Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
  • G03C1/498—Photothermographic systems, e.g. dry silver
  • G03C1/49836—Additives
  • G03C1/49845—Active additives, e.g. toners, stabilisers, sensitisers
  • G03C1/49854—Dyes or precursors of dyes
• • 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
  • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
  • G03C1/498—Photothermographic systems, e.g. dry silver
  • G03C1/49818—Silver halides
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
  • G03C5/16—X-ray, infrared, or ultraviolet ray processes
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
  • G03C5/16—X-ray, infrared, or ultraviolet ray processes
  • G03C5/164—Infrared processes
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
  • G03C8/40—Development by heat ; Photo-thermographic processes
  • G03C8/4013—Development by heat ; Photo-thermographic processes using photothermographic silver salt systems, e.g. dry silver

Definitions

• the present invention relates to a heat-developable color light-sensitive material. More particularly, the present invention relates to a heat-developable color light-sensitive material on which electric signaled-image data can be recorded via a light-emitting element to form a stable image. Furthermore, the present invention relates to a heat-developable color light-sensitive material which exhibits a minimized image density change against the processing temperature change during the heat development and a minimized image color balance change against the change in environmental conditions (particularly temperature) during exposure and provides an image with an excellent discrimination between image area and non-image area.
• a heat-developable color light-sensitive material is known in the art.
• heat-developable light-sensitive materials and processes thereof are described in Shashin Kogaku no Kiso (Principle of Photographic Engineering) , edition of non-silver salt system photography, published by Corona Co., 1982, pp. 242-255, and U.S. Patent 4,500,626.
• a method has been recently proposed which comprises allowing imagewise release or formation of a diffusible dye by a heat development, and then transferring the diffusible dye to a dye-fixing element.
• this method both negative and positive dye images can be obtained by altering the kind of dye-providing compounds used or the kind of silver halides used. Specifically, this method is described in U.S.
• Patents 4,500,626, 4,483,914, 4,503,137, 4,559,290, JP-A-58-149046 (The term "JP-A” as used herein means an "unexamined published Japanese patent application"), JP-A-60-133449, JP-A-59-218443, JP-A-61-238056, EP-A-220746, EP-A-210660, and JIII Journal of Technical Disclosure 87-6199.
• U.S. Patent 4,559,290 discloses a method which comprises coexisting a reducing agent or a precursor thereof with an oxidized DRR compound having no capability of releasing a dye image, oxidizing the reducing agent depending on the exposure of silver halide by a heat development, and reducing the oxidized DDR compound to release a non-diffusible dye.
• EP-A-220746 and JIII Journal of Technical Disclosure 87-6199 vol. 12, No.
• CTR cathode ray tube
• LED's are used, it is necessary that three LED's, i.e., near infrared (800 nm) LED, red (670 nm) LED and yellow (570 nm) LED, be combined to provide a light source to which a color light-sensitive material having three layers spectrally sensitized to near infrared, red and yellow ranges, respectively, is exposed.
• An image recording system having such a mechanism is described in Nikkei New Material , September 14, 1987, pp. 47-57. Some systems have been put into practical use.
• JP-A-61-137149 discloses a system which comprises three LD's emitting light of 880 nm, 820 nm and 760 nm in combination to form a light source to which a color light-sensitive material having three light-sensitive layers spectral sensitivity to the respective wavelength ranges to perform recording.
• a multi-layer color light-sensitive material which is adapted to be exposed to three different spectral ranges to develop three colors, i.e., yellow, magenta, and cyan, it is usually an important technique for color reproduction to develop these colors without staining colors.
• the light-sensitive material must be designed to such an extent that the three spectral sensitivities are provided in a narrow spectral range (i.e., from the short wavelength side of red to infrared). Therefore, how the overlap of these spectral sensitivities can be minimized is essential for improving color separatability.
• JP-A-4-146431 and JP-A-5-45828 disclose a color light-sensitive material which comprises a J-band type infrared sensitizing dye having a sharp spectral sensitivity to exhibit a good color separation, a high sensitivity and a good storage stability.
• the heat-developable color light-sensitive material comprising such a J-band type infrared sensitizing dye is disadvantageous in that the resulting image is liable to a great tint change under some environmental conditions, particularly temperature, during exposure.
• It is therefore an object of the present invention to provide a heat-developable color light-sensitive material comprising at least two silver halide emulsion layers having a spectral sensitivity peak in different wavelength ranges of 700 nm or more which exhibits less image density change against the processing temperature change during heat development, less image color balance change against the change in environmental conditions, particularly temperature, during exposure, and an excellent discrimination between the image area and the non-image area.
• a heat developable color light-sensitive material comprising a support having provided thereon at least two layers having a spectral sensitivity peak in a different wavelength range of 700 nm or more, in which the at least two layers are each combined with a compound which provides a dye having a different hue, wherein the layer having a spectral sensitivity peak in the longest wavelength and/or a light-insensitive interlayer(s) adjusted thereto comprises (a) a high silver chloride emulsion of fine grains having a silver chloride content of 80 mol% or more and an average size of 0.15 ⁇ m or less or (b) an easily soluble silver salt compound.
• ⁇ CB YM
• ⁇ CB MC
• ⁇ CB CY
• the compound which provides a dye (hereinafter referred to as a dye-providing compound) combined with the layer having a spectral sensitivity peak in the longest wavelength is a compound represented by the following formula (1): wherein Dye represents a dye group or dye precursor group represented by the following formula (2), Y represents a group which makes difference in diffusibility of the dye component in correspondence or reverse correspondence to a reduction reaction of light-sensitive silver halide having an imagewise latent image to silver; X represents a single bond or bonding group; p is an integer of 1 or more; and q is 1 or 2, with the proviso that when p is 2 or more, or when q is 2, the plurality of Dye's or ((Dye) p -X)'s may be the same or different: wherein R3 represents a substituent selected from the group consisting of a halogen atom, hydroxyl group, cyano group, nitro group, carb
• the spectral sensitivity peak in the layers of the heat developable color light-sensitive material is within a wavelength range of 700 nm or more, preferably from 700 to 1,200 nm.
• the high silver chloride emulsion of fine grains for use in the present invention can be prepared in the same manner as in the preparation of the silver halide emulsion described later.
• the silver chloride content is 80% or more, preferably 90% or more, by mol.
• the average size of the grains is preferably 0.15 ⁇ m less, more preferably from 0.01 to 0.10 ⁇ m.
• Examples of the easily soluble silver salt compound include silver nitrate, silver fluoride, silver perchlorate, silver hexafluorophosphate(V) and potassium dicyano-argentate(I). Among these, silver nitrate and silver fluoride are preferred.
• the amount added of the high silver chloride emulsion of fine grains or easily soluble silver salt compound is preferably from 5 mg/m2 to 100 mg/m2, more preferably from 10 mg/m2 to 60 mg/m2, in terms of silver.
• the incorporation of the high silver chloride emulsion of fine grains or easily soluble silver salt compound are contained in at least one layer of the layer having a spectral sensitivity peak in the longest wavelength and the light-insensitive interlayer(s) adjacent thereto.
• an effect of minimizing fluctuations in the heat development and color balance fluctuations against the variation of temperature conditions during exposure can be provided.
• Such an effect is normally much more remarkable than expected.
• Such an effect is probably inherent to heat-developable color light-sensitive materials.
• the detailed principle of this effect is unknown at present. This effect is more remarkable in combination with the dye-providing compound represented by formula (1).
• Such a combined use of the above-described emulsion or easily soluble silver salt compound and the above-described dye-providing compound is preferred because the excellent properties of the dye-providing compound can be provided.
• X represents a single bond or bonding group.
• Examples of the bonding group represented by X include an alkylene group, substituted alkylene group, arylene group, substituted arylene group, heterocyclic group, -O-, -SO2-, -CO-, -NR14- (in which R14 represents a hydrogen atom, alkyl group, aryl group or aralkyl group), and bonding groups formed by combining two or more of these groups.
• Preferred examples of the bonding group represented by X include -NR14SO2-, -NR14CO-, -O-, -SO2-, and groups formed by combining these groups with substituted or unsubstituted alkylene group (e.g., methylene, ethylene, propylene) or arylene group (e.g., o-phenylene, m-phenylene, p-phenylene, 1,4-naphthylene).
• substituted or unsubstituted alkylene group e.g., methylene, ethylene, propylene
• arylene group e.g., o-phenylene, m-phenylene, p-phenylene, 1,4-naphthylene.
• substituents include the following: an alkyl group which may be substituted (e.g., methyl, trifluoromethyl, chloromethyl, dimethylaminomethyl, ethoxycarbonylmethyl, aminomethyl, acetylaminomethyl, ethyl, carboxyethyl, 3,3,3-trichloropropyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, t-butyl, n-pentyl, sec-pentyl, t-pentyl, cyclopentyl, n-hexyl, sec-hexyl, t-hexyl, cyclohexyl, n-octyl, sec-octyl, t-octyl, n-decyl, n-undecyl, n-dode
• an alkyl group which may be substituted e
• alkoxy group particularly preferred are alkoxy group, amino group, sulfamoyl group, sulfonylamino group, carboxyl group, sulfo group, and halogen atom.
• Y includes a negative-working releaser which releases a photographically useful group in correspondence to development.
• Examples of Y include a negative-working releaser which releases a photographically useful group from an oxidation product.
• a preferred example thereof includes a compound represented by the following formula (Y-1): wherein ⁇ represents a nonmetallic atomic group necessary for forming a benzene ring, and the benzene ring may be condensed with a saturated or unsaturated carbon ring or heterocyclic ring; ⁇ - represents -OZ2 or -NHZ3, in which Z2 represents a hydrogen atom or a group capable of producing a hydroxyl group by hydrolysis and Z3 represents a hydrogen atom, alkyl group, aryl group or a group capable of producing an amino group by hydrolysis; Z1 represents a halogen atom, cyano group, alkyl group, aryl group, aralkyl group, alkoxy group, alkylthio group, aryloxy group, arylthio group, acyl group, sulfonyl group, acylamino group, sulfonylamino group, carbamoyl group, sulfamoyl
• Y-1 Preferred among groups represented by formula (Y-1) are those represented by the following formulae (Y-2) and (Y-3): wherein Z2 and G each has the same meaning as defined in formula (Y-1); and Z5 and Z6 each independently represents an alkyl group, aryl group or aralkyl group which each may have one or more substituents.
• Z5 is a secondary or tertiary alkyl group, and the sum of the number of carbon atoms contained in Z5 and Z6 is from 20 to 50.
• Y is (Y-4): wherein ⁇ , G, Z1 and a have the same meaning as defined in formula (Y-1), respectively; ⁇ ' represents a nonmetallic atomic group necessary for forming a benzene ring, and the benzene ring may be condensed with a saturated or unsaturated carbon ring or heterocyclic ring.
• ⁇ is -OZ2, and ⁇ ' forms a naphthalene skeleton.
• ⁇ is -OZ2, and ⁇ ' forms a naphthalene skeleton.
• Specific examples thereof are described in U.S. Patents 3,928,312 and 4,135,929.
• Examples of the compound which releases a photographically useful group from an oxidation product by another mechanism include hydroquinone derivatives represented by the following formulae (Y-5) and (Y-6): wherein ⁇ ' has the same meaning as defined in formula (Y-4); G and Z2 have the meaning as defined in formula (Y-1), respectively; Z7 has the same meaning as Z2; Z8 represents a hydrogen atom or the same substituent as defined with reference to Z1; and Z7 and Z8 may be the same or different. Specific examples thereof are described in U.S. Patent 3,725,062.
• hydroquinone derivative releasers may have a nucleophilic group in their molecules. Specific examples thereof are described in JP-A-4-97347.
• Still further examples of Y include p-hydroxydiphenylamine derivatives as described in U.S. Patent 3,443,939, and hydrazine derivatives as described in U.S. Patents 3,844,785 and 4,684,604, and Research Disclosure ( R.D. ) No. 128, page 22.
• Y-7 Coup-G (Y-7) wherein Coup represents a group capable of coupling with an oxidation product of p-phenylenediamine or p-aminophenol, i.e., group known as a photographic coupler. Specific examples thereof are described in British Patent 1,330,524.
• examples of Y include a positive-working releaser which releases a photographically useful group in counter correspondence to development.
• Examples of the positive-working releaser include a releaser which reveals its function by reduction during processing.
• Preferred examples thereof include the following formula (Y-8): wherein EAG represents a group which receives an electron from a reducing substance; N represents a nitrogen atom; W represents an oxygen atom, sulfur atom or -NZ11-, and, after EAG receives electron, N-W bond is cleaved; Z11 represents an alkyl or aryl group; and Z9 and Z10 each represent a single bond or a monovalent or divalent substituent other than a hydrogen atom, provided that the solid line represents a bond, and the broken lines indicate that at least one of these broken lines is bonded with each other.
• a preferred example of the group represented by formula (Y-8) includes the following formula (Y-9): wherein O represents an oxygen atom (in other words, W in (Y-8) is an oxygen atom); Z12 represents an atomic group capable of forming a heterocyclic ring containing N-O bond and cleaving Z12-G bond after cleaving the N-O bond, and Z12 may have one or more substituents, and may be condensed with a saturated or unsaturated ring; and Z13 represents -CO- or -SO2-.
• a preferred example of the group represented by formula (Y-9) include the following formula (Y-10): wherein Z14 represents an alkyl group, aryl group or aralkyl group; Z15 represents a carbamoyl group or sulfamoyl group; Z16 represents an alkyl, aryl group, aralkyl group, alkoxy group, alkylthio group, aryloxy group, arylthio group, halogen atom, cyano group or nitro group; and b is an integer of 0 to 3. Also, in formula (Y-10), the nitro group is substituted at an ortho- or para-position to the nitrogen atom.
• Z15 is a C12 ⁇ 30 carbamoyl group or sulfamoyl group substituted with an alkyl group.
• positive-working releaser which reveals its function
• BEND compounds as described in U.S. Patents 4,139,379 and 4,139,389
• Carquin compounds as described in British Patent 11,445
• releasers as described in JP-A-54-126535 and JP-A-57-84453.
• the reducible releaser represented by Y such as (Y-8) is used in combination with a reducing agent.
• a reducing agent such as (Y-8)
• an LDA compound comprising a reducing group incorporated in its molecule may be used.
• the LDA compound is further described in U.S. Patent 4,551,423.
• the positive-working releaser includes releasers which are contained in a light-sensitive material as a reducing product, and are inactivated by oxidization during processing.
• Examples thereof include Fields compounds as described in JP-A-51-63618 and U.S. Patent 3,980,479, and Hinshaw compounds as described in JP-A-49-111628, JP-A-52-4819, and U.S. Patent 4,199,354.
• Y includes the following formula (Y-11): wherein Z17 and Z19 each independently represents a hydrogen atom, an acyl, alkoxycarbonyl or aryloxycarbonyl group which may be substituted; Z18 represents an alkyl, aryl, aralkyl, acyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, sulfonyl or sulfamoyl group which may be substituted; and Z20 and Z21 each independently represents a hydrogen atom or an alkyl, aryl or aralkyl group which may be substituted. Specific examples thereof are described in JP-A-62-245270 and JP-A-63-46450.
• a still further mechanism of positive-working releaser is given by a thiazolidine type releaser.
• the thiazolidine type releaser is described in, e.g., U.S. Patent 4,468,451.
• Y preferably has at least one ballast group having 10 or more carbon atoms.
• the compound represented by formula (1) can exert its effect more remarkably when it comprises a negative-working releaser.
• R3 represents a halogen atom, a hydroxyl group, cyano group, nitro group, carboxyl group, or a substituted or unsubstituted alkyl, aralkyl, cycloalkyl, aryl, heterocyclic, alkoxy, aryloxy, amino, acylamino, sulfonylamino, acyl, sulfonyl, carbamoyl, sulfamoyl, ureido, alkylthio or arylthio group.
• R1 and R2 each independently represent a hydrogen atom or a substituent as defined by R3.
• n represents an integer of 0 to 5. When n is from 2 to 5, the plurality of R3's may be the same or different.
• Dye and X are bonded to each other at any one of R1, R2 and R3.
• R1 include a substituted or unsubstituted alkyl group having from 1 to 4 carbon atoms (e.g., methyl, isopropyl, t-butyl, methoxyethyl, ⁇ -cyanoethyl, trifluoromethyl), substituted or unsubstituted alkoxy group having from 1 to 4 carbon atoms (e.g., methoxy, ethoxy, methoxyethoxy), substituted or unsubstituted aryl group having from 6 to 8 carbon atoms (e.g., phenyl, p-methoxyphenyl, p-hydroxyphenyl), hydroxyl group, cyano group, carbamoyl group, and carboxyl group.
• substituted or unsubstituted alkyl group having from 1 to 4 carbon atoms e.g., methyl, isopropyl, t-butyl, methoxyethyl, ⁇ -cyanoethyl
• R2 include a substituted or unsubstituted alkyl group having from 1 to 8 carbon atoms (e.g., methyl, butyl, methoxyethyl, ⁇ -cyanoethyl, ⁇ -acetylaminoethyl, ⁇ -methanesulfonylaminoethyl), substituted or unsubstituted aryl group having from 6 to 8 carbon atoms (e.g., phenyl, p-methoxyphenyl, p-chlorophenyl), substituted or unsubstituted aralkyl group having from 7 to 12 carbon atoms (e.g., benzyl, ⁇ -phenetyl, p-methoxyphenetyl), substituted or unsubstituted alkoxy group having from 1 to 6 carbon atoms (e.g., methoxy, ethoxy, methoxyethoxy), acylamino group having
• R3 include a hydrogen atom, halogen atom, cyano group, carboxyl group, substituted or unsubstituted carbamoyl group having from 1 to 5 carbon atoms (e.g., carbamoyl, N-methylcarbamoyl, N,N-dimethylcarbamoyl), substituted or unsubstituted sulfamoyl group having from 0 to 4 carbon atoms (e.g., sulfamoyl, N-methylsulfamoyl, N,N-dimethylsulfamoyl), substituted or unsubstituted sulfonyl group having from 1 to 4 carbon atoms (e.g., methanesulfonyl, ethanesulfonyl), methyl group, methoxy group, and methoxyethoxy group.
• carbamoyl group having from 1 to 5 carbon atoms e.g., carbamoyl,
• Dye and X are bonded to each other at any one of R1, R2 and R3, preferably R2 or R3.
• the compound represented by formula (1) is preferably incorporated in the same layer as silver halide.
• the foregoing compound may be used in a wide range of amount, i.e., from 0.01 to 5 mol, preferably from 0.05 to 1 mol, per mol of silver.
• the compound of the present invention is a yellow dye-providing compound.
• the compound of the present invention is used in combination with a magenta dye-providing compound and a cyan dye-providing compound to obtain a full-color image.
• the compound of the present invention may be used in combination with another yellow dye-providing compound.
• the dye-providing compound used in combination with the compound of the present invention is represented by the following formula (4): wherein Dye' represents a dye (particularly magenta or cyan) or dye precursor; Y' represents a group which makes difference in diffusibility of the dye component in correspondence to or in counter correspondence to a reduction reaction of light-sensitive silver halide having an imagewise latent image to silver between before and after the reaction reduction (i.e., the same meaning as Y); X' represents a single bond or bonding group (i.e., the same meaning as X); i is an integer of 1 or more; and j is 1 or 2, with the proviso that when i is 2 or more or when j is 2, the plurality of (Dye')'s or ((Dye') i -X)'s may be the same or different.
• the heat-developable light-sensitive material according to the present invention essentially comprises light-sensitive silver halide, a binder, and optionally an organic metal salt oxidizer, a dye-providing compound (the reducing agent may serve also as a dye-providing compound as mentioned later) on a support.
• the reducing agent is preferably incorporated in the heat-developable light-sensitive material but may be externally supplied, e.g., by diffusing the reducing agent from the dye-fixing material as mentioned later.
• At least three silver halide emulsion layers having light-sensitivity in different spectral ranges are used in combination.
• a combination of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer, a combination of a green-sensitive layer, a red-sensitive layer and an infrared-sensitive layer, and a combination of a red-sensitive layer, an infrared-sensitive layer (I) and an infrared-sensitive layer (II) may be used as described in JP-A-59-180550, JP-A-64-13546, JP-A-62-253159, and EP-A-479167.
• These photosensitive layers may be arranged in various orders known in the field of the ordinary type color light-sensitive materials.
• These photosensitive layers may each be divided into two or more layers as described in JP-A-1-252954, if needed.
• the heat developable light-sensitive material may be provided with various light-insensitive layers such as protective layer, undercoating layer, interlayer, yellow filter layer and antihalation layer between the foregoing silver halide emulsion layers and various auxiliary layers such as backing layer on the opposite side of the support.
• various light-insensitive layers such as protective layer, undercoating layer, interlayer, yellow filter layer and antihalation layer between the foregoing silver halide emulsion layers and various auxiliary layers such as backing layer on the opposite side of the support.
• various light-insensitive layers such as protective layer, undercoating layer, interlayer, yellow filter layer and antihalation layer between the foregoing silver halide emulsion layers and various auxiliary layers such as backing layer on the opposite side of the support.
• Patent 5,051,335, an interlayer containing a solid pigment as disclosed in JP-A-1-167838 and JP-A-61-20943, an interlayer containing a reducing agent or DIR compound as disclosed in JP-A-1-120553, JP-A-5-34884 and JP-A-2-64634, an interlayer containing an electron transfer agent as disclosed in U.S. Patents 5,017,454 and 5,139,919 and JP-A-2-235,044, and a protective layer containing a reducing agent as disclosed in JP-A-4-249245 may be provided singly or in combination.
• the support is a polyethylene laminated paper containing a white pigment such as titanium oxide
• the back layer is preferably designed to exert an antistatic effect and exhibit a surface resistivity of 1012 ⁇ cm or less.
• the silver halide for use in the present invention may be any of silver chloride, silver bromide, silver bromoiodide, silver bromochloride, silver chloroiodide and silver bromochloroiodide.
• the silver halide emulsion for use in the present invention may be a surface latent image type emulsion or an internal latent image type emulsion.
• the internal latent image type emulsion may be used as a direct reversal emulsion in combination with a nucleating agent or light fogging agent.
• the silver halide emulsion to be used in the present invention may be a so-called core-shell emulsion differing from core to shell in phase or may have different silver halide compositions connected to each other via an epitaxial junction.
• the silver halide emulsion may be monodisperse or polydisperse.
• Monodisperse silver halide emulsions may be used in admixture to control gradation as disclosed in JP-A-1-167743 and JP-A-4-223463.
• the grain size of silver halide grains is preferably from 0.1 to 2 ⁇ m, more preferably from 0.2 to 1.5 ⁇ m.
• the crystal habit of silver halide grains may be any of regular crystal such as cube, octahedron and tetradecahedron, irregular crystal such as sphere and tablet having a high aspect ratio, crystal having a crystal defect such as twinning plane, composite thereof and other crystal forms.
• desalting i.e., removal of excess salts
• noodle washing involving gelation of gelatin may be conducted.
• sedimentation method using an inorganic salt e.g., sodium sulfate
• anionic surface active agent or anionic polymer e.g., sodium polystyrenesulfonate
• polyvalent anions or gelatin derivative e.g., aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin
• gelatin derivative e.g., aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin
• the light-sensitive silver halide emulsion for use in the present invention may comprise heavy metals such as iridium, rhodium, platinum, cadmium, zinc, thallium, lead, iron and osmium for various purposes. These compounds may be used singly or in combination. The amount thereof depends on the purpose but is normally about from 10 ⁇ 9 to 10 ⁇ 3 mol per mol of silver halide. Such a compound may be uniformly incorporated in grains or may be localized inside or on the surface of grains. In some detail, an emulsion as disclosed in JP-A-2-236542, JP-A-1-116637 and JP-A-5-181246 is preferably used.
• a silver halide solvent there may be used a thiocyanate, ammonia, 4-substituted thioether compound, organic thioether derivative as disclosed in JP-B-47-11386 or sulfur-containing compound as disclosed in JP-A-53-144319.
• the emulsion can be prepared by any of the acid process, the neutral process, and the ammonia process.
• the reaction between a soluble silver salt and a soluble halogen salt can be carried out by any of a single jet process, a double jet process, and a combination thereof.
• the double jet process is preferably used to obtain a monodisperse emulsion.
• a method in which grains are formed in the presence of excess silver ions may be used. Further, a so-called controlled double jet process, in which a pAg value of a liquid phase in which silver halide grains are formed is maintained constant, may also be used.
• concentration, amount or addition rate of silver salts and halides may be raised to expedite the growth of grains (as disclosed in JP-A-55-142329, JP-A-55-158124, and U.S. Patent 3,650,757).
• the agitation of the reaction solution may be effected by any known agitation method.
• the temperature and pH of the reaction solution during the formation of silver halide grains may be arbitrarily predetermined depending on the purpose.
• the pH is preferably from 2.2 to 7.0, more preferably from 2.5 to 6.0.
• the light-sensitive silver halide emulsion is a chemically-sensitized silver halide emulsion.
• the chemical sensitization of the light-sensitive silver halide emulsion according to the present invention may be effected by chalcogen sensitization method such as sulfur sensitization method, selenium sensitization method and tellurium sensitization method, noble metal sensitization method using gold, platinum, or palladium, and reduction sensitization method, singly or in combination (as disclosed in JP-A-3-110555 and JP-A-5-241267).
• the chemical sensitization may be effected in the presence of a nitrogen-containing heterocyclic compound (as disclosed in JP-A-62-253159).
• An antifoggant as described later may be added after the completion of chemical sensitization.
• a method as described in JP-A-5-45833 and JP-A-62-40446 may be used.
• the pH value during the chemical sensitization is preferably from 5.3 to 10.5, more preferably from 5.5 to 8.5.
• the pAg value during the chemical sensitization is preferably from 6.0 to 10.5, more preferably 6.8 to 9.0.
• the coated amount of the light-sensitive silver halide emulsion according to the present invention is from 1 mg/m2 to 10 g/m2 in terms of silver.
• the light-sensitive silver halide emulsion according to the present invention is spectrally sensitized with a methine dye or the like to have color sensitivity for green, red or infrared. If necessary, the blue-sensitive emulsion may be spectrally sensitized at a blue range.
• dyes for use in the spectral sensitization include cyanine dye, melocyanine dye, composite cyanine dye, composite melocyanine dye, holopolar cyanine dye, hemicyanine dye, styryl dye and hemioxonol dye.
• sensitizing dyes as disclosed in U.S. Patent 4,617,257, JP-A-59-180550, JP-A-64-13546, JP-A-5-45828 and JP-A-5-45834 can be used.
• sensitizing dyes can be used singly or in combination.
• a combination of these sensitizing dyes is often used particularly for the purpose of wavelength adjustment in supersensitization or spectral sensitization.
• a dye which doesn't exert a spectral sensitizing effect itself or a compound which doesn't substantially absorb visible light but exerts a supersensitizing effect may be incorporated in the emulsion (as disclosed in U.S. Patent 3,615,641, and JP-A-63-23145).
• sensitizing dyes may be added in the form of solution in an organic solvent such as methanol, dispersion in gelatin or solution in a surface active agent.
• the amount of these sensitizing dyes to be added is normally from 10 ⁇ 8 mol to 10 ⁇ 2 mol per mol of silver halide.
• Additives which can be used in these processes and known light-sensitive additives which can be incorporated in the heat-developable light-sensitive material are also described in the above cited RD Nos. 17643, 18716 and 307105 as tabulated below.
• Additive RD 17643 RD 18716 RD 307105 1. Chemical Sensitizer p.23 p.648, right column (RC) p.866 2. Sensitivity Increasing Agent ditto 3. Spectral Sensitizer, Supersensitizer pp.23-24 p.648, RC to p.649, RC pp.866-868 4. Brightening Agent p.24 p.648, RC p.868 5.
• Antifoggant, Stabilizer pp.24-25 p.649, RC pp.868-870 6. Light Absorbent, Filter Dye, Ultraviolet Absorbent pp.25-26 p.649, RC to P.650, left column (LC) p.873 7. Dye Image Stabilizer p.25 p.650, LC p.872 8. Hardening Agent p.26 p.651, LC pp.874-875 9. Binder p.26 ditto pp.873-874 10. Plasticizer, Lubricant p.27 p.650, RC p.876 11. Coating Aid, Surface Active Agent pp.26-27 ditto p.875-876 12. Antistatic Agent p.27 ditto pp.876-877 13. Matting Agent pp.878-879
• the binder in the light-sensitive material or dye-fixing material is preferably hydrophilic.
• hydrophilic examples thereof include those described in the above cited RD 's and JP-A-64-13546, pp. 71-75.
• a transparent or semi-transparent hydrophilic binder is preferred.
• proteins such as gelatin and gelatin derivatives, natural compounds such as cellulose derivatives, starch, gum arabic, dextran, pullulan and other polysaccharides, and synthetic high molecular compounds such as polyvinyl alcohol, polyvinyl pyrrolidone and acrylamide.
• a high water absorption polymer as disclosed in U.S.
• Patent 4,960,681, and JP-A-62-245260 i.e., homopolymer of vinyl monomer having -COOM or -SO3M (in which M is a hydrogen atom or alkaline metal atom) or copolymer of such vinyl monomers or copolymer of such vinyl monomers with other vinyl monomers (e.g., sodium methacrylate, ammonium methacrylate, Sumikagel available from Sumitomo Chemical Co., Ltd.) may be used.
• Two or more of these binders may be used in combination.
• a combination of gelatin and the binders is preferred.
• Gelatin may be selected from the group consisting of lime-treated gelatin, acid-treated gelatin and delimed gelatin having a reduced content of calcium or the like depending on various purposes. These gelatins may be preferably used in combination.
• the high water absorption polymer In the system where heat development is effected with the supply of a slight amount of water, if the high water absorption polymer is used, water absorption can be rapidly effected. Further, if a high water absorption polymer is incorporated in the dye-fixing layer or its protective layer, the dyes can be prevented from being re-transferred from the dye-fixing element to other elements after transfer.
• the amount of the binder is preferably 20 g/m2 or less, more preferably 10 g/m2 or less, and particularly preferably from 0.5 g/m2 to 7 g/m2.
• the light-sensitive element may comprise an organic metal salt as an oxidizer in combination with the light-sensitive silver halide emulsion.
• organic silver salts are particularly preferred as organic metal salts.
• organic compounds which can be used to form such an organic silver salt as an oxidizer include benzotriazoles, aliphatic acids and other compounds as disclosed in U.S. Patent 4,500,626 (col. 52-53).
• Other useful examples of organic compounds include silver acetylene as described in U.S. Patent 4,775,613. Two or more of these organic silver salts may be used in combination.
• the above mentioned organic silver salt can be used in an amount of 0.01 to 10 mol, preferably 0.01 to 1 mol, per mol of light-sensitive silver halide.
• the sum of the coated amount of light-sensitive silver halide and organic silver salt is preferably from 0.05 mg/m2 to 10 g/m2, more preferably 0.1 g/m2 to 4 g/m2, in terms of silver.
• the reducing agent for use in the present invention include those known in the field of light-sensitive material. Reducing dye-providing compounds as described later can also be used (in this case, other reducing agents may be used in combination therewith). Further, a reducer precursor which exhibits no reducing effect itself but exerts a reducing effect by a nucleophilic reagent or heat during development can be used.
• reducing agents for use in the present invention include reducing agents and reducer precursors as disclosed in U.S. Patents 4,500,626 (col. 49-50), 4,839,272, 4,330,617, 4,590,152, 5,017,454, and 5,139,919, JP-A-60-140335 (pp.
• an electron transfer agent and/or electron transfer agent precursor can be optionally used in combination therewith to accelerate the migration of electrons between the nondiffusible reducing agent and the developable silver halide.
• those disclosed in U.S. Patent 5,139,919, and EP-A-418743 are preferably used.
• a method for stably incorporating the reducing agent to the layers as disclosed in JP-A-2-230143 and JP-A-2-235044 may be preferably used.
• the electron transfer agent or precursor thereof can be selected from the above mentioned reducing agents or precursors thereof.
• the electron transfer agent or precursor thereof preferably exhibits a greater mobility than the nondiffusible reducing agent (electron donor).
• Particularly useful electron transfer agents are 1-phenyl-3-pyrazolidones or aminophenols.
• the nondiffusible reducing agent (electron donor) to be used in combination with the electron transfer agent can be selected from compounds which don't migrate substantially in the layers constituting light-sensitive material in the above mentioned reducing agents.
• Preferred examples thereof include hydroquinones, sulfonamidephenols, sulfonamidenaphtholes, compounds described as electron donors in JP-A-53-110827 and U.S. Patents 5,032,487, 5,026,634 and 4,839,272, and nondiffusible reducing dye-providing compounds as described later.
• an electron donor precursor as disclosed in JP-A-3-160443 may be preferably used.
• the interlayer and protective layer may comprise the reducing agents incorporated therein for various purposes such as prevention of color stain and improvement in color reproducibility.
• reducing agents as disclosed in EP-A-524649, EP-A-357040, JP-A-4-249245, JP-A-2-46450 and JP-A-63-186240 are preferably used.
• development inhibitor-releasing reducing compounds as disclosed in JP-B-3-63733, JP-A-1-150135, JP-A-2-64634, JP-A-3-43735, and EP-A-451833 may be used.
• the total amount of the reducing agents to be incorporated is preferably from 0.01 to 20 mol, more preferably from 0.1 to 10 mol, per mol of silver.
• silver may be used as an image-forming substance.
• the image-forming substance includes a compound which produces or releases a mobile dye in correspondence or counter correspondence to the reduction reaction of silver ion to silver at high temperature, i.e., dye-providing compound.
• Examples of the dye-providing compounds for use in the present invention include compounds (couplers) which form a dye by an oxidative coupling reaction. These couplers may be two-equivalent or four-equivalent. Further, two-equivalent couplers containing a nondiffusible group as a separatable group which form a diffusible dye by an oxidative coupling reaction can be preferably used. These nondiffusible groups may form a polymer chain. Specific examples of color developing agents and couplers are further described in T.H. James, The Theory of the Photographic Process , 4th ed. (pp. 291-334 and pp. 354-361), RD No. 307105 (p.
• JP-A-58-123533 JP-A-58-149046, JP-A-58-149047, JP-A-59-111148, JP-A-59-124399, JP-A-59-174835, JP-A-59-231539, JP-A-59-231540, JP-A-60-2950, JP-A-60-2951, JP-A-60-14242, JP-A-60-23474 and JP-A-60-66249.
• dye-providing compound is a compound which serves to imagewise release or diffuse a diffusive dye.
• This type of a compound can be represented by the following formula [LI]: wherein DYE represents a dye group or a dye group or dye precursor group which has been temporarily shifted to a short wavelength; Y represents a single bond or bonding group; Z represents a group which makes difference in diffusibility of the compound represented by or releases to make difference in diffusibility from in correspondence or counter correspondence to a light-sensitive silver salt having an imagewise latent image; s is an integer 1 to 5; and t is 1 or 2, with the proviso that when either s or t is not 1, the plurality of DYE's may be the same or different.
• the dye-providing compound represented by formula [LI] include the following compounds (1) to (5).
• the compounds (1) to (3) form a diffusive dye image (positive dye image) in counter correspondence to the development of silver halide.
• the compounds (4) and (5) form a diffusive dye image (negative dye image) in correspondence to the development of silver halide.
• dye-providing compounds other than the above mentioned couplers and dye-providing compounds represented by formula [LI] include dye silver compounds in which an organic silver salt and a dye are connected to each other ( RD , May 1978, pp. 54-58), azo dyes for use in heat development silver dye bleaching process (U.S. Patent 4,235,957, RD , April 1976, pp. 30-32), and leuco dyes (U.S. Patents 3,985,565 and 4,022,617).
• Hydrophobic additives such as dye-providing compounds and nondiffusible reducing agents can be incorporated in the layers constituting the light-sensitive material according to any known method.
• a high boiling organic solvent as disclosed in U.S. Patents 4,555,470, 4,536,466, 4,536,467, 4,587,206, 4,555,476 and 4,599,296, and JP-B-3-62256 can be used in combination with an organic solvent having a boiling point as low as 50°C to 160°C, if necessary.
• Two or more of these dye-providing compounds, nondiffusible reducing agents and high boiling organic solvents may be used in combination.
• the amount of the high boiling organic solvent is 10 g or less, preferably 5 g or less, and more preferably from 0.1 g to 1 g, per g of dye-providing compound used, and 1 ml or less, preferably 0.5 ml or less, more preferably 0.3 ml or less, per g of binder used.
• a compound substantially insoluble in water can be finely dispersed in the binder rather than using the above mentioned methods.
• colloids When a hydrophobic compound is dispersed in a hydrophilic colloid, various colloids can be used.
• compounds disclosed as surface active agents in JP-A-59-157636 (pp. 37-38) and the above cited RD 's can be used.
• a compound which activates development and stabilizes an image may be incorporated in the light-sensitive material.
• Preferable examples thereof are described in U.S. Patent 4,500,626 (col. 51-52).
• various compounds may be incorporated in the layers constituting the heat-developable light-sensitive material for fixing or decoloring undesirable dyes or colored matters to improve the properties of the white background of the resulting image.
• the layers constituting the heat-developable light-sensitive material according to the present invention can comprise various pigments or dyes incorporated therein for improving color separatability or raising sensitivity.
• a dye-fixing element is used in combination with the heat-developable light-sensitive material.
• the dye-fixing element may be separately applied to a support different from that for the light-sensitive material or may be applied to the same support as the light-sensitive material.
• those disclosed in U.S. Patent 4,500,626 can apply to the present invention.
• the dye-fixing element which can be preferably used in the present invention comprises at least one layer containing a mordant and a binder.
• a mordant there may be used one known in the art.
• Specific examples of such a mordant include mordants as disclosed in U.S. Patent 4,500,626 (col. 58-59), JP-A-61-88255 (pp. 32-41) and JP-A-1-161236 (pp. 4-7), and mordants as disclosed in JP-A-62-244043 and JP-A-62-244036.
• dye-accepting high molecular compounds as disclosed in U.S. Patent 4,463,079 may be used.
• binder to be incorporated in the dye-fixing element according to the present invention there may be preferably used the foregoing hydrophilic binder.
• carrageenans as disclosed in EP-A-443529 may be preferably used as well.
• the dye-fixing element may comprise auxiliary layers such as protective layer, peel layer and anticurling layer, if necessary.
• auxiliary layers such as protective layer, peel layer and anticurling layer, if necessary.
• a protective layer is advantageously provided.
• the layers constituting the heat-developable photographic light-sensitive material and dye fixing element can comprise a plasticizer, a lubricant or a high boiling organic solvent as an agent for improving the peelability between the light-sensitive material and the dye fixing element.
• a plasticizer e.g., polyethylene glycol dimethacrylate copolymer, polymethyl methacrylate copolymer, polymethyl methacrylate copolymer, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, poly
• silicone oils ranging from dimethyl silicone oil to modified silicone oils obtained by incorporating various organic groups in dimethyl siloxane
• Useful examples of such silicone oils are various modified silicone oils described in Modified Silicone Oil (technical report published by Shin-Etsu Silicone Co., Ltd.), page 6-18B, particularly carboxy-modified silicone (trade name: X-22-3710).
• silicone oils as disclosed in JP-A-62-215953 and JP-A-63-46449 can also be effectively used.
• the heat-developable light-sensitive material or dye fixing element may comprise a discoloration inhibitor.
• a discoloration inhibitor examples thereof include oxidation inhibitor, ultraviolet absorbent, and some kinds of metal complexes.
• oxidation inhibitor examples include chroman compounds, coumaran compounds, phenol compounds (e.g., hindered phenols), hydroquinone derivative, hindered amine derivative, and spiroindan compounds. Further, compounds as described in JP-A-61-159644 can also be effectively used as oxidation inhibitors.
• ultraviolet absorbents examples include benzotriazole compounds (U.S. Patent 3,533,794), 4-thiazolidone compounds (U.S. Patent 3,352,681), benzophenone compounds (JP-A-46-2784), and compounds (JP-A-54-48535, JP-A-62-136641, JP-A-61-88256). Further, ultraviolet-absorbing polymers as disclosed in JP-A-62-260152 can also be effectively used as ultraviolet absorbents.
• metal complexes examples include compounds as disclosed in U.S. Patents 4,241,155, 4,245,018 (col. 3-36), and 4,254,195 (col. 3-8), and JP-A-62-174741, JP-A-61-88256 (pp. 27-29), JP-A-63-199248, JP-A-1-75568 and JP-A-1-74272.
• the discoloration inhibitor for inhibiting the transfer of a dye which has been transferred to the dye fixing material may be previously incorporated in the dye fixing element or supplied into the dye fixing element externally, e.g., from the light-sensitive material.
• oxidation inhibitors ultraviolet absorbents and metal complexes may be used in combination.
• the heat-developable light-sensitive material or dye fixing element may comprise a fluorescent brightening agent.
• the fluorescent brightening agent is preferably incorporated in the dye fixing element or supplied into the dye fixing element externally, e.g., from the light-sensitive material.
• the fluorescent brightening agent include compounds as disclosed in K. Veenkataraman, The Chemistry of Synthetic Dyes , vol. V, Chapter 8, and JP-A-61-143752.
• Specific examples of the fluorescent brightening agent include stilbene compounds, coumarine compounds, biphenyl compounds, benzoxazolyl compounds, naphthalimide compounds, pyrazoline compounds, and carbostyryl compounds.
• the fluorescent brightening agent can be used in combination with a discoloration inhibitor or ultraviolet absorbent.
• JP-A-62-215272 pp. 125-137
• JP-A-1-161236 pp. 17-43
• film hardeners to be incorporated in the layers constituting the heat-developable light-sensitive material or dye fixing element include those described in the above cited RD 's, U.S. Patents 4,678,739 (col. 41), 4,791,042, JP-A-59-116655, JP-A-62-245261, JP-A-61-18942 and JP-A-4-218044.
• film hardeners include aldehyde film hardeners (e.g., formaldehyde), aziridine film hardeners, epoxy film hardeners, vinylsulfone film hardeners (e.g., N,N'-ethylene-bis(vinylsulfonylacetamido)ethane), N-methylol film hardeners (e.g., dimethylolurea), and high molecular film hardeners (e.g., compounds as described in JP-A-62-234157).
• aldehyde film hardeners e.g., formaldehyde
• aziridine film hardeners e.g., epoxy film hardeners
• vinylsulfone film hardeners e.g., N,N'-ethylene-bis(vinylsulfonylacetamido)ethane
• N-methylol film hardeners e.g., dimethylolurea
• high molecular film hardeners e.g
• the film hardener may be used in an amount of 0.001 g to 1 g, preferably 0.005 g to 0.5 g, per g of gelatin coated. Such a film hardener may be incorporated in any of the layers constituting the light-sensitive material or dye-fixing element or may be separately incorporated in two or more layers.
• the layers constituting the heat-developable light-sensitive material or dye-fixing element may comprise various antifoggants or photographic stabilizers or precursors thereof. Specific examples of these compounds are disclosed in the above cited RD 's, U.S. Patents 5,089,378, 4,500,627, 4,614,702, 4,775,610, 4,628,500, 4,983,494, JP-A-64-13546 (pp. 7-9, pp. 57-71, pp. 81-97), JP-A-62-174747, JP-A-62-239148, JP-A-1-150135, JP-A-2-110557, JP-A-2-178650, and RD No. 17,643 (1978, pp. 24-25).
• These compounds are preferably used in an amount of 5 ⁇ 10 ⁇ 6 to 1 ⁇ 10 ⁇ 1 mol, more preferably 1 ⁇ 10 ⁇ 5 to 1 ⁇ 10 ⁇ 2 mol, per mol of silver.
• the layers constituting the heat-developable light-sensitive material or dye fixing element can comprise various surface active agents for aiding coating, improving peelability and slip properties, inhibiting electrification, accelerating development or like purposes.
• Specific examples of the surface active agents are described in the above cited RD 's, JP-A-62-173463 and JP-A-62-183457.
• the layers constituting the heat-developable light-sensitive material or dye fixing element can comprise an organic fluoro compound incorporated therein for improving slip properties and peelability, inhibiting electrification or like purposes.
• organic fluoro compound include fluoro surface active agents as disclosed in JP-B-57-9053 (col. 8-17), JP-A-61-20944 and JP-A-62-135826, and hydrophobic fluorine compounds such as oil fluorinic compound (e.g., fluorine oil), and solid fluorine compound resin (e.g., ethylene tetrafluoride resin).
• the heat-developable light-sensitive material or dye fixing element can comprise a matting agent.
• the matting agent include silicon dioxide, polyolefin and polymethacrylate as described in JP-A-61-88256 (p. 29), and benzoguanamine resin beads, polycarbonate resin beads and AS resin beads as described in JP-A-63-274944 and JP-A-63-274952. Further, compounds as disclosed in the above cited RD 's may be used.
• the layers constituting the heat-developable photographic light-sensitive material and dye fixing element may comprise a heat solvent, an anti-foaming agent, a bactericide, a mildewproofing agent, a colloidal silica, etc.
• a heat solvent an anti-foaming agent, a bactericide, a mildewproofing agent, a colloidal silica, etc.
• the heat-developable light-sensitive material and/or dye fixing element can comprise an image formation accelerator.
• the image formation accelerator serves to accelerate the redox reaction of a silver salt oxidizer and a reducing agent, accelerate reaction such as production or decomposition of a dye from a dye-providing substance and release of a diffusible dye from a dye-providing substance or accelerate the migration of a dye from the heat-developable light-sensitive material layer to the dye fixing layer.
• the image formation accelerator can be classified as base or base precursor, nucleophilic compound, high boiling organic solvent (oil), heat solvent, surface active agent, compound interacting with silver or silver ion, and the like. However, these substance groups normally have composite functions and exert some of these accelerating effects in combination.
• Examples of the base precursors include salts of organic acid and base which undergo decarboxylation on heating, and compounds which undergo intramolecular nucleophilic substitution reaction, Lossen rearrangement or Beckman rearrangement to release amines. Specific examples of the base precursors are disclosed in U.S. Patents 4,514,493 and 4,657,848.
• a base and/or base precursor is preferably incorporated in the dye-fixing element to enhance the preservability of the heat-developable light-sensitive material.
• a combination of a difficultly soluble metal compound and a compound capable of undergoing complexing reaction with metal ions constituting the difficultly soluble metal compound (i.e., complexing compound) as disclosed in EP-A-210660 and U.S. Patent 4,740,445 and a compound which undergoes electrolysis to produce a base as disclosed in JP-A-61-232451 may be used as base precursors.
• the former is effective.
• the difficultly soluble metal compound and the complexing compound are advantageously incorporated separately in the heat-developable light-sensitive material and the dye-fixing element.
• the heat-developable light-sensitive material and/or dye fixing element may comprise various development stop agents for the purpose of obtaining an invariably constant image quality against the fluctuation of processing temperature and time during development.
• the development stop agent is a compound which rapidly neutralizes or reacts with a base after a proper development to reduce the base concentration in the film to stop development or a compound which interacts with silver or a silver salt after a proper development to inhibit development.
• Specific examples of the development stop agent include an acid precursor which releases an acid under heating, an electrophilic compound which undergoes substitution reaction with a base present therewith under heating, a nitrogen-containing heterocyclic compound, and a mercapto compound and precursor thereof. These compounds are further described in JP-A-62-253159 (pp. 31-32).
• the support for the heat-developable light-sensitive material and dye fixing element is preferably a support material which can withstand the processing temperature.
• photographic supports such as paper and synthetic high molecular compounds (film) as disclosed in Shashin Kogaku no Kiso - Ginen Shashin hen (Base of Photographic Engineering - Silver Salt Photography Edition) , Society of Photographic Science and Technology of Japan, Corona Co., Ltd., 1979, pp. 223-240, are used.
• the support materials include polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, cellulose (e.g., triacetyl cellulose), support materials obtained by incorporating a pigment such as titanium oxide in these films, paper obtained by film process synthesis of polypropylene, mixed paper made from a synthetic resin pulp such as polyethylene and a natural pulp, Yankee paper, baryta paper, coated paper (particularly cast coat paper), metal, cloth, and glass.
• These support materials can be used directly or in the form of laminate with a synthetic high molecular compound such as polyethylene on one or both sides thereof.
• support materials as disclosed in JP-A-62-253159 (pp. 29-31), JP-A-1-161236 (pp. 14-17), JP-A-63-316848, JP-A-2-22651, JP-A-3-56955 and U.S. Patent 5,001,033 can be used.
• a hydrophilic binder Onto the surface of these support materials may be coated a hydrophilic binder, an oxide of semiconducting metal such as alumina sol and tin oxide, carbon black, and other antistatic agents.
• Examples of methods for imagewise exposing the heat-developable light-sensitive material to record an image thereon include method which comprises directly photographing scene or persons using a camera or the like, method which comprises exposure through a reversal film or negative film using a printer or enlarger, method which comprises scanning exposure to an original image through a slit using an exposing apparatus in a copying machine, method which comprises exposure to light emitted by a light emitting diode or various lasers excited by an electrical signal representative of image data, and method which comprises exposure directly or through an optical system to image data outputted to an image display apparatus such as CRT, liquid crystal display, electroluminescence display and plasma display.
• an image display apparatus such as CRT, liquid crystal display, electroluminescence display and plasma display.
• Examples of light sources for recording an image on the heat-developable light-sensitive material include natural light, tungsten lamp, light emitting diode, laser, CRT, and other light sources as described in U.S. Patent 4,500,626, 56th column, JP-A-2-53378 and JP-A-2-54672.
• a wavelength conversion element in which a nonlinear optical material is combined with a coherent light source such as laser can be used to effect imagewise exposure.
• the nonlinear optical material is a material capable of developing nonlinearity between polarization and electric field created when a strong photoelectric field such as laser is given.
• Inorganic compounds such as lithium niobate, potassium dihydrogenphosphate (KDP), lithium iodate and BaB2O4, urea derivatives, nitroaniline derivatives, nitropyridine-N-oxide derivatives such as 3-methyl-4-nitropyridine-N-oxide (POM), and compounds as described in JP-A-61-53462 and JP-A-62-210432.
• Examples of wavelength conversion elements include single crystal light guide type wavelength conversion element and fiber type wavelength conversion element. Any of these types of wavelength conversion elements can be effectively used.
• Examples of the image data to which the present invention can be applied include image signal obtained from video camera or electronic still camera, television signal stipulated by National Television Signal Code (NTSC), image signal obtained by dividing an original image into many pixels by a scanner, and image signal produced by computers such as CG and CAD.
• NTSC National Television Signal Code
• the heat-developable light-sensitive material and/or dye-fixing element according to the present invention may comprise an electrically conductive heating element layer as a heating means for heat development and diffusion transfer of dye.
• heating element disclosed in JP-A-61-145544 can be used.
• the heating temperature at the heat development process is normally from about 50°C to 250°C, particularly about 60°C to 180°C.
• the diffusion transfer of a dye may be effected at the same with or after the heat development process. In the latter case, the transfer of a dye can be effected at a heating temperature ranging from the heat development temperature to room temperature, particularly preferably 50°C to a temperature about 10°C lower than the heat development temperature.
• the migration of a dye can be effected by heat alone.
• a solvent may be used.
• the system is preferably heated in the presence of a small amount of a solvent (particularly water) to simultaneously or continuously effect development and transfer.
• the heating temperature is preferably from 50°C to a temperature lower than the boiling point of the solvent, e.g., from 50°C to 100°C if the solvent is water.
• solvents for accelerating development and/or diffusing and transferring a dye to the dye fixing layer include water, and a basic aqueous solution containing an inorganic alkaline metal salt or organic base (these bases include those described with reference to the image formation accelerator). Further, a low boiling solvent, and a mixture of a low boiling solvent and water or the foregoing basic aqueous solution may be used. Moreover, a surface active agent, a fog inhibitor, a difficultly soluble metal salt, a complexing compound, a preservative, and a germicide, may be contained in these solvents.
• Water is preferably used as the solvent employable in the heat development and diffusion transfer processes.
• the water may be any commonly used water. Specific examples of the water include distilled water, tap water, well water, and mineral water.
• water may be used up or may be recycled. In the latter case, water exuding from the materials is reused. Further an apparatus and water as disclosed in JP-A-63-144354, JP-A-63-144355, JP-A-62-38460 and JP-A-3-210555 may be used.
• These solvents may be provided to either or both of the heat-developable light-sensitive material and the dye fixing element.
• the amount of these solvents to be used may be not more than the weight thereof corresponding to the maximum swellable volume of the coated film.
• JP-A-62-253159 page 5
• JP-A-63-85544 can be used for providing these solvents to the heat-developable light-sensitive layer or dye fixing layer.
• these solvents may be previously in either or both of the heat-developable light-sensitive material and the dye fixing element in the form of microcapsule or hydrate.
• the temperature of water to be provided to these photographic materials may be from 30°C to 60°C as disclosed in JP-A-63-85544.
• a hydrophilic heat solvent which stays solid at normal temperature but becomes soluble at an elevated temperature may be incorporated in the heat-developable light-sensitive material and/or dye fixing element for accelerating the migration of a dye.
• the layer in which the hydrophilic heat solvent is incorporated may be any of light-sensitive silver halide emulsion layer, interlayer, protective layer and dye fixing layer, preferably dye fixing layer and/or its adjacent layers.
• hydrophilic heat solvent examples include ureas, pyridines, amides, sulfonamides, imides, alcohols, oxims, and other heterocyclic groups.
• Examples of the heating means at the development and/or transfer process include method which comprises bringing the material into contact with a heated block or plate, a hot plate, a hot presser, heat roller, halogen lamp heater, infrared lamp heater, or far infrared lamp heater, and method which comprises passing the material through a high temperature atmosphere.
• a process described in JP-A-61-147244 (page 27) may be used as the process for the lamination of the heat-developable light-sensitive material and the dye-fixing element.
• the processing of the photographic elements of the present invention can be accomplished by means of any of various heat development apparatus.
• apparatus as described in JP-A-59-75247, JP-A-59-177547, JP-A-59-181353, JP-A-60-18951, JU-A-62-25944 (the term "JU-A” as used herein means a "published Japanese utility model application"), JP-A-6-95338 and JP-A-6-95267 may be preferably used.
• Examples of commercially available heat development apparatus for use in the present invention include Pictrostat 100, Pictrostat 200, Pictrography 3000, and Pictrography 2000 available from Fuji Photo Film Co., Ltd.
• the emulsion was then rinsed and desalted by an ordinary method (pH kept to 4.1 with a precipitant (a)).
• To the emulsion was then added 22g of lime-treated osein gelatin so that it was adjusted to pH 6.0 and pAg 7.9.
• the emulsion was then chemically sensitized at a temperature of 60°C with compounds set forth in Table 3.
• 630 g of a monodisperse emulsion of cubic silver bromochloride grains having a coefficient of variation of 10.2% and an average grain size of 0.20 ⁇ m was obtained.
• the emulsion was then rinsed and desalted by an ordinary method (pH kept to 3.9 with a precipitant (b)).
• To the emulsion was then added 22 g of lime-treated osein gelatin (calcium content: 150 ppm or less).
• the emulsion was then redispersed at a temperature of 40°C.
• To the emulsion was then added 0.39 g of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene so that it was adjusted to pH 5.9 and pAg 7.8.
• the emulsion was then chemically sensitized at a temperature of 70°C with compounds set forth in Table 6.
• sensitizing dyes (2) and (3) were added to the emulsion in the form of methanol solution (solution having the formulations set forth in Table 7).
• the emulsion was allowed to cool to a temperature of 40°C where 200 g of a gelatin dispersion of a stabilizer (1) described later was then added thereto.
• the emulsion was thoroughly stirred and then recovered.
• 938 g of a monodisperse emulsion of cubic silver bromochloride grains having a coefficient of variation of 12.6% and an average grain size of 0.25 ⁇ m was obtained.
• the emulsion was then rinsed and desalted by an ordinary method (pH kept to 3.8 with a precipitant (a)).
• To the emulsion was then added 22 g of lime-treated osein gelatin so that it was adjusted to pH 7.4 and pAg 7.8.
• the emulsion was then chemically sensitized at a temperature of 60°C with compounds set forth in Table 10. As a result, 680 g of a monodisperse emulsion of cubic silver bromochloride grains having a coefficient of variation of 9.7% and an average grain size of 0.32 ⁇ m was obtained.
• Gelatin dispersions of yellow dye-providing compound, magenta dye-providing compound and cyan dye-providing compound were prepared in accordance with the formulations set forth in Table 13. That is, various oil phase components were mixed at a temperature of about 70°C to make a uniform solution. To the solution was then added aqueous components which had been heated to a temperature of about 60°C. The mixture was stirred, and then subjected to dispersion at 10,000 rpm for 10 minutes. To the dispersion was then added water. The mixture was then stirred to obtain a uniform dispersion.
• the gelatin dispersion of cyan dye-providing compound was then repeatedly diluted and condensed with water by means of an ultrafiltration module (ultrafiltration module ACV-3050 available from Asahi Chemical Industry Co., Ltd.) so that the amount of ethyl acetate was reduced to 1/17.6 of the initial amount set forth in Table 13.
• an ultrafiltration module (ultrafiltration module ACV-3050 available from Asahi Chemical Industry Co., Ltd.) so that the amount of ethyl acetate was reduced to 1/17.6 of the initial amount set forth in Table 13.
• a gelatin dispersion of a reducing agent (2) was prepared in accordance with the formulations set forth in Table 14. In some detail, various oil phase components were mixed at a temperature of about 60°C to make a solution. To the solution were then added various phase components which had been heated to a temperature of about 60°C. The mixture was stirred, and then subjected to dispersion with a homogenizer at 10,000 rpm for 10 minutes to obtain a uniform dispersion. Ethyl acetate was removed from the dispersion by means of a vacuum organic solvent remover.
• a gelatin dispersion of a stabilizer (1) was prepared in accordance with the formulations set forth in Table 15. In some detail, various oil phase components were mixed at room temperature to make a solution. To the solution were then added aqueous components which had been heated to a temperature of about 40°C. The mixture was stirred, and then subjected to dispersion at 10,000 rpm by means of a homogenizer for 10 minutes. To the dispersion was then added water. The mixture was then stirred to obtain a uniform dispersion.
• a gelatin dispersion of zinc hydroxide was prepared in accordance with the formulations set forth in Table 16. In some detail, various components were mixed to make a solution. The solution was subjected to dispersion with glass beads having an average grain diameter of 0.75 mm by means of a mill for 30 minutes. The glass beads were then removed to obtain a uniform dispersion. (The zinc hydroxide grains used had an average grain size of 0.20 ⁇ m) TABLE 16 Composition of dispersion Zinc hydroxide 15.9 g Carboxymethyl cellulose 0.7 g Sodium polyacrylate 0.07 g Lime-treated gelatin 4.2 g Water 100 ml High boiling solvent (4) 0.4 g
• the preparation of the gelatin dispersion of matting agent to be incorporated in the protective layer will be described hereinafter. That is, a solution of PMMA in methylene chloride was added to gelatin with a small amount of a surface active agent. The mixture was then stirred at a high speed to effect dispersion. Methylene chloride was then removed by means of a vacuum solvent remover to obtain a uniform dispersion having an average grain size of 3.6 ⁇ m.
• Intrinsic viscosity [ ⁇ ] 1.6 (0.1 N NaCl, 30°C) Molecular weight ⁇ 1,000,000
• the light-sensitive material 101 was prepared in the same manner as in the light-sensitive material 100 except that the yellow dye-providing compound (1) to be contained in the yellow dispersion to be incorporated in the 1st layer was replaced by 9.9 g of a yellow dye-providing compound (2) having the following structural formula and 6.2 g of a development accelerator having the following structural formula was emulsion-dispersed in an oil phase of the yellow dispersion set forth in Table 13.
• An emulsion (1b) was prepared in the same manner as in the emulsion (1a) except that Solutions (I) to (IV) having the formulations set forth in Table 20 were added. As a result, 530 g of a monodisperse emulsion of silver bromochloride grains (Br content: 10 mol%) having an average grain size of 0.08 ⁇ m was obtained. TABLE 20 Solution (I) Solution (II) Solution (III) Solution (IV) AgNO3 50 g - 50 g - NaCl - 21 g - 21 g KBr - 3.5 g - 3.5 g Total amount (water to make) 100 ml 100 ml 100 ml 100 ml 100 ml 100 ml 100 ml 100 ml
• An emulsion (1c) was prepared in the same manner as in the emulsion (1a) except that Solutions (I) to (IV) having the formulations set forth in Table 21 were added. As a result, 530g of a monodisperse emulsion of silver bromochloride grains (Br content: 20 mol%) having an average grain size of 0.08 ⁇ m was obtained. TABLE 21 Solution (I) Solution (II) Solution (III) Solution (IV) AgNO3 50 g - 50 g - NaCl - 19 g - 19 g g KBr - 7 g - 7 g Total amount (water to make) 100 ml 100 ml 100 ml 100 ml 100 ml 100 ml 100 ml 100 ml
• An emulsion (1b) was prepared in the same manner as in the emulsion (1d) except that Solutions (I) to (IV) having the formulations set forth in Table 22 were added. As a result, 530 g of a monodisperse emulsion of silver bromochloride grains (Br content: 40 mol %) having an average grain size of 0.08 ⁇ m was obtained. TABLE 22 Solution (I) Solution (II) Solution (III) Solution (IV) AgNO3 50 g - 50 g - NaCl - 16 g - 16 g KBr - 14 g - 14 g Total amount (water to make) 100 ml 100 ml 100 ml 100 ml 100 ml 100 ml 100 ml 100 ml
• Emulsions (1e), (1f) and (1g) having an average grain size of 0.12 ⁇ m, 0.20 ⁇ m and 0.05 ⁇ m, respectively, were prepared in the same manner as in the emulsion (1a) except that the temperature of the aqueous solution set forth in Table 18 were 42°C, 50°C and 32°C, respectively. The yield of these emulsions were each 530 g.
• Light-sensitive materials 102 to 115 were prepared from these emulsions in the same manner as the light-sensitive material 100 except that alteration was made as set forth in Table 23.
• First layer Third layer Remarks Yellow dye-donating compound Additive Amount added (mg/m2) Additive Amount added (mg/m2) 100 (1) - - - - Comparison 101 (2) - - - - " 102 (2) Emulsion (1a) 40 - - Invention 103 (2) Emulsion (1a) 80 - - " 104 (2) Emulsion (1a) 10 - - " 105 (2) Emulsion (1b) 40 - - " 106 (2) Emulsion (1c) 40 - - " 107 (2) Emulsion (1d) 40 - - Comparison 108 (2) Emulsion (1e) 40 - - Invention 109 (2) Emulsion (1f) 40 - - " 110 (2) Emulsion (1g) 40 - - " 111 (1) Emulsion (1a) 40 -
• These light-sensitive materials 100 to 115 were each processed by a Type PG-3000 digital color printer Fujix Pictrography available from Fiji Photo Film Co., Ltd. with PG-SG for PG-3000 as a dye-fixing material to effect image output.
• a solid gray image was first outputted in an atmosphere of 25°C and 50%RH. The tint of the image was properly adjusted. Under the same exposure conditions, image output was effected in an atmosphere of 15°C and 50%RH and 30°C and 50%RH.
• the gray images obtained in these atmospheres were then measured for density by means of a Type X-rite 304 reflection densitometer available from X-rite Corp.
• a gray image having Y, M and C color reflection densities of 1.0 was outputted each on these photographic light-sensitive materials under standard image outputting conditions at 25°C and 50%RH under the conditions set forth in Table 25. Thereafter, the heat development temperature was changed to +5°C and -5°C. The other conditions were not changed. Under these conditions, a grain image was then outputted each on these photographic light-sensitive materials. The images thus obtained were each measured for change of color densities by means of a Type X-rite 304 reflection densitometer.
• the light-sensitive materials of the present invention exhibit a minimized image density change against the processing temperature change during the heat development and a minimized image color balance change against the change in environmental conditions (particularly temperature) during exposure, providing an image with an excellent discrimination between image area and non-image area.

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