Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
  • G03C8/40—Development by heat ; Photo-thermographic processes
  • G03C8/4013—Development by heat ; Photo-thermographic processes using photothermographic silver salt systems, e.g. dry silver
  • G03C8/4046—Non-photosensitive layers

Definitions

• the present invention relates to a heat-­developable color light-sensitive material and, in particular, to that which may form a color image having a high image density but a low stain and which has an excellent storage stability.
• the heat-developable light-sensitive materials to be used in said methods for forming color images are ones of a non-fixable type
• the silver halide would still remain in the material even after formation of images. Accordingly, such materials have a serious problem that the white portion in the material is gradually colored after it has been exposed to a strong light or has been stored for a long period of time.
• the known methods generally require a relatively long period of time for development, and these have an additional drawback that the image formed is noticeably fogged and has a low image density.
• the development temperature is still high and the storage stability of the light-sensitive material processed by the method could not be said to be sufficient.
• a method of heat-developing a light-sensitive material and transferring the dye formed in the presence of a base or base precursor and a slight amount of water whereby development is accelerated, the development temperature is lowered and the processing step is simplified, as illustrated in JP-A-59-218443 and JP-A-61-238056 and European Patent 210,660A2.
• U.S. Patent 4,559,290 has proposed a method where a compound of an oxidized form with no dye-releasing function, which has been derived from a so-called DRR compound, is used in the presence of a reducing agent or a precursor thereof, the said reducing agent is oxidized by heat development in accordance with the exposed amount of the silver halide, and the compound of oxidized form is reduced with the reducing agent which has not been oxidized by the heat development but has remained as it is so as to release a diffusible dye therefrom.
• European Patent 220,746A and Kokai Giho , 87-6199 Vol. 12, No.
• the aforesaid heat-developable color light-sensitive material has a problem of forming colored substances by decomposition or other side-reaction of the dye providing substance during photographic processing or by side-reaction of other components constituting the light-sensitive material during photographic processing thereby to give transferred stains in the white background portion and to worsen the S/N ratio.
• the light-sensitive material has another problem of having the above-mentioned unfavorable transferred stains when stored for a long period of time and therefore the storage stability of the light-­sensitive material is bad.
• the object of the present invention is to improve the S/N ratio and storage stability of a heat-­developable color light-sensitive material at least having a light-sensitive silver halide, a binder and a dye providing compound capable of releasing or forming a diffusible dye in correspondence or reverse correspondence with the reaction of reducing the silver halide into silver on a support.
• a heat-develop­able color light-sensitive material comprising a support having provided thereon a light-sensitive silver halide, a binder, and a dye providing compound capable of releasing or forming a diffusible dye in correspondence or reverse correspondence with the reaction of reducing the silver halide into silver, said light-sensitive material having a hydrophilic binder layer containing an adsorbent substance capable of adsorbing a color substance formed during the step of processing the light-sensitive material for forming an image therewith.
• any adsorbent can be employed regardless of the adsorbing type of physical adsorption or chemical adsorption, such as, for example, active charcoal, carbon black, cation or anion exchange resins, silica gel, aluminosilica gel, active alumina, etc. Specific examples of some of these adsorbents will be mentioned below.
• Active Charcoal This is defined in JIS K-1474­75 and has a physical adsorbing capacity. It is either powdery or granular. Manufacturers of the substance include Sanwa Carbon Co., Ltd., Tsurumi Coal Co., Ltd., Fujisawa Pharmaceutical Co., Ltd., Hokuetsu Carbon Co., Kuraray Co., Ltd., Takeda Chemical Industries, Ltd. and Wako Pure Chemical Industries, Ltd.
• Ion Exchange Resins As commercial products, there are Amberlite® IR-120B (Japan Organo Co., Ltd.) and Dowex® (Muromachi Chemicals Co.) as strong acidic cation exchange resins; Amberlite® IRC-50 and Diaion® WK10 as weak acidic cation exchange resins; Amberlite® IRA-401, Amberlite® IRA-410, Diaion® SA-11A, Diaion® SA-­20A, Dowex® I and Dowex® Z as strong basic anion exchange resins; and Amberlite® IR-4B, Amberlite® IR-­45, Diaion® WA20 and Dowex® 3 as weak basic anion exchange resins.
• Amberlite® IR-120B Japanese Organo Co., Ltd.
• Dowex® Moromachi Chemicals Co.
• the color substances to be formed in the light-sensitive material of the present invention is essentially a dissociating dye, anion exchange resins are preferred so as to adsorb the substance.
• aluminosilica gel and silica gel commercial products of Sumitomo Aluminium Co., Mizusawa Chemicals Co., Catalysts & Chemicals Industries Co., Ltd. and Wako Pure Chemical Industries, Ltd. can be employed.
• the adsorbent employed in the present invention may be in the form of an aqueous dispersion containing fine solid grains thereof (0.2 to 1 ⁇ m).
• mordant polymers which are known in U.S.
• Patent 4,500,626, JP-A-61-88256, JP-A-62-244036, JP-A-60-57836, JP-A-60-60643, JP-A-60-118834, JP-A-60-119557, JP-A-60-­122940, JP-A-60-122941, JP-A-60-122942, JP-A-61-46948 and JP-A-62-244043 can also be employed in the present invention.
• any method of adding the same to the light-sensitive layer or of adding to the interlayer or protective layer can be employed.
• one or more additional layers containing the adsorbent substance, other than the foregoing layers, may be provided in any desired position of the multilayer light-sensitive material of the present invention.
• an interlayer may be provided between the adsorbent substance containing layer and other layers.
• the adsorbent substance of the present invention is in a hydrophilic binder in the light-­sensitive material, it may efficiently adsorb any color substances which are unnecessary for forming images.
• the hydrophilic binder to be used for the purpose can be selected from hydrophilic colloids and biders which are known usable for light-sensitive materials and/or dye-­fixing materials and which will be mentioned in detail hereunder.
• the amount of the adsorbent substance to be incorporated into the light-sensitive material of the present invention is, though varying in accordance with the kind of the substance and the layer to which the substance is to be added and the amount and affinity of dye, generally from 1 mg to 2 g, especially from 10 mg to 500 mg, per m2 of the support.
• the heat-developable light-sensitive materials herein are essentially characterized in that light-­sensitive silver halides and a binder are provided on a support.
• the heat-developable light-­sensitive material optionally may comprise an organo­metallic salt oxidizing agent, a dye providing compound or the like. (As described later, a reducing agent may concurrently serve as a dye providing compound.)
• These components may be incorporated in the same layer but may be incorporated in separate layers if they are reactive with each other. For example, if a colored dye providing compound is present in an underlayer of a silver halide emulsion, it can inhibit a decrease in sensitivity.
• the reducing agent may be preferably incorporated in the heat-developable light-sensitive material. However, the reducing agent may be supplied from other elements. For example, the reducing agent may be diffused into the heat-developable light-­ sensitive material from a dye-fixing material as described later.
• At least three silver halide emulsion layers having sensitivity in different spectral regions may be used in combination.
• Examples of such a combination of silver halide emulsion layers include a combination of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer and a combination of a green-sensitive layer, a red-sensitive layer and an infrared-sensitive layer.
• These light-­sensitive layers may be arranged in various orders commonly used for ordinary color light-sensitive materials.
• These light-sensitive layers may be optionally divided into two or more layers.
• the heat-developable light-sensitive material may comprise various auxiliary layers such as a protective layer, subbing layer, interlayer, yellow filter layer, antihalation layer or backing layer.
• the silver halide which may be used in the present invention may be any of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide and silver chloroiodobromide.
• the silver halide emulsion used 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 a light fogging agent.
• the light-­sensitive silver halide emulsion may be a core/shell emulsion in which the interior and the surface of the grain are different from each other in phase.
• the light-sensitive silver halide emulsion may be a monodisperse or polydisperse emulsion or a mixture thereof.
• the grain size of the emulsion is preferably in the range of from 0.1 to 2 ⁇ m, particularly from 0.2 to 1.5 ⁇ m.
• the crystal habit of the silver halide grains may be cubic, octahedral, tetradecahedral or tabular with a high aspect ratio.
• silver halide emulsions as described in U.S. Patents 4,500,626 and 4,628,021, Research Disclosure , No. 17029 (1978), and JP-A-62-­253159 may be used in the present invention.
• the silver halide emulsion may be used unripened but is normally used after being chemically sensitized.
• known sulfur sensitization processes, reduction sensitization processes and noble metal sensitization processes may be used singly or in combination. These chemical sensitization processes may be optionally effected in the presence of a nitrogen-containing heterocyclic compound as disclosed in JP-A-62-253159.
• the amount of the light-sensitive silver halide emulsion coated is in the range of from 1 mg to 10 g/m2 (calculated in terms of amount of silver).
• organometallic salts may be used as oxidizing agents in combination with the light-sensitive silver halide.
• organo­metallic salts organic silver salts are particularly preferably used.
• organic compounds which can be used to form such an organic silver salt oxidizing agent include benzotriazoles, fatty acids, and other compounds as described in U.S. Patent 4,500,626 (52nd column to 53rd column).
• Other useful examples of such organic compounds include carboxylic acid silver salts containing an alkynyl group such as silver phenyl­propiolate as described in JP-A-60-113235, and silver acetylide as described in JP-A-61-249044. These organic silver salts may be used in combination.
• organic silver salts are generally used in an amount of from 0.01 to 10 mols, preferably from 0.01 to 1 mol, per mol of light-sensitive silver halide.
• the total amount of light-sensitive silver salt and organic silver salt coated is preferably in the range of from 50 mg to 10 g/m2 (calculated in terms of amount of silver).
• fog inhibitors or photographic stabilizers may be used.
• fog inhibitors or photographic stabilizers include azoles or azaindenes as described in Research Disclosure , No. 17643 (1978), pp. 24-25, nitrogen-­containing carboxylic acids or phosphoric acids as described in JP-A-59-168442, mercapto compounds and metal salts thereof as described in JP-A-59-111636, and acetylenic compounds as described in JP-A-62-87957.
• the light-sensitive silver halide used in the present invention may be conventionally spectrally sensitized with a methine dye or the like.
• dyes include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.
• dyes include sensitizing dyes as described in U.S. Patent 4,617,257, JP-A-59-­180550, JP-A-60-140335, and Research Disclosure , No. 17029 (1978), pp. 12-13.
• sensitizing dyes may be used singly or in combination.
• combinations of sensitizing dyes are often used for the purpose of supersensitiza­tion.
• the light-sensitive silver halide emulsion may comprise a dye which does not exhibit a spectral sensitizing effect by itself or a compound which does not substantially absorb visible light but exhibits a supersensitizing effect (as described in U.S. Patent 3,615,641 and JP-A-63-23145) together with such a sensitizing dye.
• sensitizing dyes may be incorporated in the emulsion during, before or after chemical sensitization.
• the sensitizing dye may be incorporated in the emulsion before or after the nucleation of light-­sensitive silver halide grains as described in U.S. Patents 4,183,756 and 4,225,666.
• the amount of sensitizing dye incorporated is normally in the range of from 10 ⁇ 8 to 10 ⁇ 2 mol per mol of light-sensitive silver halide.
• hydrophilic binder As suitable binders incorporated in the light-­sensitive material or dye-fixing material there may be used a hydrophilic binder.
• hydrophilic binders include those described in JP-A-62-253159 (pp. 26-28).
• specific examples of such hydrophilic binder include transparent or semi-transparent hydrophilic binders such as proteins (e.g., gelatin, gelatin derivative), polysaccharides (e.g., cellulose deriva­tives, starch, gum arabic, dextran, pullulan), and synthetic high molecular compounds (e.g., polyvinyl alcohol, polyvinylpyrrolidone, acrylamide polymers).
• a high water-absorbing polymer as described in JP-A-62-245260 i.e., a homopolymer of a vinyl monomer containing -COOM or -SO3M (wherein M represents a hydrogen atom or alkali metal) or a copolymer of such vinyl monomers or such a vinyl monomer with other vinyl monomers (e.g., sodium methacrylate, ammonium methacrylate, SUMIKAGEL® L-5H made by Sumitomo Chemical Co., Ltd.) may be used. These binders may be used singly or in combination.
• the above described high water-absorbing polymer may be used to expedite the absorption of water.
• a high water-absorbing polymer may be incorporated in the dye fixing layer or in a protective layer therefor to prevent dye which has been transferred from being re-transferred from the dye-­fixing material to other elements.
• the amount of the binder coated is preferably in the range of 20 g or less, more preferably 10 g or less, particularly 7 g or less per m2.
• the layers (including backing layer) consti­tuting the light-sensitive material or dye-fixing material of the present invention can contain various polymer latexes for the purpose of improving the film property of the material, for example, for the purpose of dimensional stabilization, curling prevention, blocking prevention, film cracking prevention and prevention of pressure sensitization and desensitization pressure marks).
• polymer latexes described in JP-A-62-245258, JP-A-62-136648 and JP-A-62-110066 can be employed for the purpose.
• reducing agents for the present invention there may be used conventional reducing agents known in the field of heat-developable light-sensitive materials.
• reducing dye providing compounds as described later may be used. These reducing dye providing compounds may be used in combination with other reducing agents.
• a reducing agent precursor which does not exhibit a reducing effect but undergoes reaction with a nucleophilic reagent or under heating to exhibit a reducing effect may be used in the present invention.
• reducing agents used in the present invention include reducing agents or reducing agent precursors as described in U.S. Patents 4,500,626 (49th column to 50th column), 4,483,914 (30th column to 31st column), 4,330,617, and 4,590,152, JP-A-60-140335, JP-A-­57-40245, JP-A-56-138736, JP-A-59-178458, JP-A-59-53831, JP-A-59-182449, JP-A-59-182450, JP-A-60-119555, JP-A-60-­128436, JP-A-60-128437, JP-A-60-128438, JP-A-60-128439, JP-60-198540, JP-A-60-181742, JP-A-61-259253, JP-A-62-­244044, JP-A-62-131253, JP-A-62-131254, JP-A-62-131255, and JP-A-
• an electron transfer agent and/or electron transfer agent precursor may optionally be used in combination therewith in order to accelerate the transfer of electrons between the non-diffusible reducing agent and the developable silver halide.
• Such an electron transfer agent or its precursor may be selected from the above described reducing agents or precursors thereof.
• Such an electron transfer agent or its precursor is preferably greater than the non-­diffusible reducing agent (electron donor) in mobility.
• Particularly useful electron transfer agents are 1-­phenyl-3-pyrazolidones or aminophenols.
• non-diffusible reducing agents used in combination with such an electron transfer agent there may be used any of the above described reducing agents which are substantially non-­diffusible in the layer of light-sensitive material in which they are located.
• Preferred examples of such non-­diffusible reducing agents include hydroquinones, sulfonamidophenols, sulfonamidonaphthols, compounds described as electron donors in JP-A-53-110827, and non-­diffusible reducing dye providing compounds as later described.
• the amount of such reducing agent(s) incorporated is preferably in the range of from 0.01 to 20 mols, particularly from 0.1 to 10 mols per mol of silver.
• silver may be used as an image-forming substance.
• a compound which produces or releases a mobile dye in correspondence or counter correspondence to the reduction of silver ions to silver at elevated temperature, i.e., dye providing compounds, may be incorporated in the light-sensitive material.
• Examples of such dye providing compounds which may be used in the present invention include compounds which undergo an oxidation coupling reaction with a color developing agent to form a dye (coupler).
• a coupler may be a two-equivalent coupler or four-­equivalent coupler.
• a two-equivalent coupler containing a non-diffusible group as a split-off group which undergoes oxidation coupling reaction to form a diffusible dye is preferably used.
• suitable developing agents and couplers are described in T.H. James, The Theory of the Photographic Process , pp.
• Examples of different dye providing compounds include compounds which serves to imagewise release or diffuse a diffusible dye.
• Such a compound can be repre­sented by the following general formula (LI): (Dye-Y) n -Z (LI) wherein Dye represents a dye group, a dye group which has been temporarily shifted to a short wavelength range or a dye precursor group; Y represents a mere bond or connecting group; Z represents a group which makes a difference in the diffusibility of the compound repre­sented by (Dye-Y) n -Z in corresponding or counter-­corresponding to light-sensitive silver salts having a latent image distributed imagewise or releases Dye in corresponding or counter-corresponding to light-­sensitive silver salts having a latent image distributed imagewise to make no difference in the diffusibility between Dye thus released and (Dye-Y) n -Z; and n represents an integer of 1 or 2. If n is 2, two (Dye-­Y)'s may be the same or different
• the dye providing compound represented by the general formula (LI) include the following compounds i to v.
• the compounds i to iii form a diffusible dye image (positive dye image) in counter-­corresponding to the development of silver halide while the compounds iv and v form a diffusible dye image (negative dye image) in corresponding to the development of silver halide.
• Dye developing agents comprising a hydro­quinone developing agent connected to a dye component as described in U.S. Patents 3,134,764, 3,362,819, 3,597,200 3,544,545, and 3,482,972. These dye develop­ing agents are diffusible in alkaline conditions but become non-diffusible upon reaction with silver halide.
• Non-diffusible compounds which release a diffusible dye in alkaline conditions but lose their function upon reaction with silver halide as described in U.S. Patent 4,503,137.
• Examples of such compounds include compounds which undergo intramolecular nucleo­philic displacement reactions to release a diffusible dye as described in U.S. Patent 3,980,479, and compounds which undergo an intramolecular rewinding reaction of the isooxazolone ring to release a diffusible dye as described in U.S. Patent 4,199,354.
• Non-diffusible compounds that react with a reducing agent left unoxidized after being developed to release a diffusible dye as described in U.S. Patent 4,559,290, European Patent 220,746A2, and Kokai Giho , 87-6,199.
• Examples of such compounds include compounds which undergo intramolecular nucleophilic displacement reaction after being reduced to release a diffusible dye as described in U.S. Patents 4,139,389 and 4,139,379, and JP-A-59-185333, and JP-A-57-84453, compounds which undergo an intramolecular electron transfer reaction after being reduced to release a diffusible dye as described in U.S. Patent 4,232,107, JP-A-59-101649, JP-­A-61-88257, and Research Disclosure , No. 24,025 (1984), compounds which undergo cleavage of a single bond after being reduced to release a diffusible dye as described in West German Patent 3,008,588A, JP-A-56-142530, and U.S.
• Patents 4,343,893, and 4,619,884 nitro compounds which receive electrons to release a diffusible dye as described in U.S. Patent 4,450,223, and compounds which receive electrons to release a diffusible dye as described in U.S. Patent 4,609,610.
• Preferred examples of such compounds include compounds containing an N-X bond (wherein X represents oxygen atom, sulfur atom or nitrogen atom) and an electrophilic group in one molecule as described in European Patent 220,746A2, Kokai Giho , 87-6,199, JP-A-­63-201653, and JP-63-201654, compounds containing an SO2-X group (wherein X is as defined above) and an electrophilic group in one molecule as described in U.S.
• Particularly preferred among these compounds are compounds containing an N-X bond and an electrophilic group in one molecule.
• Specific examples of such compounds include Compounds (1) to (3), (7) to (10), (12), (13), (15), (23) to (26), (31), (32), (35), (36), (40), (41), (44), (53) to (59), (64), and (70) described in European Patent 220,746A2, and Compounds (11) to (23) described in Kokai Giho , 87-6,199.
• Couplers containing a diffusible dye as the split-off group which reacts with an oxidation product of a reducing agent to release a diffusible dye include those described in British Patent 1,330,524, JP-B-48-­39165, and U.S. Patents 3,443,940, 4,474,867, and 4,483,914.
• DDR compound Compounds which are capable of reducing silver halide or organic silver salts and release a diffusible dye after reducing silver halide or organic silver salts (DDR compound). These compounds are advantageous in that they need no other reducing agents. They eliminate image staining due to the action of oxidation decomposition products of reducing agents. Typical examples of such compounds are described in U.S.
• DRR compounds include compounds as described in U.S.
• Patent 4,500,626, 22nd column to 44th column and particularly preferred among these compounds are compounds (1) to (3), (10) to (13), 16) to (19), (28) to (30), (33) to (35), (38) to (40), and (42) to (64).
• Other preferred examples of such compounds include those described in U.S. Patent 4,639,408, 37th column to 39th column.
• dye providing compounds other than the above described couplers and compounds of the general formula [LI] include silver dye compounds comprising an organic silver salt connected to a dye as described in Research Disclosure (May 1978, pp. 54-58), azo dyes for use in heat developable silver dye bleaching processes as described in U.S. Patent 4,235,957 and Research Disclosure (April 1976, pp. 30-­32), and leuco dyes as described in U.S. Patents 3,985,565 and 4,022,617.
• a hydrophobic additive such as a dye providing compound or a non-diffusible reducing agent in a layer of light-sensitive material
• a hydrophobic additive such as a dye providing compound or a non-diffusible reducing agent
• a high boiling organic solvent as described in JP-A-59-83154, JP-A-59-178451, JP-A-59-178452, JP-A-59-178453, JP-A-59-178454, JP-A-59-­178455, and JP-A-59-178457 may optionally be used in combination with a low boiling organic solvent having a boiling point of from 50 to 160°C.
• the amount of such a high boiling organic solvent incorporated is generally in the range of from 1 to 10 g, preferably 5 g or less, per gram of dye providing compound used or 1 cc or less, preferably 0.5 cc or less, particularly preferably 0.3 cc or less, per gram of binder.
• JP-B-51-­39853 A dispersion process as described in JP-B-51-­39853 (the term "JP-B” as used herein means an "examined Japanese Patent Publication") and JP-A-51-­59943 which comprises using a polymerization product may also be used.
• a compound which is substantially insoluble in water it may be incorporated in the binder in the form of dispersion of finely divided particles rather than by the above described processes.
• various surface active agents can be used.
• examples of such surface active agents which may be used in this dispersion process include those described as surface active agent in JP-A-59-157636 (pp. 37-38).
• a compound which serves both to accelerate the development of light-­sensitive materials and stabilize images may be used.
• Specific examples of such compounds preferably used in the present invention are described in U.S. Patent 4,500,626 (51st column to 52nd column).
• a dye-fixing material is used in combination with the light-sensitive material.
• a dye-fixing material may be either coated on a separate support from the light-sensitive material or coated on the same support as the light-sensitive material.
• the support and a white reflecting layer which can be used, those described in U.S. Patent 4,500,626 (57th column) are useful.
• the dye-fixing material preferably used in the present invention may comprise at least one layer containing a mordant and a binder.
• mordants there may be used those known in the field of photography. Specific examples of such mordants include those described in U.S. Patent 4,500,626 (58th column to 59th column), JP-A-61-88256 (pp. 32-41), JP-A-62-244043 and JP-A-62-244036.
• a dye-receiving high molecular weight compound as described in U.S. Patent 4,463,079 may be used.
• the dye-fixing material may optionally comprise auxiliary layers such as a protective layer, strippable layer or anti-curling layer.
• auxiliary layers such as a protective layer, strippable layer or anti-curling layer.
• a protective layer can be advantageously incorporated in the dye-­fixing material.
• the constituent layers of the light-sensitive material or dye-fixing material may comprise a high boiling organic solvent as a plasticizer, lubricant or agent for improving the strippability of the light-­sensitive material from the dye-fixing material.
• a high boiling organic solvent include those described in JP-A-62-253159 (page 25) and JP-A-62-245253.
• various silicone oils ranging from dimethyl silicone oil to modified silicone oil obtained by incorporating various organic groups into dimethylcycloxane may be used.
• various modified silicone oils particularly carboxy-modified silicone (trade name: X-22-3710), described at pp. 6-8 of "Modified Silicone Oil", technical data reported by Shin-Etsu Silicone Co., Ltd., may be effectively used.
• Silicone oils as described in JP-A-62-215953 and JP-A-63-46449 may also be effectively used.
• the light-sensitive material or dye-fixing material may comprise a discoloration inhibitor.
• a discoloration inhibitor there may be used an antioxidant, ultraviolet absorber or certain kinds of metal complexes.
• antioxidants examples include chroman compounds, coumaran compounds, phenol compounds (e.g., hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds.
• Other useful antioxidants include compounds as described in JP-A-61-159644.
• suitable ultraviolet absorbers include benzotriazole compounds as described in U.S. Patent 3,533,794, 4-thiazolidone compounds as described in U.S. Patent 3,352,681, benzophenone compounds as described in JP-A-46-2784, and compounds as described in JP-A-54-48535, JP-A-62-136641, and JP-A-61-8256.
• Other useful ultraviolet absorbers include ultraviolet-­absorbing polymers as described in JP-A-62-260152.
• suitable metal complexes include compounds as described in U.S. Patents 4,241,155, 4,245,018, (3rd column to 36th column), and 4,254,195 (3rd column to 8th column), JP-A-62-174741, JP-A-61-­88256 (pp. 27-29), and JP-A-63-199248.
• a discoloration inhibitor for inhibiting discoloration of a dye to be transferred to the dye-­fixing material may be previously incorporated in the dye-fixing material or supplied into the dye-fixing material from other elements such as light-sensitive material.
• antioxidants ultraviolet absorbers and metal complexes may be used in combination.
• the light-sensitive material or dye-fixing material may comprise a fluorescent brightening agent.
• a fluorescent brightening agent may be incorporated in the dye-fixing material or supplied into the dye-fixing material from other materials such as light-sensitive material.
• fluorescent brightening agents include compounds as described in K. Veenkataraman, The Chemistry of Synthetic Dyes , Vol. V, Chapter 8, and JP-A-61-143752. Specific examples of such compounds include stilbene compounds, coumarin compounds, biphenyl compounds, benzoxazolyl compounds, naphthalimide compounds, pyrazoline compounds, and carbostyryl carboxy compounds.
• Such a fluorescent brightening agent may be used in combination with a discoloration inhibitor.
• film hardening agents which may be incoroporated in the light-sensitive material or dye-­fixing material include those described in U.S. Patent 4,678,739 (41st column), JP-A-59-116655, JP-A-62-245261, and JP-A-61-18942.
• film hardening agents include aldehyde film hardening agents (e.g., formaldehyde), aziridene film hardening agents, epoxy film hardening agents (e.g., vinylsulfone film hardening agents (e.g., N,N′-ethylenebis(vinylsulfonylacetamido)ethane), N-­methylol film hardening agents (e.g., dimethylol urea), and high molecular film hardening agents (e.g., compounds as described in JP-A-62-234157).
• aldehyde film hardening agents e.g., formaldehyde
• aziridene film hardening agents e.g., epoxy film hardening agents (e.g., vinylsulfone film hardening agents (e.g., N,N′-ethylenebis(vinylsulfonylacetamido)ethane), N-­methylol film hardening agents (e.
• the constituent layers of the light-sensitive material or dye-fixing material may comprise various surface active agents for the purpose of aiding of coating, improving strippability and lubricity, inhibit­ ing static electrification or accelerating development. Specific examples of such surface active agents are described in JP-A-62-173463 and JP-A-62-183457.
• the constituent layers of the light-sensitive material or dye-fixing material may comprise an organo­fluoro compound for the purpose of improving lubricity and strippability or inhibiting static electrification.
• organofluoro compound include fluorine surface active agents as described in JP-B-57-9053 (8th column to 17th column), JP-A-61-20944, and JP-A-62-135826, and hydrophobic fluorine compounds such as oily fluorine compounds (e.g., fluorine oil) or solid fluorine compound resins (e.g., tetrafluoro­ethylene resin).
• the light-sensitive material or dye-fixing material may comprise a matting agent.
• a matting agent examples include compounds as described in JP-A-­61-88256 (pp. 29) (e.g., silicon dioxide, polyolefin, polymethacrylate) and compounds as described in JP-A-63-­279944 and JP-A-63-274952 (e.g., benzoguanamine resin beads, polycarbonate resin beads, AS resin beads).
• constituent layers of the light-sensitive material or dye-fixing material may comprise a thermal solvent, an anti-foaming agent, an anti-bacterial and anti-fungal agent or colloidal silica. Specific examples of these additives are described in JP-A-61-88256 (pp. 26-32).
• the light-sensitive material and/or dye-fixing material may include an image formation accelerator.
• an image formation accelerator serves to accelerate a redox reaction between a silver salt oxidizing agent and a reducing agent, accelerate production or decomposition of a dye from a dye providing compound or release of a diffusible dye from the dye providing compound, or accelerate transfer of a dye from a light-sensitive material layer to a dye fixing layer.
• image formation accelerators can be classified into various groups such as base or base precursor, nucleophilic compound, high boiling organic solvent (oil), thermal solvent, surface active agent, and compounds capable of interacting with silver or silver ion. However, these groups normally have composite functions and therefore exhibit a combination of the above described accelerating effects. Details are given in U.S. Patent 4,678,739 (38th column to 40th column).
• base precursors examples include salts of an organic acid capable of being heat-decarboxylated with a base, and compounds which undergo an intramolecular nucleophilic displacement reaction, Lossen rearrangement or Beckman rearrangement to release an amine. Specific examples of such base precursors are described in U.S. Patent 4,511,493 and JP-A-62-65038.
• such a base and/base precursor may be preferably incorporated in the dye-fixing material to improve the storage stability of the light-­sensitive material.
• Suitable base precursors include a combination of a sparingly soluble metallic compound and a compound capable of complexing with metal ions constituting said metallic compound as described in European Patent 210,660A, and a compound as described in JP-A-61-232451 which undergoes electrolysis to produce a base.
• the former compound may be effect­ively used.
• the sparingly soluble metallic compound and the complexing compound may advantageously be incorporated separately in the light-sensitive material and the dye-fixing material.
• the present light-sensitive material and/or dye-­fixing material may comprise various development stopping agents for the purpose of providing images resistant against fluctuations in temperature and time for development.
• development stopping agent means a compound which readily neutralizes or reacts with a base to reduce the base concentration in the film to stopping development, or which interacts with silver or silver salt to inhibit development, after a proper development period.
• Specific examples of such compounds include acid precursors which release an acid on heating, electrophilic compounds which undergo a displacement reaction with a base present therewith on heating, and nitrogen-containing heterocyclic compounds, mercapto compounds and precursors thereof.
• a suitable support for the light-sensitive material or dye-fixing material of the present invention there may be used a material capable of withstanding the processing temperature.
• paper or a synthetic high molecular weight compound (film) may be used.
• Specific examples of such a support material which may be used in the present invention include polyethylene terephthalate, polycarbonates, polyvinyl chloride, polystyrene, polypropylene, polyimides or celluloses (e.g., triacetyl cellulose) or a material obtained by incorporating a pigment such as titanium oxide in such a film, a synthetic paper film formed of polypropylene or the like, a mixed paper made of synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, baryta paper, coated paper (particularly cast coat paper), metals, fabrics, and glass.
• Such a support material may be used as it is or in the form of a material laminated with a synthetic high molecular weight compound such as polyethylene on one or both sides thereof.
• a support material as described in JP-A-62-253159 (pp. 29-31) may be used in the present invention.
• These support materials may be coated with a hydrophilic binder, a semiconducting metal oxide such as alumina sol or tin oxide, carbon black or other antistatic agents.
• Examples of process for exposing the light-­sensitive material to light for imaging include processes which comprise using a camera to photograph scenery or persons, processes which comprise using a printer or enlarger to expose the light-sensitive material to light through a reversal film or negative film, processes which comprise using an exposing machine such as a copying machine to effect scanning exposure of the light-sensitive material to an original through a slit, processes which comprise exposing the light-­sensitive material to light representative of image data emitted by a light emitting diode or various lasers, and processes which comprise exposing the light-sensitive material directly or through an optical system to light representative of image data emitted by an image display apparatus such as a CRT, liquid crystal display, electroluminescence display or plasma display.
• an image display apparatus such as a CRT, liquid crystal display, electroluminescence display or plasma display.
• a light source for recording images on the light-sensitive material there may be used natural light, tungsten lamp, a light emitting diode, a laser, a CRT or light sources as described in U.S. Patent 4,500,626 (56th column).
• a wavelength converting element comprising a combination of a non-lienar optical material and a coherent light source such as laser rays can also be used for image exposure.
• non-linear optical material as used herein means a material capable of expressing non-linear property between the polarization to be caued by some strong photoelectric field such as laser rays and the electric field.
• inorganic compounds such as lithium niobate, potassium dihydrogenphosphate (KDP), lithium iodate and BaB2O4, as well as urea derivatives, nitroaniline derivatives, nitropyridine-N-oxide deriv­atives (e.g., 3-methyl-4-nitropyridine-N-oxide (POM) and the compounds described in JP-A-61-54362 and JP-A-62-­210432 are preferably employed in the present invention.
• KDP potassium dihydrogenphosphate
• Li iodate lithium iodate
• BaB2O4 lithium niobate
• urea derivatives such as lithium niobate, potassium dihydrogenphosphate (KDP), lithium iodate and BaB2O4
• urea derivatives such as lithium niobate, potassium dihydrogenphosphate (KDP), lithium iodate and BaB2O4
• urea derivatives such as lithium niobate, potassium dihydr
• NTSC Nippon Television Signal Code
• the light-sensitive material and/or the dye-­fixing material may be in a form that has an electroconductive heating element layer as the heating means for heat development and diffusion and transfer of the formed dyes.
• the heating element may be either transparent or opaque, and the elements described in JP-A-61-145544 can be employed.
• the electroconductive layer acts also as an antistatic layer.
• the heating temperature at which heat develop­ment can be effected is preferably in the range of from about 50°C to about 250°C, particularly from about 80°C to about 180°C.
• the dye diffusion transfer process may be effected simultaneously with or after heat develop­ment.
• the heating temperature at which dye transfer can be effected is preferably in the range of from the heating temperature for heat development to room temperature, particularly from 50°C to a temperature about 10°C lower than the heating temperature for heat development.
• the transfer of a dye can be effected by heating alone.
• a solvent may be used.
• a process as described in JP-A-­59-218443 and JP-A-61-238056 which comprises heating the light-sensitive material in the presence of a small amount of a solvent, particularly water, to effect development and dye transfer simultaneously or in sequence may be effectively used.
• the heating temperature for this process is preferably in the range of from 50°C to a temperature not higher than the boiling point of the solvent.
• the solvent is water
• the heating temperature is preferably in the range of from 50°C to 100°C.
• Examples of a solvent which may be used to accelerate development and/or transfer of a diffusible dye to the dye-fixing layer include water and a basic aqueous solution containing an inorganic alkali metal salt or organic base as described with reference to the image formation accelerators.
• Other useful examples of solvents include a low boiling solvent and a mixed solution made of such a low boiling solvent and water or a basic aqueous solution.
• Such a solvent may further comprise a surface active agent, fog inhibitor, sparingly soluble metal salt, complexing compound or the like.
• solvents may be incorporated in either or both of the light-sensitive material and the dye-fixing material.
• the amount of the solvent incorporated in the light-sensitive material and/or dye-fixing material may be small such as not more than the weight of the solvent in a volume corresponding to the maximum swelling volume of the total coated films (particularly, not more than the value obtained by subtracting the weight of the entire coated film(s) from the weight of the solvent in a volume corresponding to the maximum swelling volume of the entire coated film(s)) in the light-sensitive or dye-fixing solvent.
• the solvent may be incorporated in either or both of the light-sensitive material and the dye-­fixing material in a microcapsule form or like form.
• a hydrophilic thermal solvent which stays solid at normal temperature but dissolves at an elevated temperature may be incorporated in the light-sensitive material or dye-­fixing material.
• a hydrophilic thermal solvent may be incorporated in either or both of the light-sensitive material and the dye-fixing material.
• the layer in which the solvent is incorporated may be any one of emulsion layer, interlayer, protective layer and dye fixing layer, preferably the dye-fixing layer and/or a layer adjacent thereto.
• hydrophilic thermal solvent examples include ureas, pyridines, amides, sulfonamides, imides, anisoles, oximes and other heterocyclic compounds.
• a high boiling organic solvent may be incorporated in the light-sensitive material and/or dye-fixing material.
• heating processes at development and/or the dye transfer step include processes which comprise bringing the light-sensitive material into contact with a heated block or plate, processes which comprise bringing the light-sensitive material into contact with a heating plate, hot presser, heat roller, halogen lamp heater, infrared or far infrared lamp heater or the like, and processes which comprises passing the light-sensitive material through a high temperature atmosphere.
• the light-­sensitive material or dye-fixing material may be provided with a resistive heating element layer so that it is heated by passing an electric current through the resistive heating element layer.
• a resistive heating element layer there may be used the one described in JP-A-61-145544.
• any suitable heat developing apparatus may be employed.
• Examples of such a heat developing apparatus preferably used in the present invention include those described in JP-A-59-75247, JP-A-59-177547, JP-A-59-­181353, JP-A-60-18951, and JP-A-U-62-25944 (the term "JP-A-U” as used herein means an "unexamined published Japanese utility model application").
• Emulsion (I) for the first layer was prepared as mentioned below.
• Solution (I), Solution (II) and Solution (III) were simultaneously added to a well stirred aqueous gelatin solution (prepared by adding 20 g of gelatin, 1 g of potassium bromide and 0.5 g OH(CH2)2S(CH2)2OH to 800 ml of water and heated at 50°C) all at the same flow rate over a period of 30 minutes. Accordingly, a dye-adsorbed monodispersed silver bromide emulsion having a mean grain size of 0.42 ⁇ was prepared.
• Emulsion (II) for the third layer was prepared as mentioned below.
• Solution (I) and Solution (II) were simultaneously added to a well stirred aqueous gelatin solution (prepared by adding 20 mg of gelatin, 0.30 g of potassium bromide, 6 g sodium chloride and 0.015 g of the following Compound (A) to 730 ml of water and heated at 60.0°C) all at the same flow rate over a period of 60 minutes.
• aqueous gelatin solution prepared by adding 20 mg of gelatin, 0.30 g of potassium bromide, 6 g sodium chloride and 0.015 g of the following Compound (A) to 730 ml of water and heated at 60.0°C) all at the same flow rate over a period of 60 minutes.
• Solution (III) methanol solution containing Sensitizing Dye (c)
• Emulsion (III) for the fifth layer was prepared as mentioned below.
• Solution (I) and Solution (II) were simultaneously added to a well stirred aqueous gelatin solution (prepared by adding 30 g of gelatin, 3 g of potassium bromide and 0.5 g of HO(CH2)2S(CH2)2S­(CH2)2OH to 600 ml of water and heating at 65°C) over a period of 20 minutes.
• aqueous gelatin solution prepared by adding 30 g of gelatin, 3 g of potassium bromide and 0.5 g of HO(CH2)2S(CH2)2S­(CH2)2OH to 600 ml of water and heating at 65°C
• Solution (III) and Solution (IV) were simultaneously added thereto over a period of 30 minutes.
• 20 g of lime-processed ossein gelatin was added and the resulting emulsion was adjusted to a pH of 6.2 and pAg of 8.5.
• the dye providing substance-containing gelatin dispersion was prepared as follows:
• a magenta dye providing substance dispersion and a cyan dye providing substance dispersion were also prepared in the same manner as the yellow dye providing substance dispersion, but using Magenta Dye Providing Substance (2)* and Cyan Dye Providing Substance (3)*, respectively.
• a multilayer color light-sensitive material (Sample No. 101) having the layers mentioned below was prepared.
• Sixth Layer Protective Layer Gelatin 0.92 (g/m2 - the same shall apply hereunder) Zn(OH2) 0.46 Matting Agent (Silica) 0.03 Water-soluble Polymer (1)* 0.02 Surfactant (1)* 0.06 Surfactant (2)* 0.13 Hardening Agent (1)* 0.01
• Fifth Layer Blue-sensitive Emulsion Layer Emulsion (III) 0.35 as Ag Gelatin 0.48 Sensitizing Dye (d) 2.50 ⁇ 10 ⁇ 3 Antifoggant (1)* 5.00 ⁇ 10 ⁇ 4 Yellow Dye Providing Substance (1) 0.41 High Boiling Point Organic Solvent (1)* 0.21 Electron Donor (1)* 0.28 Surfactant (3)* 0.05 Electron Transfer Agent (1)* 0.04 Hardening Agent (1)* 0.004 Water-soluble Polymer (1)* 0.01
• Fourth Layer Interlayer Gelatin 0.70 Surfactant (1)* 0.02 Surfactant (3)*
• Heat-developable light-sensitive materials (Sample Nos. 102 to 106) were prepared in the same manner as Sample No. 101, except that each of the following layers (A) to (E) was provided between the first layer and the support.
• Layer (A) for Sample No. 102 Gelatin 0.2 (g/m2 - the same shall apply hereunder)
• sample Nos. 107 to 112 heat-developable color light-sensitive material (Sample Nos. 107 to 112) were prepared also in the same manner as Sample No. 101, except that the 2nd, 4th and 6th layers were changed to those mentioned in Table 1 below.
• Active Charcoal (1)* Active Charcoal manufactured by Wako Pure Chemical Industries, Ltd. (powder) Anion Exchange Resin (1)*: Diaion® SA-11A Alumina Gel (1)*: Neutral Active Alumina (manufactured by Wako Pure Chemical Industries, Ltd.: WOELM®)
• Example 1 The active charcoal, anion exchange resin and alumina gel used in Example 1, which were in the form of a solid powder, were formed into the gelatin dispersion, as mentioned below, and added to the corresponding layers.
• Dye-Fixing Material Sample (R-1). Constitution of Dye-Fixing Material (R-1): Third Layer : Gelatin 0.05 (g/m2 - the same shall apply hereunder) Matting Agent (Silica) 0.02 Silicone Oil (*1) 0.04 Surfactant (*2) 0.001 Surfactant (*3) 0.02 Surfactant (*4) 0.10 Guanidine Picolinate 0.45 Polymer (*5) 0.24 Second Layer : Mordant (*6) 2.35 Polymer (*7) 0.60 Gelatin 1.40 Polymer (*5) 0.21 High Boiling Point Organic Solvent (*8) 1.40 Guanidine Picolinate 1.80 Surfactant (*2) 0.02 First Layer : Gelatin 0.45 Surfactant (*4) 0.01 Polymer (*5) 0.04 Hardening Agent (*9) 0.30
• First Backing Layer Gelatin 3.25 Hardening Agent (*9) 0.25 Second Backing Layer : Gelatin 0.44 Silicone Oil (*1) 0.08 Surfactant (*5) 0.002 Matting Agent (*10) 0.09
• the multilayer color light-sensitive material samples prepared above were exposed with a tungusten lamp of 5000 luxes through a B-G-R-gray color separation filter having a gradually varying color density.
• the thus exposed samples were conveyed at linear velocity of 20 mm/sec and water was applied to the emulsion surface in an amount of 15 ml/m2 with a wire bar, and immediately thereafter, they were attached to the image-receiving material sample with the coated obverse surfaces facing to each other.
• Each combined sample was heated with a heat roller whose temperature was so adjusted that the temperature of the water-absorbed surface could be 85°C, for 15 seconds.
• the image-receiving material was peeled off, and a sharp and gradually varying image having blue, green, red and gray colors in corres­pondence to the B-G-R-gray color separation filter used was formed on the image-receiving material.
• light-sensitive material sample Nos. 103 to 112 of the present invention formed images with lower Dmin and thus less stain than light-sensitive material sample Nos. 101 and 102.
• the organic silver salt emulsion was prepared as follows: 20 g of gelatin and 5.9 g of 4-acetylamino­phenylpropiolic acid were dissolved in 1,000 ml of 0.1% aqueous sodium hydroxide solution and 200 ml of ethanol. The resulting solution was stirred at 40°C. To the solution was added a solution of 4.5 g of silver nitrate dissolved in 200 ml of water over a period of 5 minutes. Next, the excess salts were removed by the well known sedimentation method. Afterwards, the pH was adjusted to 6.3, and 300 g of an organic silver salt dispersion was obtained.
• the antifoggant precursor (1)* having the structure mentioned below was added to the dye providing substance in an amount of 0.2 molar time the substance and was formed into an oil dispersion together with the dye providing substance and electron donor, like the method of Example 1.
• Photographic material sample Nos. 202 to 206 were prepared in the same manner as Sample No. 201, except that the additives as indicated in Table 3 below were added. TABLE 3 Sample No. Layer Additives Amount Added (g/m2) 202 First Layer Active Charcoal (1)* 0.05 Surfactant (1)* 0.01 Surfactant (4)* 0.003 Surfactant (5)* 0.006 203 Second Layer Same as those added to the first layer of No. 202 204 Sixth Layer Same as those added to the first layer of No.
• Example 2 The previously prepared light-sensitive material samples were exposed in the same manner as Example 1 and then uniformly heated on a heat block heated at 140°C for 30 seconds.
• the thus combined sample was passed through a laminator heated at 80°C at a linear velocity of 12 mm/sec and then the both materials were peeled off from each other.
• the dye-fixing material sample had a positive image with an excellent S/N ratio.
• light-sensitive material sample Nos. 203 to 206 of the present invention gave an image with less stain than light-sensitive material sample Nos. 201 and 202.
• the silver halide emulsions for the fifth layer and first layer were prepared as mentioned below.
• 600 ml of an aqueous solution containing both sodium chloride and potassium chloride and an aqueous silver nitrate solution (formed by dissolving 0.59 mol of silver nitrate in 600 ml of water) were simul­taneously added to a well stirred aqueous gelatin solution (containing 20 g of gelatin and 3 g of sodium chloride in 1,000 ml of water and heated at 75°C) all at the same flow rate over a period of 40 minutes. Accordingly, a monodispersed cubic silver chlorobromide emulsion (bromine content: 50 mol%) having a mean grain size of 0.40 ⁇ m was prepared.
• the silver halide emulsion for the third layer was prepared as mentioned below.
• 600 ml of an aqueous solution containing both sodium chloride and potassium bromide and an aqueous silver nitrate solution prepared by dissolving 0.59 mol of silver nitrate in 600 ml of water
• aqueous gelatin solution containing 20 g of gelatin and 3 g of sodium chloride in 1,000 ml of water and heated at 75°C
• a monodispersed cubic silver chlorobromide emulsion (bromine content: 80 mol%) having a mean grain size of 0.35 ⁇ m was prepared.
• the silver benzotriazole emulsion was prepared as mentioned below.
• the resulting silver benzotriazole emulsion was adjusted to the determined pH and the excess salts were removed therefrom by sedimentation. Afterwards, the pH was adjusted to 6.30, and 400 g of the intended silver benzotriazole emulsion was obtained.
• the silver acetylene emulsion was prepared as mentioned below.
• gelatin dispersion of dye providing substance was prepared as mentioned below.
• a magenta dye providing substance dispersion was prepared in the same manner as above, except that Magenta Dye Providing Substance (5)* was used and 2.5 g of tricresyl phosphate was used as the high boiling point solvent.
• a cyan dye providing substance dispersion was also prepared in the same manner as that preparing the yellow dye providing substance dispersion except that Cyan Dye Providing Substance (6)* was used.
• the thus prepared light-sensitive material sample Nos. 301 to 307 were exposed with a tungusten lamp of 500 luxes through a G-R-IR three color separation filter having a continuously varying color density for one second.
• the filter was composed of 500 to 600 nm band pass filter for G, 600 to 700 band pass filter for R and filter of passing 700 nm or more for IR.
• the thus combined material was heated for 30 seconds with a heat roller whose temperature was so adjusted that the temperature of the water-absorbed layer could be 88 or 98°C, and then the dye-fixing material was peeled off from the light-sensitive material.
• light-sensitive material sample Nos. 304 to 307 of the present invention gave an image with a lower Dmin than the light-sensitive material samples Nos. 301 to 303.

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• 1988
  • 1988-08-05 JP JP63195783A patent/JPH0830885B2/ja not_active Expired - Fee Related
• 1989
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