrene =                                              
                     (50 mg/m.sup.2)                                      
        31/69 by weight)                                                  
2 (Comp. Ex.)                                                             
        butadiene-sytrene                                                 
                     I-16 (50 mg/m.sup.2)                                 
                              600     "     100 B    G    2               
        copolymer latex                                                   
        (butadiene/styrene =                                              
        31/69 by weight)                                                  
3 (Comp. Ex.)                                                             
        butadiene-sytrene                                                 
                     I-16 (50 mg/m.sup.2)                                 
                              160     3.2   99  B    B    3               
        copolymer latex                                                   
        (butadiene/styrene =                                              
        31/69 by weight)                                                  
4 (Invention)                                                             
        butadiene-sytrene                                                 
                     I-16 (50 mg/m.sup.2)                                 
                              "       2.4   100 G    G    3               
        copolymer latex                                                   
        (butadiene/styrene =                                              
        31/69 by weight)                                                  
5 (Invention)                                                             
        butadiene-sytrene                                                 
                     I-17 (60 mg/m.sup.2)                                 
                              "       "     99  G    G    4               
        copolymer latex                                                   
        (butadiene/styrene =                                              
        31/69 by weight)                                                  
6 (Invention)                                                             
        butadiene-sytrene                                                 
                     II-8 (60 mg/m.sup.2)                                 
                              "       "     98  G    G    5               
        copolymer latex                                                   
        (butadiene/styrene =                                              
        31/69 by weight)                                                  
 ##STR17##                                                                
Comparative compound (a)                                                  
7 (Comp. Ex.)                                                             
        aqueous polyester                                                 
                     I-16 (50 mg/m.sup.2)                                 
                              80      2.4   100 B    G    6               
        WD-SIZE (Eastman                                                  
        Kodak Co.)                                                        
8 (Comp. Ex.)                                                             
        polyacrylic ester                                                 
                     I-16 (50 mg/m.sup.2)                                 
                              "       "     99  B    G    7               
        Julymer ET410 (Nippon                                             
        Junyaku KK)                                                       
9 (Invention)                                                             
        vinylidene chloride latex                                         
                     I-16 (50 mg/m.sup.2)                                 
                              "       "     98  G    G    8               
        (vinylidene chloride/                                             
        methacrylic acid/methyl-                                          
        acrylate/methylmethacryl-                                         
        ate/acrylonitrile = 90/0.3/                                       
        4/4/1.7 by weight)                                                
__________________________________________________________________________
It is clearly seen from the results shown in Table 1 that the photographic materials of the present invention have high sensitivity and exellent rapid-processability.
It is also be seen from the results shown in Table 1 that the photographic materials of the present invention do not suffer from the problem of the residual color.
Evaluation of Drying Property
Films having a size of 24.5×30.5 cm were processed in an automatic processor. The films which left the drying zone of the processor were immediately touched with the hand, and the dry state of the films was examined. The criterion of evaluation is as follows:
The mark G: Dry to touch.
The mark B: The film leaving the drying zone was damp to touch and insufficiently dried.
Evaluation of Residual Color
The evaluation of residual color was made by visually observing Dmin. The results obtained are shown in Table 1 above.
The mark G: Presents no problem for practical use.
The mark B: Not acceptable for practical use.
EXAMPLE 2
Preparation of Supports 9 and 10
A biaxially stretched blue-colored polyethylene terephthalate film of 175 μm in thickness was subjected to corona discharging treatment. The polyethylene terephthalate film contained 1,4-bis(2,6-diethylanilino)anthraquinone. The following hydrophobic polymer layer was coated on the film in such amount as to provide the following coating weights. The coating was carried out using a wire bar coater. The coated film was dried at 175° C. for one minute.
Hydrophobic Polymer Layer
______________________________________                                    
Hydrophobic Polymer Layer                                                 
______________________________________                                    
Polymer (Compound shown in Table 2                                        
                        0.322  g/m.sup.2                                  
below)                                                                    
Sodium Salt of 2,4-Dichloro-6-                                            
                        8.4    mg/m.sup.2                                 
hydroxy-s-triazine                                                        
______________________________________
The latex solution contained 0.4 wt % of the following emulsifying dispersant (a) based on the amount, on a solid basis, of the latex.
Emulsifying Dispersant (a) ##STR18##
Subsequently, the following hydrophilic colloid layer was coated thereon in an amount to provide the following coating weight. The coating was carried out using a wire bar coater. The coated film was dried at 150° C. for one minute.
Second Subbing Layer (Hydrophilic Colloid Layer)
______________________________________                                    
Gelatin          amount shown in                                          
                 Table 2 below                                            
Polyethylene Acrylate                                                     
                   20 mg/m.sup.2                                          
C.sub.12 H.sub.25 O(CH.sub.2 CH.sub.2 O).sub.10 H                         
                   4 mg/m.sup.2                                           
 ##STR19##       0.27 mg/m.sup.2                                          
Dye              Compound and                                             
                 amount shown in                                          
                 Table 2 below                                            
______________________________________
Preparation of Silver Halide Emulsion
34 g of gelatin was dissolved in 850 ml of H2 O in a container. To the container containing the resulting aqueous gelatin solution heated to 65° C., there were added 1.7 g of sodium chloride, 0.1 g of potassium bromide and 70 mg of the following compound (A).
HO--(CH.sub.2).sub.2 S--(CH.sub.2).sub.2 --S--(CH.sub.2).sub.2 --OH
Subsequently, 500 ml of an aqueous solution containing 170 g of silver nitrate and 500 ml of an aqueous solution containing potassium hexachloroiridate (III) (in such an amount as to give a ratio by mol of iridium to the resulting silver halide of 5×10-7), 12 g of sodium chloride and 98 g of potassium bromide were added thereto by means of the double jet process to prepare cubic monodisperse silver chlorobromide grains having a mean grain size of 0.4 μm. After the resulting emulsion was desalted, 50 g of gelatin was added thereto. The pH of the emulsion was adjusted to 6.5, and the pAg thereof was adjusted to 8.1. Subsequently, 2.5 mg of sodium thiosulfate and 5 mg of chloroauric acid were added thereto, and chemical sensitization was carried out at 65° C. Further, 0.2 g of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene was added thereto, and the emulsion was quenched to solify the same (Emulsion A).
Separately, cubic monodisperse silver chlorobromide grains having a mean grain size of 0.3 μm were prepared in the same manner as Emulsion A, except that the gelatin solution was heated to 40° C. After desalting, 50 g of gelatin was added thereto. The pH of the emulsion was adjusted to 6.5, and the pAg thereof was adjusted to 8.1. Subsequently, 2.5 mg of sodium thiosulfate and 5 mg of chloroauric acid were added thereto, and chemical sensitization was carried out at 65° C. Further, 0.2 g of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene was added thereto, and the emulsion was quenched to solidify the same, thereby obtaining Emulsion B.
Emulsion A and Emulsion B in a ratio of 1:1 by weight were mixed, and the following additives were added to the emulsion mixture to obtain an emulsion coating solution, each amount being per mol of silver halide.
______________________________________                                    
Formulation of Emulsion Coating Solution                                  
______________________________________                                    
Spectral Sensitizing Dye (2)                                              
                      1.0 × 10.sup.-4 mol                           
Supersensitizing Agent (3)                                                
                      0.7 × 10.sup.-3 mol                           
Preservability Improver (4)                                               
                        1 × 10.sup.-3 mol                           
Polyacrylamide (Mol. Wt. = 40,000)                                        
                      10        g                                         
Dextran               10        g                                         
Trimethylol Propane   1.6       g                                         
Polystyrenesulfonic Acid (Na salt)                                        
                      1.2       g                                         
Latex of poly(ethyl acrylate/                                             
                      12        g                                         
methacrylic acid)                                                         
N,N'-Ethylenebis(vinyl-                                                   
                      3.0       g                                         
sulfonacetamide)                                                          
1-Phenyl-5-mercaptotetrazole                                              
                      50        mg                                        
Stabilizer (9)        100       mg                                        
______________________________________                                    
 Spectral Sensitizing Dye (2)                                             
 ##STR20##                                                                
 Supersensitizing Agent (3)                                               
 ##STR21##                                                                
?                                                                         
 Preservability Improver (4)                                              
 ##STR22##                                                                
?                                                                         
 Stabilzer (9)                                                            
 ##STR23##                                                                
?   Preparation of Coating Solution for Surface Protective Layer of       
 Emulsion Layer
A container was heated to 40° C. and the following additives were added thereto to prepare the coating solution.
______________________________________                                    
Formulation of Coating Solution for Surface Protective                    
Layer of Emulsion Layer                                                   
______________________________________                                    
Gelatin                   100     g                                       
Polyacrylamide (Mol. Wt. = 40,000)                                        
                          12      g                                       
Polysodium Styrenesulfonate                                               
                          0.6     g                                       
(Mol. Wt. = 600,000)                                                      
N,N'-Ethylenebis(vinyl sulfon-                                            
                          2.2     g                                       
acetamide)                                                                
Polymethyl Methacrylate (fine                                             
                          2.7     g                                       
particles having an average                                               
particle size of 2.0 μm)                                               
Sodium t-Octylphenoxyethoxy-                                              
                          1.8     g                                       
ethanesulfonate                                                           
C.sub.16 H.sub.33 O(CH.sub.2 O).sub.10H                                   
                          4.0     g                                       
Polysodium Acrylate       6.0     g                                       
C.sub.8 F.sub.17 SO.sub.3 K                                               
                          70      mg                                      
C.sub.8 F.sub.17 SO.sub.2 N(C.sub.3 H.sub.7)(CH.sub.2 CH.sub.2 O).sub.4   
(CH.sub.2).sub.4SO.sub.3 Na                                               
                          70      mg                                      
NaOH (1N)                 6       ml                                      
Methanol                  90      ml                                      
1-Phenyl-5-mercaptotetrazole                                              
                          80      mg                                      
Compound (5)              0.06    g                                       
 ##STR24##                                                                
______________________________________
Preparation of Photographic Materials 10 and 11
The above emulsion coating solution and the above coating solution for the surface protective layer were coated on each of Supports 9 and 10 in such amount as to provide a total silver coating weight (as Ag) of 2.3 g/m2 to prepare each of Photographic Materials 10 and Ill. The gelatin coating weight of the emulsion layer was 1.4 g/m2, and the gelatin coating weight of the surface protective layer was 1.0 g/m2.
The sensitivity of each emulsions was measured by the following sensitometry.
Sensitometry
The sensitometry of the thus-prepared Photographic Materials 10 and 11 was carried out in the following manner to measure the sensitivity and the gamma (contrast) value. Photographic Materials 10 and 11 were stored at 25° C. and 60% RH for 7 days after coating, and subjected to scanning exposure at room temperature using a semiconductor laser of 780 nm ("FCR Laser Image Printer type CR-LP414" manufactured by Fuji Photo Film Co., Ltd.). The photographic materials were then processed using an automatic processor FCR (manufactured by Fuji Photo Film Co., Ltd.) under conditions of a development temperature of 35° C., and a Dry to Dry time of 67 seconds. The conveying speed was mm/min. The replenishment rate of the developing solution was 23 ml/m2 of the photographic material, and that of the fixing solution was 23 ml/m2 of the photographic material.
The reciprocal of the exposure amount providing an optical density of the density of the unexposed area +1.0 is referred to as the sensitivity. The sensitivity is represented relative to the sensitivity of the Photographic Material 11 taken as 100.
The processing solutions had the following compositions.
______________________________________                                    
Developing Solution                                                       
KOH                      57.5   g                                         
Na.sub.2 SO.sub.3        87.5   g                                         
K.sub.2 SO.sub.3         110    g                                         
Diethylenetriaminepentaacetic Acid                                        
                         5      g                                         
Boric Acid               25     g                                         
K.sub.2 CO.sub.3         32.5   g                                         
Hydroquinone             87.5   g                                         
Diethylene Glycol        125    g                                         
4-Hydroxymethyl-4-methyl-l-phenyl-                                        
                         10     g                                         
3-pyrazolidone                                                            
5-Methylbenzotriazole    0.15   g                                         
2,3,5,6,7,8-Hexahydro-2-thioxo-4-(1H)-                                    
                         0.25   g                                         
quinazolinone                                                             
Sodium 2-Mercaptobenzimidazole-5-                                         
                         0.35   g                                         
sulfonate                                                                 
KBr                      7.5    g                                         
1-Phenyl-5-mercaptotetrazole                                              
                         0.15   g                                         
Water to make            one liter                                        
Fixing Solution                                                           
Ammonium Thiosulfate     145    g                                         
Disodium Ethylenediaminetetraacetate                                      
                         30     mg                                        
Dehydrate                                                                 
Na.sub.2 S.sub.2 O.sub.3.5H.sub.2 O                                       
                         15     g                                         
Sodium Metabisulfite     13.3   g                                         
NaOH                     12.6   g                                         
Acetic Acid (90 wt %)    30     g                                         
KI                       0.5    g                                         
Water to make            one liter                                        
______________________________________                                    

                                  TABLE 2                                 
__________________________________________________________________________
                              Amount of                                   
                                      Amount of                           
                      Dye in  Gelatin in                                  
                                      Gelatin                             
Photographic          Subbing Layer                                       
                              Subbing Layer                               
                                      per One Side                        
Material No.                                                              
        Polymer in Subbing Layer                                          
                      (Amount)                                            
                              (mg/m.sup.2)                                
                                      (g/m.sup.2)                         
                                             Sensitivity                  
                                                   Support                
__________________________________________________________________________
                                                   No.                    
10 (Comp. Ex.)                                                            
        butadiene-styrene copolymer                                       
                      Comparative                                         
                              160     2.4    70     9                     
        latex (butadiene/styrene =                                        
                      Compound (b)                                        
        31/69 by weight)                                                  
                      (30 mg/m.sup.2)                                     
11 (Invention)                                                            
        butadiene-styrene copolymer                                       
                      I-18 (50 mg/m.sup.2)                                
                              "       "      100   10                     
        latex (butadiene/styrene =                                        
        31/69 by weight)                                                  
 ##STR25##                                                                
Comparative compound (b)                                                  
__________________________________________________________________________
It is clearly seen from the results shown in Table 2 that according to the present invention, a photographic material having high sensitivity is obtained.
EXAMPLE 3
Preparation of Support 11
The following subbing layers were provided on the side opposite to that on which the subbing layers were previously coated in preparation of Support 3 of Example 1.
The side on which the subbing layers were previously coated is referred to as the front side, and the side on which the following subbing layers are provided is referred to as the back side.
The following first subbing layer was coated on the back side in such amount as to provide the following coating weights. The coating was carried out using a wire bar coater. The coated support was dried at 185° C. for one minute.
______________________________________                                    
First Subbing Layer                                                       
______________________________________                                    
Butadiene-Styrene Copolymer Latex                                         
                        0.322  g/m.sup.2                                  
(butadiene/styrene = 31/69 by weight)                                     
Sodium Salt of 2,4-Dichloro-6-                                            
                        8.4    mg/m.sup.2                                 
hydroxy-s-triazine                                                        
______________________________________
The latex solution contained 0.4 wt % of the following emulsifying dispersant (a) based on the amount, on a solid basis, of the latex.
Emulsifying Dispersant (a) ##STR26##
Subsequently, the following second subbing layer was coated on both sides of the support in such amount as to provide the following coating weights. The coating was carried out using a wire bar coater. The coated support was dried at 150° C. for one minute.
______________________________________                                    
Second Subbing Layer                                                      
______________________________________                                    
Gelatin               80     mg/m.sup.2                                   
Polyethyl Acrylate    20     mg/m.sup.2                                   
C.sub.12 H.sub.25 O(CH.sub.2 CH.sub.2 O).sub.10 H                         
                      4      mg/m.sup.2                                   
 ##STR27##            0.27   mg/m.sup.2                                   
______________________________________
Preparation of Photographic Material 12
The following insensitive hydrophilic colloid layer and the following polymer layer were coated (in this order) on the back side of Support 11 in such amount as to provide the following coating weights. The coated support was dried at 50° C. for 5 minutes.
______________________________________                                    
(1) Insensitive Hydrophilic Colloid Layer                                 
Gelatin                  1.5   g/m.sup.2                                  
Polymethyl methacrylate (fine                                             
                         50    mg/m.sup.2                                 
particles having an average                                               
particle size of 3 μm)                                                 
Sodium Dodecylbenzenesulfonate                                            
                         10    mg/m.sup.2                                 
Polysodium Styrenesulfonate                                               
                         20    mg/m.sup.2                                 
N,N'-Ethylenebis(vinylsulfonacetamide)                                    
                         30    mg/m.sup.2                                 
Ethyl Acrylate Latex (average particle                                    
                         1.0   g/m.sup.2                                  
size: 0.1 μm)                                                          
(2) Polymer Layer                                                         
Latex of Styrene:Butadiene:                                               
                         1     g/m.sup.2                                  
Divinylbenzene:Methacrylic                                                
Acid = 20:72:6:2                                                          
C.sub.8 F.sub.17 SO.sub.3 K                                               
                         5     mg/m.sup.2                                 
Sodium salt of 2,4-Dicholor-6-                                            
                         5     mg/m.sup.2                                 
hydroxy-s-triazine                                                        
______________________________________
The emulsion layer and the surface protective layer were coated on the front side of Support 11 in the same manner as in preparation of Photographic Material 4 of Example 1.
Evaluation of Drying Property
The evaluation of drying property was made in the same manner as in Example 1.
Evaluation of Curling
The obtained Samples were cut into test pieces of 5 cm (long) by 1 cm (wide), stored at 25° C. and 60% RH for 3 days and then transferred to an atmosphere of 25° C. and 10% RH. After 2 hours, the extent of curling of the test pieces was measured.
The curling value is determined by the following formula.
Curling value=1/(Curvature Radius (cm) of Sample)
When the emulsion side is the inner side, the curling value is given as a positive value, and when the emulsion side is the outer side, the curling value is given as a negative value. A practically acceptable curling value is in the range of from -0.02 to +0.02. The results obtained are shown in Table 3 below.
              TABLE 3                                                     
______________________________________                                    
Photographic                                                              
           Back     Drying           Support                              
Material No.                                                              
           Layer    Property  Curling                                     
                                     No.                                  
______________________________________                                    
 4 (Invention)                                                            
           omitted  G         0.1     3                                   
12 (Invention)                                                            
           provided G         0.01   11                                   
______________________________________
It is clearly seen from the results shown in Table 3 that according to the present invention, curling is effectively balanced by providing the specified back layer without deteriorating the drying property.
It will be understood from the above disclosure that the present invention provides silver halide photographic materials having high sensitivity and good image quality, which photographic materials are well adapted for rapid processing.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

Claims (8)

What is claimed is:
1. A silver halide photographic material comprising a transparent support having thereon a dye layer comprising a hydrophilic colloid, a hydrophobic polymer layer and at least one light-sensitive silver halide emulsion layer, wherein the dye layer contains at least one dye represented by formulae (I) to (VIII) dispersed in the form of fine solid particles, the dye layer is disposed between the at least one light-sensitive silver halide emulsion layer and the support, the hydrophilic colloid coating weight of the dye layer is 0.5 g/m2 or less, and the hydrophobic polymer layer is disposed between the dye layer and the support: ##STR28## wherein T10, T11 and T12 independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carboxyl group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, a carbamoyl group, an amino group, a sulfonamido group, a carbonamido group, a ureido group, a sulfamido group, a hydroxyl group, a vinyl group or an acyl group; R13 and R14 independently represent a hydrogen atom, a halogen atom, an alkoxy group, an alkyl group, an alkenyl group, an aryloxy group or an aryl group; R15 and R16 independently represent a member selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxy group, and a halogen atom; and R17 and R18 independently represent an alkyl group, an aryl group, a vinyl group, an acyl group or an alkyl- or arylsulfonyl group; or T11 and T12, R13 and R15, R14 and R16, R17 and R18, R15 and R17 or R16 and R18 may be combined together to form a ring; ##STR29## wherein R21 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group; R22 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, COR24 or SO2 R24 ; R23 represents a hydrogen atom, a cyano group, a hydroxyl group, a carboxyl group, an alkyl group, an aryl group, COOR24, OR24, NR25 R26, CONR25 R26, NR25COR24, NR25 SO2 R24 or NR25 CONR25 R26 ; R24 represents an alkyl group or an aryl group; R25 and R26 each represents a hydrogen atom, an alkyl group or an aryl group; L21 L, 22 and L23 each represents a methine group; and n21 represents 1 or 2; ##STR30## wherein X41 and X42 each represents a hydrogen atom, a hydroxyl group, a carboxyl group, --COOR41, --COR41, --CONH2, --CONR41 R42, an alkyl group, an aryl group or a heterocyclic group; Y41 and Y42 each represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group; Z41 and Z42 each represents a hydrogen atom, --CN, a carboxyl group, --COOR43, --COR43, --CONH2, --CONR43 R44, --NHCOR43, --NHSO2 R43, --SO2 R43, an alkyl group, an aryl group or a heterocyclic group; R41 and R43 each represents an alkyl group or an aryl group; R42 and R44 each represents a hydrogen atom, an alkyl group or an aryl group; L41, L42, L43, L44 and L45 each represents a methine group; and m41 and n41 each represents an integer and the sum of m41 and n41 is 2; ##STR31## wherein R51 and R52 each represents an alkyl group, an alkenyl group or an aryl group; L51 represents a bonding group formed by bonding five or seven methine groups through conjugated double bonds; Z51 represents an atomic group required for completing an aromatic ring; and X.sup.⊖ represents an anion; ##STR32## wherein R61 represents a hydrogen atom, an alkyl group or an aryl group; R62, R63, R64 and R65 each represents a hydrogen atom, an alkyl group, a halogen atom, an alkoxy group, an alkoxycarbonyl group, a carboxyl group, a hydroxyl group or an amino group; and L61, L62, L63, L64 and L65 each represents a methine group; and m61 amd n61 each represents an integer and the sum of m61 and n61 is 2; ##STR33## wherein L71 represents a nitrogen atom or a group formed by bonding five or seven methine groups through conjugated double bonds; E represents O, S or NR79 ; R70 and R79 independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an amino group, a hydrazino group or a diazenyl group; R71 represents a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, an alkynyl group or a heterocyclic group; R72 represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, a carboxyl group, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amino group, an acyloxy group, a carbamoyl group, a sulfamoyl group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group or an alkynyl group; R70 and R79 may be combined together to form a ring; R73 and R74 independently represent a hydrogen atom, a halogen atom, an alkoxy group, an alkyl group, an alkenyl group, an aryloxy group or an aryl group; R75 and R76 independently represent a member selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxy group, and a halogen atom; and R77 and R78 independently represent an alkyl group, an aryl group, a vinyl group, an acyl group or an alkyl- or arylsulfonyl group; or R73 and R75, R74 and R76, R77 and R78, R75 and R77 or R76 and R78 may be combined together to form a ring; ##STR34## wherein X81 represents a hydrogen atom, a hydroxyl group, COOR87, CONR87 R88, alkyl group or an aryl group; Y82 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group or NR87 R88 ; Z81 represents a hydrogen atom, an alkyl group, an aryl group, a cyano group, COOR89, CONR87 R88, COR89, SO2 R89, NR88 COR89, a nitro group or a pyridyl group; R81, R82, R83 and R84 each represents a hydrogen atom, an alkyl group, OR89, NR89 COR87, COOR89, CONR87 R88 or a halogen atom; R85 and R86 each represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group; and R87, R88 and R89 each represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group; or R81 and R82 , R85 and R86, R82 and R85, R83 and R86 or R87 and R88 may be combined together to form a five-membered or six-membered ring; ##STR35## wherein R91, R92 and R93 each represents a hydrogen atom, an alkyl group or an aryl group; Q1 represents an atomic group required for forming a basic heterocyclic ring; L91, L92, L93, L94, L95 and L96 each represents a methine group; and p91, m91 and n91 each represents 0 or 1 and p91 +m91l +n91 is an integer of at least 2, provided that the compound represented by formula (VIII) has at least one member selected from the group consisting of a carboxyl group, a sulfonic acid arylamido group and a phenolic hydroxyl group contained in the molecular structure thereof.
2. The silver halide photographic material as in claim 1, wherein the total hydrophilic colloid coating weight is 3 g/m2 or less per each side of the support.
3. The silver halide photographic material as in claim 1, wherein the hydrophobic polymer layer comprises a styrene-butadine copolymer or a vinylidene chloride copolymer.
4. The silver halide photographic material as in claim 1, further comprising a light-insensitive hydrophilic colloid layer containing a hydrophilic colloid as a binder provided on a second side of the support opposite the side having thereon at least one silver halide emulsion layer and a hydrophobic polymer layer provided on the second side of the support further away from the support than the light-insensitive hydrophilic colloid layer, and the light-insensitive hydrophilic colloid layer and the hydrophobic polymer layer are substantially not swollen when contacted with a processing solution.
5. The silver halide photographic material as in claim 1, wherein the fine solid particles have a particle size of 1.0 μm or smaller.
6. The silver halide photographic material as in claim 1, wherein the dye represented by formulae (I) to (VIII) is contained in the dye layer in an amount of from 5 to 300 mg/m2.
7. The silver halide photographic material as in claim 1, wherein the hydrophilic colloid coating weight of the dye layer is from 0.05 to 0.3 g/m2.
8. The silver halide photographic material as in claim 1, wherein the support comprises a polyethylene terephthalate film or a cellulose triacetate film.
US08/113,755 1992-09-03 1993-08-31 Silver halide photographic material Abandoned USH1515H (en)

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EP0911694A1 (en) * 1997-10-20 1999-04-28 Agfa-Gevaert N.V. A photosensitive silver halide material comprising a layer assembly
US5919610A (en) * 1995-12-27 1999-07-06 Agfa-Gevaert, N.V. Dyes for use in diverse applications

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EP0911694A1 (en) * 1997-10-20 1999-04-28 Agfa-Gevaert N.V. A photosensitive silver halide material comprising a layer assembly

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