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
  • G03C1/49818—Silver halides

Definitions

• the present invention relates to heat-­developable light-sensitive materials, and in particular to heat-developable light-sensitive materials that have an excellent shelf life and high sensitivity.
• Heat-developable light-sensitive materials are well known. Heat-developable light-sensitive materials and processes thereof are mentioned, for example, in "Fundamentals of Photographic Engineering” Non-Silver Salt Photographic Edition (1982, Corona Co.), pp. 242 to 255; and U.S. Patent 4,500,626.
• a method of forming a dye image by a coupling reaction between the oxidation product of a developing agent and a coupler is described in U.S. Patents 3,761,270 and 4,021,240. Further, a method of forming a color positive image using light-sensitive silver dye bleaching process is described in U.S. Patent 4,235,957.
• Another method of forming a color image involves imagewise releasing or forming diffusible dyes by heat development, and transferring this diffusible dye to a dye fixing element. In this method, by changing the kind of dye providing compound or the kind of silver halide utilized, both a negative dye image and a positive dye image can be obtained. Further details of this are described in U.S.
• U.S. Patent 4,559,290 proposes a method in which a DDR compound which has been converted into oxidized form having no dye-releasing ability and a reducing agent or a precursor of a reducing agent are placed together, when this combination is subjected to heat development, the reducing agent is oxidized in proportion to the degree of exposure of the silver halide, and a diffusible dye is released by reduction by the remaining unoxidized reducing agent.
• EP-A-220746 and Kokai Giho 87-6199 Vol. 12, No. 22
• a heat-developable color light-sensitive material is described which uses a compound which similarly releases a diffusible dye by the reductive cleavage of a N-X bond (where X represents an oxygen atom, nitrogen atom or sulfur atom).
• heat fog is a major problem in image formation.
• heat fog is related to an increase in minimum density.
• heat fog causes a reduction in the maximum density.
• antifoggants In order to prevent heat fog, organic compounds known as antifoggants have generally been utilized. However, because known antifoggants are not very effective at controlling fog, or effectively control fog and simultaneously reduce sensitivity significantly.
• the silver halide emulsions in use in heat-­developable light-sensitive materials have required the use of large quantities of antifoggants in order to prevent fogging. Further, chemical sensitization in the emulsions is insufficient to give low-fog silver halide grains. For these reasons, increases in sensitivity, decreases in sensitivity, gradation changes, and the like during the time before utilization are much greater than in common conventional light-sensitive materials.
• An object of the present invention is to obtain a heat-developable high-sensitivity light-sensitive material that has an excellent shelf life.
• a heat-developable light-sensitive material having a light-sensitive layer containing a silver halide emulsion which comprises multiple-­structure silver chlorobromide grains that are gold-­sulfur sensitized in the presence of a sensitizing dye and have layers of differing halide composition.
• the silver halide grains used in the present invention have the following three features:
• JP-A-63-261357 describes multiple-structure grains with triple or more layered structure that are used together with an organic compound.
• the present invention uses double structure, core/shell grains that have only one layer of a different silver halide composition from the composition of the grain's interior; or multiple-­structure grains that have more than one different layer.
• the general configuration of the multiple-­structure grains of the present invention is a double structure grain. In some cases, however, grains with 3, 4 or more superposed layers give better performance.
• the interior (core) and surface (shell) are preferably in a relative volume ratio of core to shell of from 0.1:99.9 to 99.9:0.1. More preferably, the ratio is from 1:9 to 9:1.
• the average grain size of the silver halide grains used in the present invention is from 0.1 ⁇ m to 2.0 ⁇ m, preferably 0.1 ⁇ m to 1.3 ⁇ m, and more preferably 0.2 ⁇ m to 1.0 ⁇ m.
• an emulsion consisting of monodisperse silver halide grains refers to an emulsion consisting of silver halide grains, for which the value given by the standard deviation S of the grain diameter divided by the average grain diameter r and multiplied by 100 (the "coefficient of variation") is 16% or less as defined by the following formula:
• grain diameter is the diameter in the case of spherical silver halide grains, or for nonspherical grains it is the diameter of the projected image calculated as the circular image with the same surface area.
• the average grain size r is the average value of the grain diameter as defined by the following formula when there are n i grains of diameter r i .
• the crystal habit of these silver halide grains may be cubic, octahedral, tetradecahedral, tabular, pebble-like or spherical.
• the most preferred crystal habit is cubic, consisting of substantially (100) faces.
• JP-B-47-­11386 organic thioether derivatives as described in JP-B-47-­11386 (the term "JP-B” as used herein means an "examined Japanese patent publication”); or sulfur-containing compounds as described in JP-A-53-144319.
• the nitrogen-containing compounds such as those described in JP-B-46-7781, JP-A-60-222842, and JP-A-60-­122935, can be added during the formation of the silver halide grains.
• gelatin as a protective colloid and as a hydrophilic colloid binder during the preparation of the emulsion of the present invention.
• hydrophilic colloids may be used.
• various synthetic hydrophilic macromolecular substances such as gelatin derivatives, graft polymers of gelatin and other macromolecules, albumin, casein and similar proteins; hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfate esters and similar cellulose derivatives; sodium alginate, starch derivatives and similar saccharide derivatives; and polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinyl-­pyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole and similar homo- or copolymers.
• gelatin in addition to lime-processed gelatin and acid-processed gelatin, oxygen-processed gelatin as described in Bull. Soc. Sci. Phot. , Japan, No. 16, p. 30 (1966) may also be used as can the hydrolysis products or enzymolysis products of gelatin.
• Soluble salts ate normally eliminated from the emulsion after precipitate formation or physical ripening. This is done, for example, using the noodle washing method in which the gelatin is gelled. It is also possible to use flocculation methods utilizing inorganic salts formed from polyvalent anions (for example, sodium sulfate); anionic surfactants; anionic polymers (for example, polystyrenesulfonic acid); or gelatin derivatives (for example, aliphatic acylated gelatin, aromatic acylated gelatin, and aromatic carbamoylated gelatin).
• polyvalent anions for example, sodium sulfate
• anionic surfactants for example, polystyrenesulfonic acid
• gelatin derivatives for example, aliphatic acylated gelatin, aromatic acylated gelatin, and aromatic carbamoylated gelatin.
• the process of eliminating the soluble salts may also be omitted.
• the method of forming grains in the presence of excess of silver ions can also be used.
• the double jet method the controlled double jet method to keep the pAg constant in the liquid phase can also be used.
• the concentration, quantity, or speed of addition of silver salt and halide salt may be increased as disclosed in JP-A-55-142329, JP-A-55-158124, and U.S. Patent 3,650,757.
• the silver halide grain surface may be substituted by a halogen that forms a sparingly soluble silver halide grain.
• reaction liquid stirring method Any conventional stirring method may be used as the reaction liquid stirring method. Further, the temperature and pH of the reaction liquid may be set arbitrearliest during silver halide grain formation.
• the silver halide emulsion of the present invention may contain iridium, rhodium, platinum, cadmium, zinc, lead, thallium and the like, for the prevention of high-intensity, low-intensity reciprocity law failure, or fogging.
• Metals of this kind can be introduced by using iridium salts, rhodium salts, platinum salts, cadmium salts, zinc salts, lead salts or thallium salts together or separately during the grain-formation or the physical-ripening stage.
• the halogen composition of the grains of the present invention involves silver chlorobromide grains consisting of silver chloride and silver bromide. That is, the average halogen composition is substantially silver chlorobromide.
• Part of the multiple structure can be pure silver bromide or pure silver chloride, and may contain 3 mol% or less of silver iodide.
• the preferred average halogen composition is a silver bromide content of from 5 mol% to 98 mol%. More preferably, it is from 25 mol% to 97 mol%. The most preferable range is 35 mol% to 95 mol%.
• the preferred range for the halogen composition of the outermost layer of the multiple structure is a silver bromide content of about 25 mol% to 100 mol%. More preferably it is about 35 mol% to 100 mol%, and most preferably about 60 mol% to 100 mol%.
• the interior of the multiple structure have a layer with a lower silver bromide content than that of the outermost layer; in this case, the silver bromide content of this interior layer is more desirably about 10 mol% to 35 mol% lower than the outermost layer.
• the present invention is not limited by the silver bromide content of the interior layers.
• the third characteristic of the present invention is gold-sulfur sensitization in the presence of a sensitizing dye.
• Dyes usable in emulsions of the present invention include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.
• sensitizing dyes may be used singly, or in combination. Combinations of sensitizing dyes are frequently used, particularly to achieve super-­sensitization.
• the emulsion may contain dyes that show supersensitization, and have no spectral sensitizing action, or compounds that show supersensitization and do not substantially absorb visible light (for example, those described in U.S. Patent 3,615,641, Japanese Patent Application 61-226294 (corresponding to JP-A-63-23145), etc.).
• Such sensitizing dyes may be added to the emulsion during chemical sensitization (chemical ripening) or before it; they may be present in the reaction system of soluble silver salt (silver nitrate for example) and a halogen compound (potassium bromide for example) before the formation of silver halide grains (as described in U.S. Patent 4,183,756); or they may be added to this reaction system after the formation of the nucleus of the silver halide grains before completion of the silver halide grain formation process (as described in U.S. Patent 4,225,666).
• the sensitizing dye may also be present in the reaction solution of this reaction system simultaneously with the mixing of the silver salt and the halogen compound. Light-sensitive material containing an emulsion prepared in this manner shows better gradation and storage properties in a high temperature state.
• the total quantity of dye may be added all at once or in portions over a period of time.
• Dye may also be added to the reaction system in the form of an admixture with the soluble silver salt and/or the halogen compound.
• sensitizing dye it is possible to add sensitizing dye to the liquid surface or into the liquid, and any known method of stirring can be used.
• Sensitizing dye used in the present invention may be added dissolved in methanol, ethanol, propanol, a fluorinated alcohol, methyl cellosolve, dimethyl-­formamide, acetone, and other known organic solvents that are compatible with water, or water (they may be alkaline or acidic), or two or more of the above-­mentioned solvents may be used together. Further, sensitizing dye may be added in dispersed form via a water/gelatin dispersion system; in the form of a freeze-dried powder; as a powder dispersed using surfactants; or in the form of a solution.
• the quantity of sensitizing dye used is suitably 0.001 g to 20 g, and preferably 0.01 g to 2 g per 100 g of silver used in producing the emulsion.
• the concentration of sensitizing dye used in the reaction liquid in silver halide grain formation is suitably about 1 wt% or less, preferably about 0.1 wt% or less.
• the silver halide emulsion of the present invention is a gold-sulfur sensitized emulsion.
• Useful sulfur sensitizers include active gelatin sulfur-containing compounds that react with silver. Examples of such compounds are thiosulfate, allylthio­carbamide, thiourea, allyl isothiocyanate, cystine, p-­toluenethiosulfonate, rhodanine, and mercapto compounds. Such compounds are described in U.S. Patents 1,574,944; 2,410,689; 2,278,947; 2,728,668; and 3,656,955.
• Sulfur sensitizer can be used in a quantity of about 10 ⁇ 7 to 10 ⁇ 2 mol per mol of silver.
• Useful gold sensitizers are those with a gold oxidation number of +1 or +3. Examples of these are the chloroaurates, potassium chloroaurate, auric trichlo­ride, potassium auric thiocyanate, potassium iodoaurate, and tetracyanoauric acid.
• the amount of gold sensitizer useful is about 1x10 ⁇ 7 to 1x10 ⁇ 2 mol per mol of silver.
• the temperature during chemical sensitization can be from about 40 to 90°C, preferably 45 to 75°C.
• the pH during chemical sensitization can be from about 3 to 9, preferably 4 to 8, and the pAg can be from about 5 to 11, preferably 7 to 10.
• the gold sensitizer may be added simultaneously with the addition of the sulfur sensitizer, before the sulfur sensitizer, or after the sulfur sensitizer.
• Useful selenium sensitizers are aliphatic isoselenocyanates such as allyl isoselenocyanate, selenoureas, selenoketones, selenoamides, seleno­carboxylic acids and esters, selenophosphates, and selenides such as diethyl selenide and diethyl diselenide. Specific examples of these are described in U.S. Patents 1,574,944; 1,602,592; and 1,623,499.
• Selenium sensitizers can be used in a quantity of about 10 ⁇ 7 to 10 ⁇ 2 mol per mol of silver.
• chemical sensitizers notably gold sensitizers
• a silver halide photographic emulsion by known methods.
• water-soluble compounds are added as aqueous solutions
• compounds soluble in organic solvents are added as solutions of organic solvents that are easily miscible with water (for example, methanol or ethanol).
• This chemical sensitization can also be performed in the presence of nitrogen-containing heterocyclic compounds as described in British Patent 1,315,755; JP-A-50-63914; JP-A-51-77223; JP-A-58-­126526; and JP-A-58-215644.
• JP-B-39-22067 and JP-B-39-220608 it is also useful to perform chemical sensitization in the presence of acetylenic compounds, as low-fog silver halide emulsions are obtained.
• silver halide solvents are the thiocyanates and the solvents described in JP-A-63-­151618.
• the heat-developable light-sensitive materials of the present invention are basically light-sensitive silver halide and a binder on a support containing, as required, organic metal salt oxidizing agents or dye providing compounds (as mentioned below that may also act as reducing agents) in the same layer, or if they are in a reactive state in separate layers.
• organic metal salt oxidizing agents or dye providing compounds as mentioned below that may also act as reducing agents
• dye providing compounds as mentioned below that may also act as reducing agents
• reducing agents may be supplied from outside by a method of diffusion from dye fixing materials mentioned as discussed below.
• At least three silver halide emulsion layers sensitive to the different spectral regions are used in combination.
• a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer; or a green-sensitive layer, a red-sensitive layer, and an infrared-sensitive layer could be used.
• Various sequences common in color light-sensitive materials can be used for the various light-sensitive layers.
• these light-­sensitive layers may be separated into two or more layers as required.
• auxiliary layers such as protective layers, undercoating layers, intermediate layers, yellow filter layers, antihalation layers, and backing layers can be provided in the heat-developable light-sensitive materials of the invention.
• silver halides may be used together with silver chlorobromide in the multiple grain structure of the present invention. Any of the following silver halides may be used together: silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide, and silver chloroiodobromide.
• the coating quantity of the light-sensitive silver halide utilized in the present invention is about 1 mg to 10 g per m2, calculated as silver.
• Organic metal salts may be used jointly as oxidizing agents together with light-sensitive silver halide in the present invention.
• Organic silver salts are particularly preferred.
• Organic compounds which may be utilized in forming the organic silver salt oxidizing agents used in the invention are benzotriazoles and fatty acids and other compounds as described in U.S. Patent 4,500,626. Further, silver phenylpropiolate and similar silver salts of carboxylic acids possessing alkinyl groups as described in JP-A-60-113235; and acetylene silver as described in JP-A-61-249044, are also useful. Two or more kinds of organic silver salts may be used together.
• Per mol of light-sensitive silver halide 0.01 to 10 mol, preferably 0.01 to 1 mol, of the organic silver salts described above can be used simultaneously.
• the total coating amount of the light-sensitive silver halide and the organic silver salts is suitably between about 50 mg and 10 g per m2, calculated as silver.
• antifoggants or photographic stabilizers can be used in the present invention such as the azoles and azaindenes described in RD 17643 (1978), pp. 24 to 25; the nitrogen-containing carboxylic acids and phosphoric acids described in JP-A-59-168442; the mercapto compounds and their metal salts described in JP-A-59-111636; and the acetylenic compounds described in JP-A-62-87957.
• R1, R2, R3 each represents a hydrogen atom; a substituted or unsubstituted aliphatic group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heterocyclic group.
• One set or both sets of R2 and R3 together and/or R1 and R2 together may bond together to form a 5 to 7 membered carbocyclic or heterocyclic ring.
• X represents a sulfur atom or an oxygen atom.
• Non-limiting examples of nitrogen-containing heterocyclic compounds represented by general formula (I) or (II) are given below.
• Antifoggants are normally used in the present invention in a quantity of 10 ⁇ 7 to 10 mol per mol of silver halide.
• An advantage of the silver halide emulsions of the present invention is that even when comparatively large amounts of antifoggants are used (for example, 10 ⁇ 4 to 1 mol/mol Ag), high sensitivities are still achieved.
• Various polymer latexes can be included in the layers constituting the light-sensitive materials or dye fixing materials as well as in the backing layer. Such latexes can be used for dimensional stabilization, curl prevention, adhesion prevention, film cracking prevention, pressure sensitization prevention, and other improvements of film characteristics.
• a polymer latex with a low glass transition point 40°C or less
• a curl prevention effect is obtained by using a polymer latex with a high glass transition point in the backing layer.
• any of the polymer latexes described in JP-A-62-245258, JP-A-62-136648, JP-A-62-110066 can be utilized.
• reducing agents in the field of heat-­developable light-sensitive materials can be used in the present invention.
• Dye providing compounds that have reducing properties can also be used. Such dye providing compounds can be simultaneously with other reducing agents.
• Reducing agent precursors that manifest reducing properties when activated by nucleophilic reagents or heat can also be used.
• reducing agents used in the present invention are the reducing agents and reducing agent precursors described in U.S. Patent 4,500,626, columns 49 to 50; U.S. Patent 4,483,914, columns 30 to 31; U.S. Patent 4,330,617; U.S.
• electron transfer agents and/or electron transfer agent precursors can be used in combination as required to promote electron transfer between the nondiffusible reducing agent and the developable silver halide.
• Electron transfer agents or their precursors can be selected, for example, from the reducing agents or their precursors cited above.
• the mobility of such electron transfer agents or their precursors is preferably greater than that of the nondiffusible reducing agents (electron donors).
• Particularly useful electron transfer agents are 1-phenyl-3-pyrazolidones or aminophenols.
• Nondiffusible reducing agents useful in combination with electron transfer agents are those which have substantially no mobility in the layers of light-sensitive material.
• these are hydroquinones, sulforamidophenols, sulfonamidonaphthols, the compounds described in JP-A-53-110827 as electron donors, and dye providing compounds possessing nondiffusing reducing properties.
• the quantity of reducing agents added in the present invention is 0.001 to 20 mol, preferably 0.01 to 10 mol, per mol of silver.
• Silver can be used as the image forming substance in the present invention. Further, when silver ions are reduced to silver at a high temperature state, compounds which can form or release mobile dye corresponding or countercorresponding to this reaction, namely dye providing compounds, can be included.
• Couplers compounds which form dyes by an oxidative coupling reaction
• These couplers may be 4-equivalent or 2-equivalent couplers.
• the 2-equivalent couplers that are preferred have a nondiffusible group as an elimination group and form a diffusible dye by an oxidative coupling reaction. This nondiffusible group may form a polymer chain.
• Specific examples of color developers and couplers are described in detail in T.H. James, "The Theory of the Photographic Process", 4th edition, pp. 291 to 334 and pp.
• 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.
• Another example of a useful type of dye providing compounds are compounds having a mechanism of imagewise release or diffusion of diffusible dye. These kinds of compounds can be represented by the following formula (LI). ( Dye -Y) n -Z (LI)
• Dye represents a dye group, a transiently short-­waved dye group, or a dye precursor group.
• Y represents a single bond or a linking group.
• Z represents groups possessing properties such that differences in the diffusibility of the compounds represented by ( Dye -Y) n -Z are caused to arise, or Dve is released, and differences in the diffusibility between the released Dye and ( Dye -­Y) n -Z are caused to arise, corresponding or counter-­corresponding to a light-sensitive silver salt imagewise possessing a latent image.
• n represents 1 or 2; when n is 2, each ( Dye -Y) may be the same or different.
• Specific examples of the dye providing compounds represented by general formula (LI) are compounds (1) to (5), below.
• Compounds (1) to (3), below are compounds that form a diffusible dye image (positive dye image) countercorresponding to the development of the silver halide.
• Compounds (4) and (5) are compounds that form a diffusible dye image (negative dye image) corresponding to the development of the silver halide.
• Patents 4,343,893 and 4,619,884 that release a diffusible dye through the opening of a single bond after reduction.
• X represents an oxygen, sulfur or nitrogen atom
• the compounds described in Japanese Patent Application 62-106885 corres­ponding to JP-A-1-26842) that have in one molecule a SO2-X bond (X is the same as above) and an electron attracting group.
• JP-A-63-271341 that have in one molecule a C-X′ bond (X′ represents the same as X, or -SO2-) and an electron attracting group.
• X′ represents the same as X, or -SO2-
• the compounds described in Japanese Patent Application Nos. 62-319989 and 62-320771 that release a diffusible dye by opening of a single bond after reduction by means of ⁇ -bonds conjugated to an electron accepting group.
• Specific examples of these are 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 EP-A-220746 or U.S. Patent 4,783,396; and Compounds (11) to (23) in Kokai Giho 87-6199.
• Additional dye providing compounds apart from the couplers and compounds of general formula (LI), are dye silver compounds with organic silver salts and dyes bonded together ( Research Disclosure (RD), (May, 1978), pp. 54 to 58); azo dyes used in heat-developable silver dye bleach methods (U.S. Patent 4,235,957, Research Disclosure (RD) (April, 1976), pp. 30 to 32); and leuco dyes (U.S. Patents 3,985,565 and 4,022,617).
• Dye providing compounds, nondiffusible reducing agents, and similar hydrophobic additives can be introduced into the light-sensitive material layers using known methods such as those described in U.S. Patent 2,322,027.
• High-boiling organic solvents such as those 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 together with low-boiling organic solvents having a boiling point 50°C to 160°C can be used as required.
• the quantity of high-boiling organic solvent used is 10 g or less per 1 g of dye providing compound, preferably 5 g or less.
• surfactants For hydrophobic compounds dispersed in a hydrophilic colloid, various surfactants can be used. Such surfactants are mentioned in JP-A-59-157636, at pages (37) to (38).
• Compounds can be used in the present invention that simultaneously provide for activation of the development of the light-sensitive material and stabilization of the image. Specific examples of preferred compounds described in U.S. Patent 4,500,626, columns 51 to 52.
• a dye fixing material can be used together with the light-sensitive material.
• the dye fixing material may be coated on a separate support from the light-sensitive material, or it may be coated on the same support as the light-sensitive material.
• the relationship between the light-sensitive material and the dye fixing material, its relationship with the support, and with the white reflecting layer described in U.S. Patent 4,500,626, column 57, are also suitable relationships for the present application.
• the dye fixing material used for preference in this invention has at least one layer containing a mordant and a binder.
• the mordant can be one that is well known in the field of photography. Specific examples of such mordants are described in U.S. Patent 4,500,626, columns 58 to 59; and JP-A-61-88256, pages (32) to (41); and, in particular, those described in JP-­A-62-244043 and JP-A-62-244036.
• the macromolecular dye accepting compounds described in U.S. Patent 4,463,079 can also be used.
• the dye fixing material can be provided as required with a protective layer, peelable layer, curl preventing layer, and other kinds of auxiliary layers.
• a protective layer is particularly useful.
• Plasticizers, slip agents, or high-boiling organic solvents to improve the peeling of the light-­sensitive material and the dye fixing material, can be used in the layer constituting the light-sensitive material and the dye fixing material. Specific examples of these are described in JP-A-62-253159, page (25), and JP-A-62-245253.
• Various kinds of silicone oil can also be utilized. Examples of these are the modified silicone oils described in "Modified Silicone Oils" published by Shin'etsu Silicone (Co.) technical data, p. 6-18B, and the silicone oils described in JP-A-62-215953 and JP-A-­63-46449. Particularly effective are carboxy-modified silicone (Trade name X-22-3710).
• Discoloration inhibitors may be used in the light-sensitive material or the dye fixing material. These can be, for example, antioxidants, ultraviolet absorbers, or certain metal complexes.
• antioxidants are chroman compounds, coumaran compounds, phenolic compounds (for example, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindan compounds.
• phenolic compounds for example, hindered phenols
• hydroquinone derivatives for example, hindered phenols
• hindered amine derivatives for example, hindered amines
• spiroindan compounds examples include chroman compounds, coumaran compounds, phenolic compounds (for example, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindan compounds.
• the compounds described in JP-A-61-159644 are also effective.
• Ultraviolet absorbents that are useful are benzotriazole compounds (U.S. Patent 3,533,794), 4-­thiazolidone compounds (U.S. Patent 3,352,681), benzophenol compounds (JP-A-46-2784), and the compounds described in JP-A-54-48535, JP-A-62-136641 and JP-A-61-­88256, and the ultraviolet-absorbing polymers described in JP-A-62-260152.
• Discoloration inhibitors to prevent the fading of the dye transferred to the dye fixing materials may be included in the dye fixing materials, or supplied to the dye fixing materials from outside, for example from the light-sensitive materials.
• oxidation inhibitors ultraviolet absorb­ents, and metal complexes, described above may be used in combination with each other.
• Brightening agents may be used in the light-­sensitive materials and dye fixing materials. Brightening agents are preferably incorporated into the dye fixing material, or supplied from outside, for example from the light-sensitive material. Examples of these are described in K. Veenkataraman, "The Chemistry of Synthetic Dyes", Volume V, Chapter 8, and in JP-A-61-­143752. More specifically, stilbene-based compounds, coumarin-based compounds, biphenyl-based compounds, benzoxazole-based compounds, naphthalimido compounds, pyrazoline-based compounds, carbostyryl compounds can be used.
• Brightening agents can be used in combination with discoloration inhibitors.
• Hardening agents that can be used in a layer containing the light-sensitive material and dye fixing material are described in U.S. Patent 4,678,739 column 41; JP-A-59-116655; JP-A-62-245261; and JP-A-61-­18942.
• aldehyde-based hardening agents (formaldehyde and the like); azylidene-based hardening agents; epoxy-based hardening agents like vinylsulfone-based hardening agents (N,N-ethylene-­bis(vinylsulfonylacetamido)ethane); N-methylol-based hardening agents (dimethylolurea); and macromolecular hardening agents (compounds described in JP-A-62-234157) are useful.
• surfactants can be utilized in the layers constituting the light-sensitive material and the dye fixing material as coating aids for separability improvement, slip improvement, static electricity prevention, and development acceleration. Specific examples of surfactants are described in JP-A-62-173463 and JP-A-62-183457.
• Organofluorine compounds may be contained in the layers constituting the light-sensitive material and the dye fixing material for slip improvement, static electricity prevention, and separability improvement.
• organofluorine compounds are the fluorine-based surfactants described in JP-B-57-9053 columns 8 to 17; JP-A-61-20944; JP-A-62-135826; fluorinated oils and oily fluorine compounds; tetra-­fluoroethylene resins, solid fluorine compound resins, and the hydrophobic fluorine compounds.
• Matting agents can be used in the light-­sensitive material and dye fixing material.
• matting agents other than silicon dioxide, polyolefins or polymethacrylates and the like, as described in JP-A-61-­88256 page (29), there are the benzoguanamine resin beads, polycarbonate resin beads, AS resin beads the like compounds described in Japanese Patent Applications Nos. 62-110064 and 62-110065 (corresponding to JP-A-63-­274944 and JP-A-63-274952, respectively).
• Thermal solvents, antifoaming agents, antifungal agents, colloidal silica and other known additive may be included in the layers constituting the light-sensitive material and the dye fixing material. Specific examples of these additives are described in JP-A-61-88256, pages 26 to 32.
• Image formation accelerators can be used in the light-sensitive material and/or the dye fixing material in the present invention.
• the function of image formation accelerators is to accelerate the oxidation-­reduction reactions of the silver salt oxidizing agent and the reducing agent; to accelerate the reaction of dye formation, dye decomposition, or release of diffusible dye from dye providing substances; and to accelerate the transfer of dye from the light-sensitive material layer to the dye fixing layer.
• They are classified according to physicochemical function as bases or base precursors, nucleophilic compounds, high-­boiling organic solvents (oils), thermal solvents, surfactants, and compounds that interact with silver or silver ions. These groups of substances generally have more than one function, and usually have some accelerating effect.
• These accelerators are described, for example, in U.S. Patent 4,678,739, columns 38 to 40.
• Useful base precursors are the salts of organic acids and bases from which carbon dioxide is released by heat; and compounds that release an amino group by Rossen rearrangemen, Beckmann rearrangement, or an intramolecular nucleophilic substitution reaction. Specific examples of these are described in U.S. Patent 4,511,493 and JP-A-62-65038.
• the base and/or base precursor In a system in which heat development and dye transfer take place simultaneously in the presence of a small amount of water, it is preferable for the base and/or base precursor to be included in the dye fixing material. Such an arrangement gives a light-sensitive material with a long shelf life.
• base precursors can be formed from the combination of sparingly soluble metallic compounds and compounds that react with the metallic ions in these sparingly soluble compounds to form complexes (termed “complex forming compounds"). These are described in EP-A-210660 and U.S. Patent 4,740,445. This method is particularly effective. These sparingly soluble metal compounds and complex forming compounds are advan­tageously added separately to the light-sensitive material and the dye fixing material. Also useful are compounds that produce bases upon electrolysis as described in JP-A-61-232451.
• a development stop agent can normally be used in the light-sensitive material and/or in the dye fixing material of the present invention in order to obtain an image.
• a development stop agent is a compound that after appropriate development quickly neutralizes or reacts with the base to reduce the concentration of base in the film and stop development, or a compound which inhibits development by interacting with silver and silver salt.
• Such agents are acid precursors that liberate acid on heating; electrophilic compounds that initiate a substitution reaction with base that is present on heating; heterocyclic nitrogen-containing compounds; and mercapto compounds and their precursors can be mentioned. These are described in JP-A-62-­253159, pages 31 to 32.
• Useful supports for the light-sensitive material and dye fixing material of the present invention are materials which can withstand the processing temperature.
• paper and synthetic polymers films are useful.
• These materials can be used independently, or as supports that have been laminated on one or both faces with polyethylene or similar synthetic macromolecules.
• Hydrophilic binders and semiconductive metallic oxides such as alumina sol and tin oxide, carbon black, and other antistatic agents may be coated on to the surface of these supports.
• the methods of recording an image on the light-­sensitive material by direct exposure using a camera; by exposure through reversal film or negative film using a printer or enlarger; by scanning exposure of an original image through a slit using the exposure device of a copying machine; by exposure using a light emitting diode or a laser for image recording via electrical signals; and for recording the image output of a CRT, liquid crystal display, electroluminescent display, or plasma display either directly or via an optical system can be used.
• Light sources useful for recording the image on the light-sensitive material are natural light, a tungsten lamp, a light emitting diode, a laser light source, a CRT light source, and the light sources described in U.S. Patent 4,500,626, column 56.
• the image can be exposed using a wavelength conversion element obtained by combining nonlinear optical material and a laser or other coherent light source.
• the nonlinear optical material is a material which can manifest nonlinearity between the polarization and the electric field appearing when a strong photoelectric field such as laser light has been applied.
• inorganic compounds such as lithium niobate; potassium dihydrogen phosphate (KDP); lithium iodate and BaB2O4; and urea derivatives; nitroaniline derivatives; 3-­methyl-4-nitropyridine-N-oxide (POM) and nitropyridine-­N-oxide derivatives; and the compounds described in JP-­A-61-53462 and JP-A-62-210432.
• Single crystal photo­conductive wave path form and fiber form are known as configurations of wavelength conversion elements that are useful.
• An image data can utilize image signal obtained from video cameras, or electronic still cameras, television signals as represented by the Nippon television signal code (NTSC), image signals obtained by dividing an original image into a plurality of pixels in a scanner, or images made using computer graphic or computer-aided design programs.
• NTSC Nippon television signal code
• An electrically conducting layer that generates heat may be used as the heat source for heat development or diffusible dye transfer in the light-sensitive material and/or dye-fixing material.
• a transparent or non-transparent heat-generating element is described in JP-A-61-145544. Such conductive layers also function as antistatic layers.
• the dye diffusion-transfer process may take place simultaneously with heat development, or it may proceed after the end of the heat development process.
• transfer is possible from the temperature of the heat development to room temperature.
• the temperature for transfer is preferably from 50°C to the temperature about 10°C lower than the temperature in the heat development process.
• the migration of dye can take place due to heat alone, but a solvent may be used to accelerate dye migration.
• the heating temperature is preferably 50°C or above, and below the boiling point of the solvent.
• the solvent in particular, water
• the preferred temperature would be 50°C or above and 100°C or below.
• Useful solvents to accelerate development and/or migration of the diffusible dye to the dye fixing layer are water and a basic aqueous solution containing an inorganic alkali metal salt and one of the organic bases described in the image-forming accelerator section.
• Low boiling point solvents; mixed solutions of low-boiling solvents and water or basic aqueous solutions can be utilized.
• Surfactants, antifoggants, sparingly soluble metallic salts, and complex-forming compounds may be present in the solvent.
• solvents can be used with methods that allow them in the dye fixing material, light-sensitive material, or both the dye fixing material and the light-­sensitive material.
• the amount of solvent utilized may be at most the weight of solvent corresponding to the maximum swelling volume of the whole coated film (in particular, a quantity not more than the difference of the weight of solvent corresponding to the maximum swelling volume of the whole coated film and the weight of the whole coated film). This is, effectively, a small quantity.
• a method of providing solvent in the light-­sensitive layer or dye fixing layer is described in JP-­A-61-147244, page (26). Further, the solvent can be incorporated into the light-sensitive material or the dye fixing material or both beforehand in microcapsules, for example.
• a system in which a hydrophilic thermal solvent that is solid at normal temperature and melts at a high temperature is incorporated into the light-sensitive material or the dye fixing material.
• the hydrophilic thermal solvent may be incorporated into either or both of the light-sensitive material or the dye fixing material. Further, it may be incorporated into any emulsion layer, intermediate layer, protective layer, or dye fixing layer. Preferably, it is incorporated into the dye fixing layer and/or a layer adjacent to the dye fixing layer.
• hydrophilic thermal solvents examples include ureas, pyridines, amides, sulfonamides, amides, alcohols, oximes, and other heterocyclic compounds.
• a high-­boiling organic solvent may be contained in the light-­sensitive material and/or the dye fixing layer.
• heating methods useful in the development and/or transfer process are contact with a heated block or plate; contact with a hot plate, hot press, hot roller; a halogen lamp heater; an infrared or far infrared lamp heater; or passage through a high temperature environment.
• any of various known heat development devices may be used.
• the devices described in JP-A-59-75247, JP-A-59-177547, JP-A-59-181353 and JP-­A-60-18951, and JP-A-U-62-25944 are preferably utilized (the term "JP-A-U" as used herein means an "unexamined published Japanese utility model application").
• the yield was 630 g of a monodisperse emulsion of cubic silver chlorobromide grains with an average grain size of 0.4 ⁇ m. (Uniform structure, sulfur sensitized emulsion).
• Table 2 Composition of added solutions (I) (II) AgNO3 (g) 100 - KBr (g) - 49 NaCl (g) - 10.4 H2O was added to total (cc) 450 450 450
• Solutions (I) and (II) or Table 3 were mixed simultaneously with an aqueous gelatin solution (Table 1) with good stirring while maintaining the temperature at 50°C. Solutions (III) and (IV) were added simultaneously to this mixture. After water washing, desalting, and chemical sensitization, identical to Emulsion (1), a monodisperse emulsion of cubic silver chlorobromide grains of average grain size 0.4 ⁇ m was obtained. The yield was 632 g. (Core/shell structure, sulfur sensitized emulsion).
• a gold-sulfur sensitized Emulsion (3) was formulated using identical steps to those described in formulating Emulsion (2), except that 3.2 mg of sodium thiosulfate, 155 mg of 4-hydroxy-6-methyl-1,3,3a,7-­tetraazaindene, and 0.6 mg of chloroauric acid were used in chemical sensitization.
• the emulsion obtained was a monodisperse silver chlorobromide emulsion with cubic grains of average grain size 0.4 ⁇ m, at a yield of 632 g. (Core/shell structure, gold-sulfur sensitized emulsion).
• Emulsion (4) was identical to that of Emulsion (2) except at 1 minute after adding solutions (III), (IV), dye solution A of Table 4 was added.
• the resulting emulsion was a monodisperse silver chlorobromide emulsion with cubic grains of average grain size 0.4 ⁇ m, in a yield of 630 g. (Core/shell structure, emulsion sulfur sensitized in the presence of dye).
• Emulsion (5) was identical to the preparation of Emulsion (3) except 1 minute after adding solutions (III), (IV) of Table 3, dye solution A of Table 4 was added.
• the emulsion obtained was a monodisperse silver chlorobromide emulsion with cubic grains of average grain size 0.4 ⁇ m, in a yield of 632 g. (Core/shell structure, emulsion gold-sulfur sensitized in the presence of dye).
• Electron Transfer Agent (1) shown below 0.5 g of polyethylene glycol nonylphenyl ether as a dispersing agent, and 0.5 g of the Anionic Surfactant (1) shown below were added to a 5% aqueous gelatin solution, and comminuted in a mill for 60 minutes with glass beads of average diameter 0.75 mm. The glass beads were separated off, and dispersion of electron transfer agent of average particle size 0.3 ⁇ m was obtained.
• Yellow, magenta and cyan dyes were each added as shown in the Treatment Method, below, to 50 cc of ethyl acetate and dissolved to a uniform solution by warming to about 60°C.
• This solution and 100 g of a 10% aqueous solution of lime-processed gelatin, 1.5 g of sodium dodecylbenzenesulfonate and 60 cc of water were stirred and mixed, then dispersed in a homogenizer at 10,000 rpm for 10 minutes.
• These dispersion liquids are termed "gelatin dispersions of dye providing compounds”.
• Electron Donor (2) shown below, and 8.5 g of High-Boiling Solvent (1) were added to 30 cc of ethyl acetate and uniformly dissolved. This solution and 100 g of a 10% solution of lime-processed gelatin, 0.25 g of sodium hydrogen sulfite, 0.3 g of sodium dodecylbenzenesulfonate, and 30 cc of water were stirred, and then dispersed in a homogenizer at 10,000 rpm for 10 minutes. This dispersion is "Gelatin Dispersion of Electron Donor (2)".
• Positive heat-developable color light-sensitive materials were prepared, constituted as shown in Table 5, using these emulsions and dispersions.
• Example 1 The light-sensitive materials prepared in Example 1 are shown in Table 6.
• Table 6 Light-sensitive material No. Emulsion utilized Sensitizing dye 101 Emulsion (1) (comparison) Dye Solution (A) 0.8 mg/m2 102 Emulsion (2) (comparison) Dye Solution (A) 0.8 mg/m2 103 Emulsion (3) (comparison) Dye Solution (A) 0.8 mg/m2 104 Emulsion (4) (comparison) - 105 Emulsion (5) (the present invention) -
• Dye fixing materials were prepared, as shown in Table 7.
• Light-sensitive materials 101 to 105 were exposed for 1/10 second at 4000 lux using a tungsten electric lamp through B.G.R and grey color separation filters of continuously varying density.
• the emulsion surface of the exposed light-­sensitive materials were supplied with 16 ml/m2 of water (image formation solvent) by wire bar, after which the dye fixing material was superposed on the film surface. After heating for 15 seconds using temperature controlled hot rollers to raise the temperature of the absorbed film to 78°C, the dye fixing material was stripped off the light-sensitive material, and magenta images corresponding to the B.G.R. and grey color separation filters were obtained without irregularity on the dye fixing material.
• Emulsion Silver halide Grain structure Chemical sensitization Addition period of sensitizing dye Fresh After 3 day storage at 45°C, 80% RH Remarks Dmax Dmin Sensitivity Dmax Sensitivity 101 (1) AgBrCl Uniform Sulfar After chemical sensitization 2.21 0.14 0.00 2.02 -0.06 Comparison 102 (2) AgBrCl Core/shell Sulfar After chemical sensitization 2.13 0.13 +0.07 2.01 +0.03 Comparison 103 (3) AgBrCl Core/shell Gold ⁇ sulfur After chemical sensitization 2.09 0.13 +0.13 2.04 +0.15 Comparison 104 (4) AgBrCl Core/shell Sulfar Before chemical sensitization 2.21 0.14 +0.16 2.20 +0.13 Comparison 105 (5) AgBrCl Core/shell Gold ⁇ sulfur Before chemical sensitization 2.22 0.13 +0.29 2.20 +0.30 The present invention
• Table 8 shows that the light-sensitive materials of the present invention are light-sensitive materials of high sensitivity that have a high maximum density, that is a small degree of fog, in relation to the comparative materials; and even after storage for 3 days at 45°C and 80% RH, the change in sensitivity and the reduction in maximum density is small in relation to the comparative materials.
• Solutions (I) and (II) of Table 9 were added at a constant temperature of 50°C to a well stirred Aqueous Gelatin Solution (Table 1). After addition of solutions (III) and (IV), Dye Solution A of Table 4 was added. Solutions (V) and (VI) of Table 9 were then added. After water wash desalting, chemical sensitization was done exactly as described in Emulsion (3) while controlling the pH and pAg, and a monodisperse emulsion of silver chlorobromide with cubic grains having an average grain size of 0.4 ⁇ m was obtained. The yield was 632 g. (Triple structure, emulsion gold-sulfur sensitized in the presence of a dye).
• Emulsion was prepared exactly as was Emulsion (5) except that the aqueous gelatin solution (Table 1) was kept at 75°C.
• Emulsion (8) was prepared exactly as was Emulsion (5), except instead of using the additive of Table 3, solutions (I) and (II) of Table 2 were used.
• the emulsion obtained was a monodisperse silver chlorobromide cubic emulsion with average grain size 0.4 ⁇ m; the yield was 650 g. (Uniform structure, emulsion gold-sulfur sensitized in the presence of a dye).
• Emulsion (9) was prepared exactly as was Emulsion (5), except instead of using the additive solutions of Table 3, solutions (I) and (II) and also (III) and (IV) of Table 10 were added.
• the emulsion obtained was a monodisperse silver chlorobromide emulsion of cubic grains of average grain size 0.4 ⁇ m; the yield was 636 g. (Core/shell structure, emulsion gold-sulfur sensitizei in the presence of a dye).
• Emulsion (10) was prepared exactly as was Emulsion (5), except instead of dye solution A of Table 4, the dye solution B of Table 11 was used.
• the resulting emulsion was a monodisperse silver chloro­ bromide emulsion of cubic grains of average grain size 0.4 ⁇ m; the yield was 625 g. (Core/shell structure, emulsion gold-sulfur sensitized in the presence of a dye).
• the light-sensitive materials 201 to 206 were exposed for 1/10 second at 4000 lux using a tungsten electric lamp through B.G.R and grey color separation filters of continuously varying density.
• the emulsion surface of these exposed light-­sensitive materials were supplied with 16 ml/m2 of water (image formation solvent) by wire bar, after which dye fixing material as described in Example 1 was superposed on the film surface. After heating for 15 seconds using temperature controlled hot rollers to raise the temperature of the absorbed film to 78°C, the dye fixing material was stripped off the light-sensitive material, and cyan images corresponding to the B.G.R. and grey color separation filters were obtained without irregularity on the dye fixing material.
• Example 2 The light-sensitive materials prepared in Example 2 are described in Table 13. Table 13 Light-sensitive material No. Emulsion utilized 201 Emulsion (5) 202 (6) 203 (7) 204 (8) 205 (9) 206 (10)
• Emulsion Silver halide Grain structure Chemical sensitization Addition period of sensitizing dye Fresh After 6 day storage at 58°C Remarks Dmax Sensitivity Sensitivity 201 (5) AgBrCl Core/shell Gold-sulfur Before chemical sensitization 2.09 +0.19 +0.12 The present invention 202 (6) AgBrCl Triple Gold-sulfur Before chemical sensitization 2.14 +0.21 +0.20 The present invention 203 (7) AgBrCl Core/shell Gold-sulfur Before chemical sensitization 2.05 +0.34 +0.36 The present invention 204 (8) AgBrCl Uniform Gold-sulfur Before chemical sensitization 2.01 0.00 -0.16 Comparison 205 (9) AgBrCl Core/shell Gold-sulfur Before chemical sensitization 2.13 +0.17 +0.15 The present invention 206 (10) AgBrCl Core/shell Gold-sulfur Before chemical sensitization 2.11 +0.11 +0.07 The present invention
• Table 14 shows that the light-sensitive materials of the present invention have high maximum density and high sensitivity. They also exhibit little change in sensitivity when storage.
• the emulsion obtained was a monodisperse silver bromide emulsion of pebble-like grains having an average grain size 0.3 ⁇ m; the yield was 635 g.
• Emulsion (13) was prepared in exactly the same way as Emulsion (12) except instead of the addition of solutions (I) and (II) of Table 18 in Emulsion (12), solutions (III) and (IV) of Table 18 were added; and instead of solutions (III) and (IV) of Table 18, solutions (I) and (II) were added.
• Emulsion (13) was prepared with the core and shell halides inter­changed vis-a-vis Emulsion (12).
• the emulsion obtained was a monodisperse emulsion with pebble-like grains of an average size of 0.3 ⁇ m, and a yield of 610 g.
• Emulsion (14) was prepared in exactly the same way as Emulsion (12) except instead of adding solutions (I), (II), (III) and (IV) of Table 18 in Emulsion (12), solutions (I), (II), (III) and (IV) of Table 19 were added.
• the emulsion obtained was a monodisperse emulsion with pebble-like grains having an average size of 0.3 ⁇ m, in yield of 623 g.
• Table 19 (I) (II) (III) (IV) AgNO3 (g) 20 80 - - KI (g) - - 0.28 - KBr (g) - - 7 39.2 NaCl (g) - - 3.5 8.3 Water added to a total of (cc) 200 300 200 250
• Example 2 Light-sensitive materials as described in Table 12, Example 2 were prepared using these emulsions.
• Light-sensitive materials 301 to 304 were exposed for 1/10 second at 4000 lux using a tungsten electric lamp through B.G.R and grey color separation filters of continuously varying density.
• the emulsion surfaces of these exposed light-­sensitive materials were supplied with 16 ml/m2 of water (image formation solvent) by wire bar, after which dye fixing material as described in Example 1 was superposed on the film surface. After heating for 15 seconds using temperature controlled hot rollers so that the temperature of the absorbed film was raised to 78°C, the dye fixing material was stripped off the light-sensitive material, and cyan images corresponding to the B.G.R. and grey color separation filters were obtained without irregularity on the dye fixing material.
• the light-sensitive materials prepared in this Example 3 are described in Table 20.
• Table 20 Light-sensitive material No. Emulsion utilized 301 Emulsion (11) 302 (12) 303 (13) 304 (14)
• Emulsion Silver halide Grain structure Chemical sensitization Addition period of sensitizing dye Fresh Sensitivity after 6 day storage at 58°C Remarks Dmax Sensitivity 301 (11) AgBrCl Uniform Gold-sulfur Before chemical sensitization 2.10 0.00 -0.17 Comparison 302 (12) AgBrCl Core/shell Gold-sulfur Before chemical sensitization 2.21 +0.21 +0.20 The present invention 303 (13) AgBrCl Core/shell Gold-sulfur Before chemical sensitization 2.18 +0.18 +0.10 The present invention 304 (14) AgBrCl Core/shell Gold-sulfur Before chemical sensitization 2.20 +0.17 +0.18 The present invention
• Table 21 shows that light-sensitive materials of the present invention have high maximum densities and high sensitivities, that exhibit little change in sensitivity when stored.
• Solutions (I) and (II) of Table 23 were simultaneously added at a constant temperature of 55°C to well stirred aqueous gelatin solution (Table 22). Next, solutions (III) and (IV) of Table 23 were added. At 10 minutes before the addition of Solution (III) was completed, Dye Solution D of Table 24 was added over about 20 minutes. After water wash desalting, and the addition of 20 g of gelatin, the pH and pAg were adjusted and chemical sensitization optimally performed using 6 mg of sodium thiosulfate, 120 mg of 4-hydroxy-6-­methyl-1,3,3a,7-tetraazaindene and 0.45 mg of chloro­auric acid.
• the emulsion obtained was a monodisperse cubic emulsion of average grain size 0.43 ⁇ m, and a yield of 635 g.
• Table 23 Composition of Added Solutions (I) (II) (III) (IV) AgNO3 (g) 20 80 - - KBr (g) - - 9.8 53.2 KaCl (g) - - 2.1 1.4 Water added to a total of (cc) 40 160 80 160
• Emulsion (16) was prepared by adding of dye solution D directly before chemical sensitization as described for Emulsicn (15). Other conditions were the same as for Emulsion (15). The average grain size and grain form were the same as for Emulsion (15); the yield was 660 g.
• Emulsion (17) was prepared exactly as Emulsion (16) except Dye Solution D was added to the emulsion directly after the addition of the chemical sensitizer.
• Emulsion (17) had the same grain size and form as for Emulsion (16). The yield was 660 g.
• Emulsion (18) was prepared exactly as Emulsion (15) except Dye Solution D in Emulsion (15) was not added.
• the average grain size and form were the some as for Emulsion (15); the yield was 630 g.
• Yellow, magenta and cyan dyes were each added as shown in the Treatment Method, below, to 50 cc of ethyl acetate and dissolved to a uniform solution by warming to about 60°C.
• This solution and 100 g of a 10% aqueous solution of lime-processed gelatin, 0.6 g of sodium dodecylbenzenesulfonate and 50 cc of water were stirred and mixed, then dispersed in a homogenizer at 10,000 rpm for 10 minutes.
• These dispersion liquids are termed "gelatin dispersions of dye providing compounds”.
• Treatment Method (2) Yellow Magenta Cyan (g) (g) (g) Dye Providing Compound (1) (2) (3) 13 15.5 16.6 Electron Donor (1) 10.2 8.6 8.1 High-Boiling Solvent (1) 6.5 7.8 8.3 Electron Transfer Agent Precursor (1) 0.4 0.7 0.7
• Light-sensitive materials 401 to 404 were exposed for 1/10 second at 4000 lux using a tungsten electric lamp through B. G. R and grey color separation filters of continuously varying densities.
• the emulsion surface of these exposed light-­sensitive materials were supplied with 16 ml/m2 of water (image formation solvent) by wire bar, after which dye fixing material as described in Example 1 was superposed on the film surface. After heating for 15 seconds using temperature controlled hot rollers to raise the temperature of the absorbed film to 78°C, the dye fixing material was stripped off the light-sensitive material, and blue, green, red and grey images corresponding to the B. G. R. and grey color separation filters were obtained without irregularity on the dye fixing material.
• Table 26 shows that higher sensitivities and improved storage properties are achieved by using emulsions of the invention for all the light-sensitive layers in a heat-developable light-sensitive materials with a multi-layer structure.

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• 1989
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• 1990
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