JP3812583B2 - Silver halide photographic emulsion, silver halide photographic light-sensitive material containing the same, and image forming method - Google Patents

Description

The present invention relates to a silver halide color photographic light-sensitive material capable of always obtaining a stable and high-quality print regardless of a conventional analog exposure method and a recent digital exposure method, or a surface exposure method and a scanning exposure method. The present invention relates to a silver halide color print material in which a sufficient maximum density and appropriate gradation are always obtained in a wide exposure range of about 10 ^{−6 to} 100 seconds, and the quality is not impaired even when stored at room temperature for a long time.

  Silver halide photographic light-sensitive materials (hereinafter also referred to as “photographic light-sensitive materials” or simply “light-sensitive materials”) are very sensitive compared to other light-sensitive materials, such as high sensitivity and excellent gradation. Due to its excellent characteristics, it is widely used today. In recent years, as a result of improvements in equipment such as printers and automatic processors, improvements in development processing solutions, and improvements in the performance of photographic photosensitive materials, it has been easy and consistent from the development of color negative films to the production of prints even at each photo shop. So-called mini-labs that can be processed in the past have become widespread, making photography even more familiar. On the other hand, there is an increasing demand for a high-quality print image to be provided easily and stably in a short time without being a skilled engineer.

  Moreover, in the recent rapid trend toward digitization, opportunities for digital exposure using laser light or the like for photographic photosensitive materials have increased. Accompanying this, the suitability for exposure in a very short time of about milliseconds to nanoseconds with high illuminance light and the suitability for scanning exposure have been demanded. At the same time, in response to the rapid advancement of other non-silver salt output media including the ink jet system, there is a strong demand for further development of photographic light-sensitive materials advantageous in image quality, cost, and mass productivity.

  Conventionally, color paper, which is a photographic light-sensitive material for color printing, has been strongly demanded for faster processing performance. As a means for achieving this purpose, the silver halide emulsion used contains a silver chloride emulsion or silver chloride. By using a silver halide emulsion having a high rate, color development can be speeded up. For example, U.S. Pat. Nos. 4,183,756, 4,225,666, JP-A-55-26589, 58-91444, 58-95339, 58-94340, 58-95736 58-106538, 58-107531, 58-107532, 58-107533, 58-108533, 58-125612, and the like. With the introduction of these technologies, the current color paper has been devised so that a high-quality image can be obtained in a development process of only a few tens of seconds.

  On the other hand, it is generally known that doping an iridium compound is effective for improving the reciprocity failure characteristic, which is one of the problems of silver halide emulsions. For example, Japanese Patent Application Laid-Open Nos. 51-139323 and 59-171947 disclose that a group 8 metal compound of the periodic table can be incorporated to improve reciprocity failure and increase sensitivity. Japanese Patent Publication No. 49-33781, Japanese Patent Laid-Open Nos. 50-23618, 52-18310, 58-15959, 59-214028, 61-67845, etc. include rhodium compounds and iridium compounds. It is disclosed that the inclusion can improve the reconciliation failure and improve the contrast.

  However, in improving the reciprocity failure characteristics of silver chloride emulsions that have been adapted for rapid processing or silver halide emulsions with a high silver chloride content, the above-mentioned measures are not sufficient due to the deterioration of the latent image stability. Met.

  In order to solve this, for example, JP-A-1-105940 discloses a technique of doping an iridium compound into a specific region, and JP-A-3-188437 discloses that an iridium compound and an iron compound are 50% of the particle volume. There has been disclosed a technique for reducing the development density change in the processing over time after the reciprocity failure and the exposure after the exposure by containing it on the surface side. On the other hand, JP-A-5-281638 discloses a technique having a silver bromide localized phase and containing a compound such as gallium, germanium, indium and thallium, and JP-A-6-102604 discloses a specific bromine. JP-A-6-102609 discloses a technique for incorporating a metal complex having a ligand into a silver halide grain, and JP-A-6-102609 discloses a technique for incorporating two kinds of specific metal complexes inside the grain. And the stability of latent image are advocated.

  U.S. Pat. No. 4,933,272 discloses a silver halide photograph having a face-centered cubic lattice having a metal element of Groups 5 to 10 of the periodic table as a central metal and containing a complex having a nitrosyl or thionitrosyl ligand. It is disclosed that a reciprocity law failure is improved and a high-contrast characteristic can be obtained by an emulsion. Similar techniques are disclosed in JP-A-6-235994, JP-A-6-235993, JP-A-6-235990, JP-A-6-242539, and the like, and it is disclosed that a high contrast characteristic can be obtained. ing. Furthermore, JP-A-5-508036 discloses reciprocity failure and latent image stability in a silver halide emulsion containing a complex having a nitrosyl ligand and containing an iridium compound in the outer 10% of the grain volume. The improvement effect of is shown. Similar techniques are also disclosed in Japanese Patent Application Laid-Open Nos. 8-179454, 8-2111529, and 8-2153030, and it is stated that high contrast can be obtained by increasing the gradation of the leg portions.

  Various known examples are known as methods for doping silver halide grains with a target metal compound. In particular, when silver bromide fine grains previously doped with the target metal are added to the host emulsion, the target metal can be doped in the localized portion where the silver bromide content is high, with reciprocity failure and other performance improvements. This is advantageous in several patents. For example, the description can be found in JP-A Nos. 64-26837 and 3-156439, and the odors known as Lippmann particles can be found in JP-A Nos. 8-179454 and 8-2111529 mentioned above. An example is described in which a silver halide fine particle is previously doped with a target compound and added to a host emulsion.

  Japanese Patent Application Laid-Open No. 8-248553 claims a method for finishing silver halide grains comprising adding a silver halide fine grain emulsion having a photographically useful compound attached thereto to a high silver chloride emulsion. . However, the embodiment in the present invention is that the antifoggant is adsorbed to the silver bromide fine particles and epitaxy-bonded to the high silver chloride host emulsion, thereby effectively suppressing an increase in fog during long-term storage of the photosensitive material. Is the object of the invention and is completely different from the object and inventive idea of the present invention.

  Furthermore, JP-A-7-306488 discloses a silver halide grain having a guest portion having a halogen composition substantially equivalent to the surface of the host grain, containing a higher concentration of iridium ions than the iridium-containing host grains. Has been claimed. However, the embodiment in the present invention is a tabular grain having a high silver bromide composition containing a small amount of silver iodide, and is mainly intended to improve reciprocity failure in a photographic photosensitive material such as a color film. This is completely different from the present invention which presents a method for improving the digital exposure suitability of a high silver chloride emulsion for the purpose of producing a color print.

  In US Pat. No. 5,627,020, in the preparation of a silver halide emulsion in which silver bromide fine grains previously containing an iridium compound are added to a high chloride emulsion, the silver bromide content and the iridium compound content are A technique for imparting aptitude in exposure at high illuminance by defining in accordance with the correlation equation is disclosed.

  When exposing digital information to a photographic light-sensitive material, for example, a method of exposing to high illuminance in a very short time with a laser beam or the like is common. Therefore, when photographic performance that matches the digital exposure method is intended, it is necessary to provide high illumination exposure suitability in the millisecond to nanosecond range. Even in the method described in the above-mentioned US Pat. No. 5,627,020, improvement in the short-time exposure suitability at high illuminance is certainly recognized. On the other hand, in the conventional analog exposure, particularly large enlargement is achieved. It was revealed that the suitability is significantly impaired during long exposure such as.

  In addition, the technique described so far is characterized by concentrating metal compounds such as iridium in the silver bromide localized phase near the grain surface. In many cases, a device for preventing dispersion (for example, reaction temperature) is required.

  There are many problems that can be solved by forming a silver bromide localized phase in such high silver chloride grains and functionally controlling the doping, but on the other hand, the thermal stability of the silver bromide localized phase Several performance degradations presumed to be due to lowness were revealed by our studies. For example, when the pre-exposure print material produced by the above-described method is stored for a long period of time or under high temperature conditions, it has been found that fogging is so large that it is not practical.

  The inventors of the present invention are able to provide a print output material that is inexpensive regardless of the exposure method such as an analog method or a digital method, and that is not easily affected by the length of the storage period or storage conditions, and that can always stably provide a stable print. Research has been conducted with the aim of providing this information, and the disclosed technology is completely insufficient for that purpose.

  In addition, examples of adaptive techniques for the digital exposure method include chemical and color sensitization methods suitable for forming silver bromide localized phases described in US Pat. No. 601,513, and further, European Patent No. 750,222 and Although there is a method using a silver iodochloride emulsion described in JP-A-772,079, etc., it is insufficient for the realization of the object by the inventors.

  On the other hand, there are few examples in which a high silver chloride emulsion grain is used as a host and a photographically useful compound such as a metal compound is added to a silver halide fine grain having a high silver chloride content. For example, Japanese Patent Application Laid-Open No. 7-225440 describes a method in which mercury chloride is pre-doped into silver chloride fine particles as a means for introducing a mercury compound into the high silver chloride (100) tabular grain preparation process. is there. However, in this case, silver chloride fine particles are merely used for the purpose of introducing a mercury compound into the tabular grains, and the purpose as intended by the present invention is not described at all.

  As described above, most of the prior art has been performed to dope the epitaxial junction portions having different lattice constants, and the doping of the non-epitaxy junction portion or the local control of the compound-containing portion of the present invention can be performed. It was completely unexpected that such an excellent improvement effect could be obtained.

Accordingly, an object of the present invention is to form a silver halide emulsion having a high silver chloride content or a high average silver chloride content, and having a stable and sufficient maximum density and an appropriate gradation in a wide exposure range with an exposure time of about 10 ^{−6 to} 100 seconds. And a silver halide photographic light-sensitive material containing the emulsion, and scanning the photographic light-sensitive material. An object is to provide an image forming method for exposure.

  The inventors have studied color photographic materials that can always obtain stable high-quality prints in an extremely short time regardless of the conventional analog surface exposure method and the latest digital scanning exposure method. We have found that the above objective is achieved by:

(Claim 1) A high silver chloride emulsion having an average silver chloride content of 95 mol% or more, and having an emulsion grain volume of 10 ⁻⁹ to 10 ⁻⁷ mol per mol of silver halide in the interior of the grain between the center and 50%. An iridium compound containing an iridium compound and having a grain volume of 90 to 100% in the vicinity of the grain surface and 10 to 1000 times the content of the iridium compound per mole of silver halide between the center and 50% . A silver halide photographic emulsion comprising:

  (Claim 2) A silver halide photographic light-sensitive material comprising the silver halide photographic emulsion according to claim 1.

  (Claim 3) A method of forming an image, comprising subjecting the silver halide photographic light-sensitive material according to claim 2 to scanning exposure.

The color photographic light-sensitive material produced using the silver chloride according to the present invention or a silver halide emulsion containing silver chloride at a high concentration always has a maximum density sufficient in a wide exposure range of an exposure time of about 10 ^{−6 to} 100 seconds. Therefore, it was an excellent silver halide color print material that does not impair the quality even when stored at room temperature for a long period of time, that is, regardless of the exposure method or the storage conditions of the photosensitive material.

  Hereinafter, the present invention will be described in more detail.

  The silver halide photographic emulsion according to the present invention (hereinafter also referred to as the emulsion of the present invention) is a so-called high silver chloride emulsion having a high silver chloride content. In particular, a high silver chloride emulsion in which 95 mol% or more is silver chloride is preferable. In this case, it has an arbitrary halogen composition such as silver chloride, silver chlorobromide, silver chloroiodobromide, silver chloroiodide, and the like. However, silver chlorobromide and silver chloroiodide containing 97 mol% or more of silver chloride are particularly preferable. From the viewpoint of rapid processability and process stability, a silver halide emulsion containing 98 to 99.9 mol% of silver chloride is more preferable.

  As one preferred embodiment applied to the emulsion of the present invention, a photographically useful compound prepared separately in a so-called host emulsion, which is an emulsion grain having a relatively large particle size during or after the growth of the base grain And a silver halide emulsion comprising silver halide grains prepared by adding a silver halide fine grain emulsion containing the above as a so-called guest and having guest portions deposited on or in the host grains. it can.

  In this case, the temperature at which the silver halide fine grain emulsion to be a guest is added and deposited on the host emulsion may be arbitrarily selected within the range where the fine grain emulsion can be dissolved and deposited on the host emulsion, but 30 to 80 ° C. Is preferred.

  The fine grain emulsion may be added at any place in each step during formation of silver halide host grains, physical ripening after formation of silver halide host grains, or chemical sensitization. For example, it may be carried out after the grain formation, or after the desalting step, or after chemical sensitization. However, after the grain formation of the host is completed, the effect of the present invention is more fully exhibited.

  In the above preferred embodiment, after the formation of the host grains, before adding a so-called chemical sensitizer for chemical sensitization, the fine grain emulsion is added to deposit the guest portion on the surface of the host grains. It is particularly preferable to keep them. In the present invention, all compounds added for the purpose of chemical sensitization are referred to as chemical sensitizers.

  As an apparatus and method for preparing a silver halide fine grain emulsion, various methods known in the art can be used. When the reaction mother liquor is concentrated after the fine grain emulsion is prepared, concentration by ultrafiltration is preferably used.

  The average grain size of the silver halide fine grain emulsion is preferably ½ or less of the average grain size of the silver halide emulsion used as a host and preferably 0.01 μm or more, but １ ／ or less. More preferably, it is particularly preferably 1/4 or less. The average grain size of the host emulsion is not particularly limited, but is preferably in the range of 0.1 to 1.2 μm, more preferably 0.2 to 1.0 μm. In this case, the average grain size of the silver halide fine grain emulsion used as the guest The diameter is preferably 0.01 to 0.5 μm, more preferably 0.01 to 0.1 μm.

  The silver halide fine grain emulsion has any halogen composition such as silver chloride, silver chlorobromide, silver chloroiodobromide, silver chloroiodide, etc., as long as it is a so-called high silver chloride emulsion having a high silver chloride content. However, silver chlorobromide containing 80 mol% or more of silver chloride and substantially free of silver iodide is preferred. In particular, the halogen composition of the fine grain emulsion together with the host emulsion is preferably 95 mol% or more, more preferably a fine grain emulsion having a halogen composition equivalent to that of the host emulsion, and substantially from silver chloride. In the case of using a fine grain emulsion.

  The amount of the silver halide fine grain emulsion added as a guest in these embodiments can be any amount as long as the effect of the present invention is not impaired, but is 10 mol% of the silver halide emulsion serving as the host. Or less, more preferably 5 mol% or less.

  In the above, the photographically useful compound is previously contained in the silver halide fine grain emulsion to be a guest.

  The above photographically useful compounds mean all compounds used for the purpose of improving the photographic performance of the prepared silver halide emulsion. For example, compounds such as dopant agents, antifoggants, chemical sensitizers, gold sensitizers, and color sensitizing dyes all correspond to this.

The amount of these compounds added to the silver halide fine grain emulsion can be arbitrarily set according to the type and purpose of the compound, but is preferably 10 ⁻⁸ to 10 ⁻¹ mol per mol of silver halide.

  In a preferred embodiment, the high silver chloride fine grain emulsion is previously incorporated with a compound containing a Group 8 metal as a dopant agent. As the metal compound that can be used for this purpose, a compound represented by the following general formula [II] is preferable.

General formula [II] _{R n [MX m Y 6-} m]
In the formula, M represents a metal selected from Group 8 elements of the periodic table, preferably iron, cobalt, ruthenium, rhodium, osmium, nickel, palladium and iridium. R represents an ant potassium metal atom, preferably sodium or potassium. m represents an integer of 0 to 6, and n represents an integer of 2 or 3.

  X and Y represent a ligand of the above metal complex, preferably a group such as nitrosyl, thionitrosyl, or carbonyl, and a compound in which some or all of the ligands are halide ions can also be preferably used.

In particular, an iridium compound has a large effect and is preferably used. Among these, an iridium compound containing a bromine atom in at least one of the ligands is particularly preferable. Typical examples of preferred iridium compounds are shown below, but are not limited thereto.
II-1: K ₂ [IrCl ₆ ], II-2: K ₃ [IrCl ₆ ],
II-3: K ₂ [Ir (CN) ₆ ], II-4: K ₃ [Ir (CN) ₆ ],
II-5: K ₂ [Ir (NO) Cl ₅ ], II-6: K ₃ [Ir (NO) Cl ₅ ],
II-7: K ₂ [IrBr ₆ ], II-8: K ₃ [IrBr ₆ ],
II-9: Na ₂ [IrBr ₆ ], II-10: Na ₃ [IrBr ₆ ],
II-11: K ₂ [IrBr ₄ Cl ₂ ], II-12: K ₃ [IrBr ₄ Cl ₂ ],
II-13: K ₂ [IrBr ₃ Cl ₃ ], II-14: K ₃ [IrBr ₃ Cl ₃ ],
II-15: K ₂ [IrBr ₅ Cl], II-16: K ₃ [IrBr ₅ Cl],
II-17: K ₂ [IrBr ₅ I], II-18: K ₃ [IrBr ₅ I],
II-19: K ₂ [IrBr ₅ (H ₂ O)], II-20: K ₃ [IrBr ₅ (H ₂ O)]
These iridium compounds may be used in combination of a plurality of compounds, and other metal compounds or photographically useful compounds may be used in any combination as long as the effects of the present invention are not impaired. You can also. The amount of the iridium compound added to the silver halide fine grains is preferably 10 ⁻⁷ to 10 ⁻² mol, more preferably 10 ⁻⁵ to 10 ⁻³ mol, per mol of silver halide.

The amount of iridium compound to be contained in the finally prepared silver halide emulsion as a result of deposition on the host grain as a guest by fine particles is 10 ⁻⁸ to 10 ⁻⁴ mol per mol of silver halide. The amount is preferably 10 ⁻⁸ to 10 ⁻⁶ mol.

  In order to previously include a photographically useful compound in the silver halide fine grain emulsion, the compound may be added during the grain formation of the fine grain emulsion. As a preferred method, the compound may be dissolved together with the halide salt and continuously added over the whole or a part of the grain forming step, and in particular, added over the whole grain forming step. Is preferred.

  Advantageously, the above emulsion contains metal ions. In particular, it is preferable to contain metal ions in the host emulsion to which the high silver chloride fine grain emulsion containing the above photographically useful compound is added as a guest.

  Examples of such metal ions include group 8-10 metals such as iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium, cobalt, and group 12 transition metals such as cadmium, zinc, mercury, and the like. , Lead, rhenium, molybdenum, tungsten, gallium, chromium and the like. Of these, metal ions such as iron, iridium, platinum, ruthenium, gallium and osmium are preferred. These metal ions can be added to the silver halide emulsion in the form of a salt or a complex salt.

  When a metal ion forms a complex, examples of the ligand or ion include cyanide, thiocyanic acid, isothiocyanic acid, cyanic acid, chloride, bromide, iodide, nitric acid, carbonyl, and ammonia. Can do. Of these, cyanide, thiocyanic acid, isothiocyanic acid, chloride and bromide ions are preferred.

  In order to contain metal ions in the above emulsion and the host emulsion, the metal compound is added to each of the silver halide grains before the formation of silver halide grains, during the physical ripening after the formation of silver halide grains. The metal compound may be added at any place in the process, but it is preferable to add the metal compound together with the halide salt and continuously add the whole or part of the grain forming process.

The amount of the metal ion added to the host emulsion is preferably 1 × 10 ⁻⁹ to 1 × 10 ⁻² mol per mol of silver halide, particularly 1 × 10 ^{−9 to} 5 × 10 ⁻⁶ mol. preferable.

The emulsion of the present invention contains 10 ^-9 to 10 ^-7 moles of iridium compound per mole of silver halide inside the grains between 50% and 50% from the center by grain volume, and 90 to 100 from the center by grain volume. % Silver halide emulsion characterized by containing an iridium compound 10 to 1000 times the amount of iridium inside the grain in the vicinity of the grain surface.

As a method for preparing such silver halide grains, for example, a plurality of halide solutions in which a target iridium compound is dissolved together with a halide salt are prepared with different concentrations of the iridium compound, and an arbitrary one can be selected according to the purpose. The silver halide grains may be precipitated by switching at this stage. At this time, the iridium compound that is added until the formation of the target silver halide grains is completed by 50% by volume and is considered to be contained in the grains is 10 ⁻⁹ to about 10 ⁻⁹ to 1 mol of silver halide. It may be in the range of 10 ⁻⁷ mol. Then, the iridium is added after the formation of the target silver halide grains and the completion of the formation of the target silver halide grains by 90% until the completion of 100%. What is necessary is just to prepare so that a compound may become 10 to 1000 times the number of moles of an iridium compound at the time of the end of 50%.

Specifically, 10 ⁻⁹ to 10 ⁻⁷ mol of an iridium compound per mol of silver halide is contained within 50% of the grain volume, and between 90 to 100% of the grain volume near the grain surface. Further, it is preferable to contain 10 ⁻⁸ to 10 ⁻⁵ mol of iridium compound per mol of silver halide, and it is more preferable to contain iridium compound between 95 and 100% even near the grain surface.

  As the iridium compound contained in the inside of the particle and in the vicinity of the particle surface, for example, the exemplified compounds II-1 to II-20 described above can be preferably used.

  The iridium compound may contain the same compound inside the particle and in the vicinity of the particle surface, or may be different. Moreover, you may contain combining a some compound. In addition, it is also preferable to use other metal compounds in combination in any combination as long as the effects of the present invention are not impaired.

  As a further preferred embodiment of the mode applied to the emulsion of the present invention described above, a host emulsion to which the above-mentioned photographically useful compound, particularly a high silver chloride fine grain emulsion containing an iridium compound is added as a guest, It is mentioned that the metal compound satisfy | fills satisfy | filling.

Here, the condition A is the microwave photoconductivity of a silver halide emulsion composed of silver chloride cubic crystals having an average side length of 0.4 μm, in which the metal compound is uniformly added at 1 × 10 ⁻⁸ mol per mol of silver halide. The decay time of the photoconductivity signal in the induced absorption of the measurement is not more than the decay time of the photoconductivity signal of the silver halide emulsion in which the metal compound is substituted with equimolar potassium hexachloroiridium (IV).

A silver halide emulsion composed of silver chloride cubic crystals having an average side length of 0.4 μm and uniformly added with a metal compound satisfying the condition A can be prepared by a known method. For example, it can be easily prepared by the simultaneous mixing method, and is prepared by adding an amount corresponding to 1 × 10 ⁻⁸ mol of a desired metal compound contained in an aqueous chloride ion solution per mol of silver halide. This may be mixed with an aqueous silver salt solution.

  The microwave photoconductivity measurement characterizing the metal compound is a method for evaluating the physical properties of silver salt photographic emulsions well known in the art. M.M. Measurement can be performed with reference to the method described in Kellogg; Photographic Science and Engineering, Vol. 18, 378 (1974). About the microwave photoconductivity measurement in this application, it carried out according to description of Unexamined-Japanese-Patent No. 5-45758. Further, the decay time of photoconductivity in the microwave photoconductivity measurement in the present application is defined as the time required to decay to half the peak intensity.

The decay time of the photoconductivity signal in the induced absorption of microwave photoconductivity measurement was such that potassium hexachloroiridium (IV) was uniformly added at 1 × 10 ⁻⁸ mol per mol of silver halide, and the average side length was 0.4 μm. As a metal compound for obtaining an emulsion having a silver halide emulsion composed of silver chloride cubic crystals (hereinafter referred to as a comparative emulsion under Condition A) or less, a certain kind of metal complex can be preferably used. As the metal complex that can be used for this purpose, those represented by the following general formula [I] are preferable.
Formula [I] R ¹ _n1 [M ¹ X ¹ _m1 Y ¹ _6-m1 ]
In the formula, M ¹ represents a metal selected from Group 8 elements of the periodic table, preferably iron, cobalt, ruthenium, rhodium, osmium, nickel, palladium and iridium. R ¹ represents an ant potassium metal atom, preferably sodium or potassium. m ₁ represents an integer of 0 to 6, and n ₁ represents an integer of 2 to 5.

X ¹ and Y ¹ each represent a ligand of the above metal complex, preferably a group such as nitrosyl, thionitrosyl, or carbonyl, and a compound in which some or all of the ligands are halide ions is also preferably used.

The amount of the metal compound is preferably 10 ⁻⁹ to 10 ⁻⁵ mol per mol of silver halide. It is preferable that these metal compounds are present inside the particles at 50% or less of the particle volume.

The following compounds can be mentioned as typical examples of metal compounds that are preferably used.
I-1: K ₂ [RuCl ₆ ], I-2: K ₂ [PtCl ₆ ],
I-3: K ₂ [Pt (SCN) ₄ ], I-4: K ₂ [NiCl ₄ ],
I-5: K ₂ [PdCl ₆ ], I-6: K ₃ [RhCl ₆ ],
I-7: K ₂ [OsCl ₆ ], I-8: K ₂ [ReCl ₆ ],
I-9: K ₃ [RhBr ₆ ], I-10: K ₃ [Mo (OCN) ₆ ],
I-11: K ₃ [Re (CNO) ₆ ], I-12: K ₄ [Ru (CNO) ₆ ],
I-13: K ₄ [Fe (CNO) ₆ ], I-14: K ₂ [Pt (CNO) ₄ ],
I-15: K ₃ [Co (NH ₃ ) ₆ ], I-16: K ₅ [Co ₂ (CNO) ₁₁ ],
I-17: K ₃ [Re (CNO) ₆ ], I-18: K ₄ [Os (CNO) ₆ ],
I-19: Cs ₂ [Os (NO) Cl ₅ ],
I-20: K ₂ [Ru (NO) Cl ₅ ], I-21: K ₂ [Ru (CO) Cl ₅ ],
I-22: Cs ₂ [Os (CO) Cl ₅ ],
I-23: K ₂ [Fe (NO) (CN) ₅ ],
I-24: K ₂ [Ru (NO) Br ₅ ], I-25: K ₂ [Ru (NO) I ₅ ],
I-26: K ₂ [Re (NO) (CN) ₅ ],
I-27: K ₂ [Re (NO) Cl ₅ ], I-28: K ₂ [Ir (NO) Cl ₅ ]
_{I-29: K 2 [Ru} (NS) Cl 5], I-30: K 2 [Os (NS) Br 5]
I-31: K ₂ [Ru (NS) (CN) ₅ ]
I-32: K ₂ [Ru (NS) (SCN) ₅ ]
Any silver halide grains according to the present invention can be used as long as they have a high silver chloride composition. One preferable example is a cube having a (100) plane as a crystal surface. Also, U.S. Pat. Nos. 4,183,756 and 4,225,666, JP-A-55-26589, JP-B-55-42737, and The Journal of Photographic Science (J. Photogr. Sci.), Vol. 21, p. 39 (1973), etc., particles having an octahedral, tetradecahedral, dodecahedron, etc. shape can be produced and used. Furthermore, particles having twin planes may be used.

  As the silver halide grains, grains having a single shape are preferably used, but it is particularly preferable to add two or more monodispersed silver halide emulsions in the same layer.

  The grain size of the silver halide grains is not particularly limited, but is preferably 0.1 to 1.2 μm, more preferably 0.2 to 1.0 μm, considering other photographic performance such as rapid processability and sensitivity. Range. This particle size can be measured using the projected area or diameter approximation of the particle. If the particles are of a substantially uniform shape, the particle size distribution can represent this fairly accurately as a diameter or projected area.

  The particle size distribution of the silver halide grains is preferably monodispersed silver halide grains having a coefficient of variation of 0.05 to 0.22, more preferably 0.05 to 0.15, and particularly preferably 0.05. The addition of two or more monodispersed emulsions of .about.0.15 to the same layer. Here, the variation coefficient is a coefficient representing the breadth of the particle size distribution, and is defined by the following equation.

Coefficient of variation = S / R (S is the standard deviation of the particle size distribution, R is the average particle size)
The particle diameter referred to here is the diameter in the case of spherical silver halide grains, and the diameter when the projected image is converted into a circular image of the same area in the case of grains other than a cube or a sphere. Represents.

  As a silver halide emulsion preparation apparatus and method, various methods known in the art can be used.

  The silver halide emulsion may be obtained by any of the acidic method, neutral method and ammonia method. The particles may be grown at one time, or may be grown after producing seed particles. The method for producing seed particles and the method for growing them may be the same or different.

  The form of reacting the soluble silver salt and the soluble halide may be any of a forward mixing method, a back mixing method, a simultaneous mixing method, a combination thereof, and the like, but those obtained by the simultaneous mixing method are preferred. Furthermore, as one form of the simultaneous mixing method, the pAg controlled double jet method described in JP-A No. 54-48521 can also be used.

  Further, a device for supplying a water-soluble silver salt and a water-soluble halide aqueous solution from an adding device arranged in a reaction mother liquor described in JP-A-57-92523, JP-A-57-92524 and the like; An apparatus for continuously adding water-soluble silver salt and water-soluble halide aqueous solution described in No. 921,164 etc., taking out the reaction mother liquor outside the reactor described in JP-B-56-501776, etc. An apparatus that forms grains while keeping the distance between silver halide grains constant by concentrating by ultrafiltration may be used.

  Further, if necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound, or a compound such as a sensitizing dye may be added and used at the time of forming silver halide grains or after the completion of grain formation.

  The silver halide emulsion can be used in combination of a sensitizing method using a gold compound and a sensitizing method using a chalcogen sensitizer.

  As a chalcogen sensitizer applied to the silver halide emulsion, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer and the like can be used, and a sulfur sensitizer is preferred.

  Examples of the sulfur sensitizer include thiosulfate, allylthiocarbamide, thiourea, allyl isothiocyanate, cystine, p-toluenethiosulfonate, rhodanine, inorganic sulfur and the like.

The amount of sulfur sensitizer added is preferably changed depending on the type of silver halide emulsion to be applied and the magnitude of the expected effect, but 5 × 10 ^{−10 to} 5 × 10 ⁻⁵ per mole of silver halide. The mole is preferably in the range of 5 × 10 ^{−8 to} 3 × 10 ⁻⁵ mol.

As the gold sensitizer, various gold complexes such as chloroauric acid and gold sulfide can be added. Examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, mercaptotriazole and the like. The amount of gold compound used is not uniform depending on the type of silver halide emulsion, the type of compound used, ripening conditions, etc., but usually 1 × 10 ⁻⁴ to 1 × 10 ⁻⁸ mol per mol of silver halide. It is preferable that it is 1 * 10 < ^-5 > -1 * 10 <^-8> mol.

  As chemical sensitization of silver halide emulsions, reduction sensitization may be used.

  For the silver halide emulsion, known antifoggants and stabilizers are used for the purpose of preventing fogging during the preparation process of the light-sensitive material, reducing fluctuations in performance during storage, and preventing fogging during development. be able to. As an example of a preferable compound used for such purpose, there can be mentioned a compound represented by the general formula [II] described in JP-A-2-14636, page 7, lower column, and more preferable specific compounds include IIa-1 to IIa-8 and IIb-1 to IIb-7 described on page 8 of the same publication, 1- (3-methoxyphenyl) -5-mercaptotetrazole, 1- (4-ethoxyphenyl)- Mention may be made of compounds such as 5-mercaptotetrazole.

Depending on the purpose, these compounds are added in steps such as a silver halide emulsion grain preparation step, a chemical sensitization step, a chemical sensitization step, and a coating solution preparation step. When chemical sensitization is performed in the presence of these compounds, it is preferably used in an amount of about 1 × 10 ^{−5 to} 5 × 10 ⁻⁴ mol per mol of silver halide. When added at the end of chemical sensitization, the amount is preferably about 1 × 10 ⁻⁶ to 1 × 10 ⁻² mol per mol of silver halide, more preferably 1 × 10 ^{−5 to} 5 × 10 ⁻³ mol. . When added to the silver halide emulsion layer in the coating solution preparation step, the amount of 1 × 10 ^-6 to 1 × 10 ^-1 mol per mol of silver halide is preferred, 1 × 10 ^-5 ~ × 10 ^{- Two} moles are more preferred. When added to a layer other than the silver halide emulsion layer, the amount in the coating film is preferably about 1 × 10 ⁻⁹ to 1 × 10 ⁻³ mol per 1 m ² .

  For the photosensitive material, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation. For this purpose, any known compound can be used. In particular, as dyes having absorption in the visible region, dyes AI-1 to 11 described in JP-A-3-251840, page 30 and JP-A-6 The dyes described in No.-3770 are preferably used, and as the infrared absorbing dye, compounds represented by the general formulas (I), (II) and (III) described in JP-A-1-280750, page 2, lower left column are preferable. It has spectral characteristics, is not affected by photographic characteristics of photographic emulsions, and is free from contamination by residual colors. Specific examples of preferred compounds include the exemplified compounds (1) to (45) listed in the same publication, page 3, lower left column to page 5, lower left column. For the purpose of improving sharpness, the amount of these dyes added is preferably such that the spectral reflection density at 680 nm of the untreated sample of the light-sensitive material is 0.7 to 3.0, more preferably 0.8 to More preferably, it is 3.0.

  It is preferable to add a fluorescent brightening agent to the light-sensitive material because white background can be improved. Preferred examples of the compound include compounds represented by the general formula [II] described in JP-A-2-232652.

  When the light-sensitive material of the present invention is used as a color light-sensitive material, it has a layer containing a silver halide emulsion spectrally sensitized in a specific region of a wavelength region of 400 to 900 nm in combination with a yellow coupler, a magenta coupler, and a cyan coupler. . The silver halide emulsion contains one or more sensitizing dyes in combination.

  As the spectral sensitizing dye used in the present invention, any known compound can be used. As the blue-sensitive sensitizing dye, BS-1 to BS-8 described in JP-A-3-251840, page 28, are used. Can be preferably used alone or in combination. As the green photosensitive sensitizing dye, GS-1 to GS-5 described on page 28 of the same publication are preferable, and as the red photosensitive sensitizing dye, RS-1 to RS-8 described on page 29 of the same publication. Is preferably used. In addition, when performing image exposure with infrared light using a semiconductor laser or the like, it is necessary to use an infrared photosensitive sensitizing dye. As an infrared photosensitive sensitizing dye, JP-A-4-285950 is disclosed. Nos., Pages 6 to 8, and IRS-1 to IRS-11 dyes are preferably used. Further, these infrared, red, green and blue photosensitive sensitizing dyes are supersensitizers SS-1 to SS-9 described in JP-A-4-285950, pages 8 to 9 and JP-A-5-66515. No., pages 15 to 17 are preferably used in combination with compounds S-1 to S-17.

  The time for adding the sensitizing dye may be any time from the formation of silver halide grains to the end of chemical sensitization.

  As a method for adding a sensitizing dye, it may be added as a solution by dissolving in water-miscible organic solvent such as methanol, ethanol, fluorinated alcohol, acetone, dimethylformamide or water, or as a solid dispersion. Also good.

  As the coupler used in the light-sensitive material of the present invention, any compound capable of forming a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm by a coupling reaction with an oxidized form of a color developing agent is used. However, particularly representative couplers include a yellow dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, a magenta dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 500 to 600 nm, and a wavelength range of 600 to Those known as cyan dye-forming couplers having a spectral absorption maximum wavelength at 750 nm may be mentioned.

  Examples of cyan couplers that can be preferably used include couplers represented by the general formulas [CI] and [C-II] described in JP-A-4-114154, page 5, lower left column. Examples of the compound include those described as CC-1 to CC-9 in page 5, lower right column to page 6, lower left column.

Examples of magenta couplers that can be preferably used include couplers represented by the general formulas [M-I] and [M-II] described in JP-A-4-114154, page 4, upper right column. Examples of the compound include those described as MC-1 to MC-11 in page 4, lower left column to page 5, upper right column. Among the magenta couplers, more preferred is a coupler represented by the general formula [M-I], and among them, a coupler in which R _{M of the} general formula [M-I] is a tertiary alkyl group is a light fastness. And particularly preferred. MC-8 to MC-11 described in the upper column on page 5 of the same publication are preferable because they are excellent in reproducing colors ranging from blue to purple and red, and are excellent in detail descriptive power.

Examples of yellow couplers that can be preferably used include couplers represented by the general formula [YI] described in JP-A-4-114154, page 3, upper right column. What is described as YC-1 to YC-9 after the column can be mentioned. Among them, a coupler in which R _Y1 in the general formula [YI] is an alkoxy group, or a coupler represented by the general formula [I] described in JP-A-6-67388 is preferable because it can reproduce yellow having a preferable color tone. Among these, as particularly preferred compound examples, YC-8 and YC-9 described in JP-A-4-114154, page 4, upper left column and Nos. (1) to (47) described in JP-A-6-67388, pages 13-14. ) Can be mentioned. The most preferred compounds are those represented by the general formula [Y-1] described in JP-A-4-81847, pages 1 and 11-17.

  When using an oil-in-water type emulsion dispersion method to add a coupler or other organic compound used in a light-sensitive material, usually a water-insoluble high-boiling organic solvent having a boiling point of 150 ° C. or higher is used. And / or dissolved in combination with a water-soluble organic solvent, and emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. As a dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser, or the like can be used. A step of removing the low boiling point organic solvent may be added after the dispersion or simultaneously with the dispersion.

  Examples of high-boiling organic solvents that can be used to dissolve and disperse couplers include phthalic acid esters such as dioctyl phthalate, di-i-decyl phthalate, and dibutyl phthalate, and phosphoric acid such as tricresyl phosphate and trioctyl phosphate. Esters are preferably used. The dielectric constant of the high boiling point organic solvent is preferably 3.5 to 7.0. Two or more high boiling point organic solvents can be used in combination.

  Further, instead of using a high-boiling organic solvent or in combination with a high-boiling organic solvent, a water-insoluble and organic solvent-soluble polymer compound is dissolved in a low-boiling and / or water-soluble organic solvent as necessary. In addition, a method of emulsifying and dispersing by various dispersing means using a surfactant in a hydrophilic binder such as an aqueous gelatin solution can also be employed. Examples of the water-insoluble and organic solvent-soluble polymer used at this time include poly (Nt-butylacrylamide).

  Preferred compounds as surfactants used to disperse photographic additives and adjust the surface tension during application include those containing a hydrophobic group having 8 to 30 carbon atoms and a sulfonic acid group or a salt thereof in one molecule. Is mentioned. Specific examples include A-1 to A-11 described in JP-A No. 64-26854. A surfactant having a fluorine atom substituted on an alkyl group is also preferably used. These dispersions are usually added to a coating solution containing a silver halide emulsion, but it is better that the time until dispersion is added to the coating solution after dispersion and the time after addition to the coating solution is shorter. Each is preferably within 10 hours, more preferably within 3 hours and within 20 minutes.

  Each of the above couplers is preferably used in combination with an anti-fading agent in order to prevent fading of the formed dye image due to light, heat, humidity and the like. Particularly preferred compounds include phenyl ether compounds represented by general formulas [I] and [II] described on page 3 of JP-A-2-665541, and phenols represented by general formula [IIIB] described in JP-A-3-174150. Compounds, amine compounds represented by general formula [A] described in JP-A No. 64-90445, general formulas [XII], [XIII], [XIV], [XV] described in JP-A No. 62-182741 Are particularly preferred for magenta dyes. Further, compounds represented by the general formula [I] described in JP-A-1-196049 and compounds represented by the general formula [II] described in JP-A-5-11417 are particularly preferred for yellow and cyan dyes.

  For the purpose of shifting the absorption wavelength of the coloring dye, compounds such as compound d-11 described in JP-A-4-114154, page 9, lower left column, compound A'-1 described in page 10, upper left column, and the like can be used. . In addition, the fluorescent dye releasing compound described in US Pat. No. 4,774,187 can also be used.

  In light-sensitive materials, a compound that reacts with the oxidized developer is added to the layer between the light-sensitive layer to prevent color turbidity, or it is added to the silver halide emulsion layer to improve fog and the like. It is preferable. The compound for this purpose is preferably a hydroquinone derivative, more preferably a dialkyl hydroquinone such as 2,5-di-t-octyl hydroquinone. Particularly preferred compounds are compounds represented by the general formula [II] described in JP-A-4-13356, and are compounds II-1 to II-14 described on pages 13 to 14 and compounds-1 described on page 17 Is mentioned.

  In the photosensitive material, it is preferable to add an ultraviolet absorber to prevent static fogging or to improve the light resistance of the dye image. Preferred ultraviolet absorbers include benzotriazoles, and particularly preferred compounds are those represented by general formula [III-3] described in JP-A-1-250944, and general formula [III described in JP-A 64-66646. A compound represented by general formula [I] described in JP-A No. 63-187240, a compound represented by general formula [I] described in JP-A No. 4-1633, and a general formula described in JP-A No. 5-165144. Examples include compounds represented by formulas (I) and (II).

  In the light-sensitive material of the present invention, it is advantageous to use gelatin as a binder, but if necessary, gelatin derivatives, gelatin and other polymer graft polymers, proteins other than gelatin, sugar derivatives, cellulose derivatives, single or Hydrophilic colloids such as synthetic hydrophilic polymer materials such as copolymers can also be used.

  As these binder hardeners, vinylsulfone type hardeners, chlorotriazine type hardeners, and carboxyl group active hardeners are preferably used alone or in combination. It is preferable to use compounds described in JP-A Nos. 61-249054 and 61-245153. Further, in order to prevent the growth of soot and bacteria that adversely affect photographic performance and image storage stability, it is preferable to add a preservative and an antifungal agent as described in JP-A-3-157646 in the colloid layer. In order to improve the physical properties of the surface of the photosensitive material or processed sample, it is preferable to add a slipping agent or a matting agent described in JP-A-6-118543 and JP-A-2-73250 to the protective layer.

  As the support used for the photosensitive material, any material may be used, including paper coated with polyethylene or polyethylene terephthalate, paper support made of natural pulp or synthetic pulp, vinyl chloride sheet, and white pigment. Good polypropylene, polyethylene terephthalate support, baryta paper and the like can be used. Among these, a support having a water-resistant resin coating layer on both sides of the base paper is preferable.

  As the water resistant resin, polyethylene, polyethylene terephthalate or a copolymer thereof is preferable.

  As the white pigment used for the support, inorganic and / or organic white pigments can be used, and inorganic white pigments are preferably used. For example, alkaline earth metal sulfate such as barium sulfate, alkaline earth metal carbonate such as calcium carbonate, silica such as fine silicate, synthetic silicate, calcium silicate, alumina, alumina hydrate, titanium oxide, oxidation Examples include zinc, talc, and clay. The white pigment is preferably barium sulfate or titanium oxide.

  The amount of the white pigment contained in the water-resistant resin layer on the surface of the support is preferably 13% by mass or more, and more preferably 15% by mass for improving sharpness.

  The degree of dispersion of the white pigment in the water-resistant resin layer of the paper support can be measured by the method described in JP-A-2-28640. When measured by this method, the degree of dispersion of the white pigment is preferably 0.20 or less, and more preferably 0.15 or less, as the coefficient of variation described in the publication.

  Further, it is more preferable that the average surface roughness (SRa) of the support is 0.15 μm or less, and further 0.12 μm or less, because the effect of good gloss is obtained. In addition, in order to improve the whiteness by adjusting the spectral reflection density balance of the white background after processing in the white pigment-containing water-resistant resin of the reflective support or in the coated hydrophilic colloid layer, ultramarine, oil-soluble dyes, etc. It is preferable to add a small amount of a blue tinting agent or a red tinting agent.

  The photosensitive material is subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the support surface as necessary, and then directly or undercoat layer (support surface adhesion, antistatic properties, dimensional stability, friction resistance) May be applied via one or more subbing layers for improving the properties, hardness, antihalation properties, frictional properties and / or other properties.

  When coating a light-sensitive material using a silver halide emulsion, a thickener may be used to improve the coating property. As the coating method, extrusion coating and curtain coating capable of simultaneously coating two or more layers are particularly useful.

  In order to form a photographic image using the photosensitive material of the present invention, the image recorded on the negative may be optically imaged and printed on the photosensitive material to be printed. After conversion into information, the image may be formed on a CRT (cathode ray tube), and the image may be formed on a photosensitive material to be printed and printed. Baking is preferably performed by scanning with varying intensities.

  As an image forming method using a scanning exposure method, for example, Japanese Examined Patent Publication No. 62-21305 discloses a method of performing scanning exposure using a light emitting diode as a light source on a photographic photosensitive material. Japanese Patent Laid-Open No. 63-18346 discloses a scanning exposure method using a second harmonic obtained by using a semiconductor laser and an SHG element as a light source. In such print creation by digital printing in particular, it is preferable that a high-quality image can be obtained by exhibiting the effects of the present invention.

  The present invention is preferably applied to a photosensitive material in which a developing agent is not incorporated in the photosensitive material, and is particularly preferably applied to a photosensitive material that directly forms an image for viewing. Examples thereof include color paper, color reversal paper, a photosensitive material for forming a positive image, a photosensitive material for display, and a photosensitive material for color proof. In particular, it is preferably applied to a photosensitive material having a reflective support.

Known compounds can be used as the aromatic primary amine developing agent used for color development. Examples of these compounds include the following compounds.
CD-1: N, N-diethyl-p-phenylenediamine CD-2: 2-amino-5-diethylaminotoluene CD-3: 2-amino-5- (N-ethyl-N-lauryl) aminotoluene CD-4 : 4- (N-ethyl-N-β-hydroxyethyl) aminoaniline CD-5: 2-methyl-4- (N-ethyl-N-β-hydroxyethyl) aminoaniline CD-6: 4-amino-3 -Methyl-N-ethyl-N- (β-methanesulfonamido) ethylaniline CD-7: 4-amino-3-β-methanesulfonamidoethyl-N, N-diethylaniline CD-8: N, N-dimethyl -P-phenylenediamine CD-9: 4-amino-3-methyl-N-ethyl-N-methoxyethylaniline CD-10: 4-amino-3-methyl-N-ethyl-N- (β- Toxiethyl) aniline CD-11: 4-amino-3-methyl-N-ethyl-N- (γ-hydroxypropyl) ethylaniline In the present invention, a color developer containing the above developing agent is used in an arbitrary pH range. However, from the viewpoint of rapid processing, the pH is preferably 9.5 to 13.0, and more preferably pH 9.8 to 12.0.

  The processing temperature for color development is preferably 35 to 70 ° C. The higher the temperature, the shorter the treatment possible, which is preferable. However, it is preferable that the temperature is not so high from the stability of the processing solution, and it is more preferable to perform the treatment at 37 to 60 ° C.

  Conventionally, the color development time is generally about 3 minutes 30 seconds, but in the present invention, it is preferably within 40 seconds, and more preferably within 25 seconds.

  In addition to the above color developing agent, a known developer component compound can be added to the color developer. Usually, an alkali agent having a pH buffering action, a development inhibitor such as chlorine ions and benzotriazoles, a preservative, and a chelating agent are used.

  The photosensitive material is subjected to bleaching and fixing after color development. The bleaching process may be performed simultaneously with the fixing process. After the fixing process, a washing process is usually performed. Moreover, you may perform a stabilization process as an alternative of a water-washing process.

  The development processing apparatus used for processing the photosensitive material of the present invention is a roller transport type that transports the photosensitive material sandwiched between rollers arranged in a processing tank, and transports the photosensitive material fixed to the belt. Although an endless belt method may be used, a processing tank is formed in a slit shape, a processing liquid is supplied to the processing tank and a photosensitive material is conveyed, a spraying method in which the processing liquid is sprayed, and a processing liquid. A web system by contact with the impregnated carrier, a system using a viscous processing liquid, or the like can also be used. When processing in large quantities, it is usually performed using an automatic processor, but at this time, it is preferable that the replenisher is replenished in a smaller amount. The method described in the published technical report No. 94-16935 is most preferable.

  The light-sensitive material of the present invention can be preferably applied to a heat development system. Thermal development refers to a method of developing by heating the exposed photosensitive material to 50 to 250 ° C., preferably 60 to 150 ° C.

  For the heat treatment, for example, as described in JP-A-63-71850, a photosensitive material is sandwiched between a heat drum and a drum belt, or the photosensitive material is interposed between a heater and a support base. By setting and heating at the same time as pressurization, the so-called direct heating method, the method of passing a photosensitive material between far infrared heaters described in JP-A-4-240642, etc., or by irradiating microwaves A so-called indirect heating method for heating, or a method in which a direct heating method and an indirect heating method are combined can be used.

  In thermal development, as described in, for example, JP-A-63-108337, a so-called one-sheet system in which a single photosensitive material is used for exposure and thermal development to obtain a final image, or As described in Example 1 of JP-A-6-95321, Example 1 of JP-A-7-225461, etc., a photosensitive material and a dye image-receiving material are used, and an image dye formed or released by heat development is extracted from the photosensitive material. Any of the so-called two-sheet methods can be used in which a final image is obtained by diffusion transfer to a dye image-receiving material. Also, a method in which a photosensitive layer and a dye image-receiving layer are laminated on one support, and image dyes formed or released by thermal development are diffused and transferred from the photosensitive layer to the dye image-receiving layer, and then the photosensitive layer is peeled and removed. Can also be preferably used.

  In thermal development, for example, as described in Example 1 of JP-A-2-12039, a method of developing only by heating without supplying a reaction aid from the outside, or JP-A-9-5968 As described in Example 1 or the like, any of the methods of performing thermal development after supplying a small amount of a reaction aid (such as water) to the photosensitive material as necessary during thermal development can be used. When there is no supply of reaction aid from the outside, an embodiment in which a so-called thermal solvent that is solid at normal temperature but liquefies at the heat development temperature is preliminarily included in the photosensitive material is preferable. For example, compounds described in JP-A No. 1-227150, page 4, upper left column to page 9, upper right column and JP-A-4-289856, columns “0015” to “0018” can be preferably used.

  Further, it is preferable to use a base generator from the viewpoint of improving the silver developing speed and improving the diffusion speed of image dyes. As the base generating method, for example, JP-A-59-157737, page 3, lower right to page 6, 59-180537, a method using a compound that generates a base by thermal decomposition, as described in the upper left column of page 4 to the lower left column of page 7, JP-A-8-87097, European Patent Publication 210,660, US As described in Japanese Patent No. 4,740,445, etc., in the presence of a small amount of water, a complex formed by using a basic metal compound that is hardly soluble in water and a metal ion constituting the basic metal compound and water as a medium A method of generating a base by a combination of compounds that can react can be used.

  In heat development, from the viewpoint of accelerating silver development, an embodiment in which an organic silver salt is contained in the photosensitive material as necessary is also useful.

  Examples of the organic silver salt include silver salts of long-chain aliphatic carboxylic acids and silver salts of carboxylic acids having a heterocyclic ring described in JP-A-49-52626 and JP-A-53-36224. A silver salt of a compound having an imino group described in JP-A Nos. 137321 and 58-118638, or a silver salt of an acetylene compound described in JP-A No. 61-249044 can be preferably used.

  In heat development, it is preferable to use a dye mordant in combination from the viewpoint of reducing image bleeding and fading when the final image is stored. As the dye mordant, a polymer containing a tertiary amine or a quaternary ammonium salt is preferable. For example, compounds described in JP-A-9-5968 “0057” to “0060” can be preferably used.

  When the light-sensitive material of the present invention is used for heat development, examples of compounds (dye-donating substances) that form or release image dyes include, for example, JP-A-61-61157, 61-61158, and 62-44738. Couplers for forming diffusible dyes described in JP-A Nos. 62-129850, 62-129851, 62-169158, and JP-A-3-73949, and JP-A-61-88254. Leuco dyes, azo dyes described in U.S. Pat. No. 4,235,957, etc., or JP-A-59-60434, 59-65839, 59-71046, 59-87450, 59-165055. Compounds described in JP-A-59-55430, 59-165504, 59-154445, 59-116655, 59-12 327 No., the 59-152440 JP, said 64-13546 Patent, compounds capable of forming a silver development and inverse correspondence to image dye described in JP-A 6-51474 Patent and the like preferably.

  Further, for example, a photosensitive material using a microcapsule containing a polymerizable compound described in JP-A-2-293533 and JP-A-2-308162 and the above-described dye-donating substance, and imagewise or reversely imagewise by heat development. It is also possible to use a heat development method in which the microcapsules are cured by carrying out a polymerization reaction, the diffusion rate of the image dye and the physical strength of the binder are changed, and an image is formed.

  In the light-sensitive material of the present invention, an embodiment in which a developing agent or a precursor thereof is incorporated can also be used. The developing agent incorporated in the photosensitive material is required to be stable during storage of the photosensitive material and not to reduce the silver salt unnecessarily. As developing agents satisfying such requirements, paraphenylenediamine-based agents described in JP-A-62-228835, sulfonamide phenol-based agents described in JP-A-9-15806, JP-A-5-241282, Hydrazine-based active agents described in JP-A-8-234388, JP-A-8-286340, JP-A-9-152700, JP-A-9-152701, JP-A-9-152702, JP-A-9-152703, JP-A-9-152704, etc. Examples thereof include hydrazone-based active agents described in Kaihei 7-202002, 8-234390 and the like.

  When the photosensitive material contains a developing agent, development by an activator process can be preferably used in addition to the above-described heat development process. Activator processing refers to a processing method in which development processing is performed with a processing solution that does not contain a color developing agent (activator solution), and a compound necessary for color development is incorporated in the photosensitive material in advance. The activator in this case is characterized by not containing the color developing agent contained in the usual color developing solution components, and may contain other components such as alkali, auxiliary developing agent and the like. The activator treatment is exemplified in known documents such as European Patent Nos. 545,491A1 and 565,165A1.

EXAMPLES Hereinafter, although an Example demonstrates this invention, the embodiment of this invention is not limited to these.
Example 1
High-density polyethylene was laminated on both sides of a paper pulp having a basis weight of 180 g / m ² to prepare a paper support. However, on the side on which the emulsion layer was applied, a melted polyethylene containing a surface-treated anatase-type titanium oxide dispersed at a content of 15% by mass was laminated to prepare a reflective support. After the reflective support was subjected to corona discharge treatment, a gelatin subbing layer was provided, and each layer having the following constitution was further applied to produce a silver halide photographic light-sensitive material. The coating solution was prepared as follows.
First layer coating solution Yellow coupler (Y-1) 23.4 g, dye image stabilizer (ST-1) 3.34 g, (ST-2) 3.34 g, (ST-5) 3.34 g, stain prevention 60 ml of ethyl acetate was dissolved in 0.34 g of the agent (HQ-1), 5.0 g of the image stabilizer A, 3.33 g of the high boiling point organic solvent (DBP) and 1.67 g of the high boiling point organic solvent (DNP), and this solution was dissolved. A yellow coupler dispersion was prepared by emulsifying and dispersing in 220 ml of a 10% gelatin aqueous solution containing 7 ml of 20% surfactant (SU-1) using an ultrasonic homogenizer. This dispersion was mixed with a blue-sensitive silver halide emulsion prepared under the following conditions to prepare a first layer coating solution.

  Each coating solution was prepared so that the coating amounts of the second to seventh layer coating solutions were as shown in Tables 1 and 2 in the same manner as the first layer coating solution.

Moreover, (H-1) and (H-2) were added as a hardening agent. As coating aids, surfactants (SU-2) and (SU-3) were added to adjust the surface tension. Further, an antifungal agent (F-1) was added to each layer so that the total amount was 0.04 g / m ² .

SU-1: sodium tri-i-propylnaphthalenesulfonate SU-2: di (2-ethylhexyl) sulfosuccinate / sodium salt SU-3: disulfooxalate (2,2,3,3,4,4,4) 5,5-octafluoropentyl) sodium salt DBP: dibutyl phthalate DNP: dinonyl phthalate DOP: dioctyl phthalate DIDP: di-i-decyl phthalate PVP: polyvinyl pyrrolidone H-1: tetrakis (vinylsulfonylmethyl) methane H-2 : 2,4-dichloro-6-hydroxy-s-triazine sodium HQ-1: 2,5-di-t-octyl hydroquinone HQ-2: 2,5-di-sec-dodecyl hydroquinone HQ-3: 2, 5-Di-sec-tetradecylhydroquinone HQ-4: 2-sec-dodecyl-5 ec- tetradecyl hydroquinone HQ-5: 2,5-di [(1,1-dimethyl-4-hexyloxycarbonyl) butyl] hydroquinone image stabilizer A: p-t-octylphenol

(Preparation of blue-sensitive silver halide emulsion)
The following (A ₀ solution) and (B ₀ solution) were simultaneously added to 1 liter of 2% gelatin aqueous solution kept at 40 ° C. over 15 minutes while controlling pAg = 7.3 and pH = 3.0. The following (C ₀ solution) and (D ₀ solution) were simultaneously added over 180 minutes while controlling pAg = 8.0 and pH = 5.5. At this time, pAg was controlled by the method described in JP-A-59-45437, and pH was controlled using sulfuric acid or an aqueous sodium hydroxide solution.
(A ₀ solution)
Sodium chloride 1.03g
Potassium bromide 0.01g
60ml with water
(B ₀ solution)
Silver nitrate 3g
60ml with water
(C ₀ liquid)
Sodium chloride 102.7g
K ₂ IrCl ₆ 4 × 10 ⁻⁸ mol / mol Ag
K ₄ Fe (CN) ₆ 2 × 10 ⁻⁵ mol / mol Ag
Potassium bromide 1.0g
600ml with water
(D ₀ solution)
300 g of silver nitrate
600ml with water
After completion of the addition, desalting was performed using a 5% aqueous solution of Demol N made by Kao Atlas and a 20% aqueous solution of magnesium sulfate, and then mixed with an aqueous gelatin solution to obtain an average particle size of 0.71 μm and a coefficient of variation in particle size distribution A monodispersed cubic emulsion (EMP-1) having 0.07 and a silver chloride content of 99.5 mol% was obtained.

Next, an average particle size of 0.64 μm was obtained in the same manner as EMP-1 except that the addition time of (A ₀ solution) and (B ₀ solution) and the addition time of (C ₀ solution) and (D ₀ solution) were changed. A monodispersed cubic emulsion (EMP-1B) having a coefficient of variation of 0.07 and a silver chloride content of 99.5 mol% was obtained.

  The above EMP-1 was optimally chemically sensitized at 60 ° C. using the following compounds. Similarly, after EMP-1B was optimally chemically sensitized, sensitized EMP-1 and EMP-1B were mixed at a silver ratio of 1: 1 to obtain a blue-sensitive silver halide emulsion ( Em-B101) was obtained.

Sodium thiosulfate 0.8mg / mol AgX
Chloroauric acid 0.5mg / mol AgX
Stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX
Stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX
Stabilizer STAB-3 3 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye BS-2 1 × 10 ⁻⁴ mol / mol AgX
STAB-1: 1- (3-acetamidophenyl) -5-mercaptotetrazole STAB-2: 1-phenyl-5-mercaptotetrazole STAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole (green sensitive halogen) Preparation of silver halide emulsion)
Same as EMP-1, except that the addition time of (A ₀ solution) and (B ₀ solution) and the addition time of (C ₀ solution) and (D ₀ solution) were changed. A monodispersed cubic emulsion (EMP-2) having 0.08 and a silver chloride content of 99.5% was obtained.

  Next, a monodispersed cubic emulsion (EMP-2B) having an average particle size of 0.50 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5% was obtained.

  The EMP-2 was optimally chemically sensitized at 65 ° C. using the following compounds. Similarly, EMP-2B was also optimally chemically sensitized, and then sensitized EMP-2 and EMP-2B were mixed at a silver ratio of 1: 1 to obtain a green sensitive silver halide emulsion ( Em-G101) was obtained.

Sodium thiosulfate 1.5mg / mol AgX
Chloroauric acid 1.0mg / mol AgX
Stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX
Stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX
Stabilizer STAB-3 3 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX
(Preparation of red-sensitive silver halide emulsion)
(Preparation of silver halide host emulsion)
The following (A ₁ solution) and (B ₁ solution) were simultaneously added to 1 liter of a 2% gelatin aqueous solution kept at 40 ° C. over 30 minutes while controlling pAg = 7.3 and pH = 3.0. The following (C ₁ solution) and (D ₁ solution) were simultaneously added over 120 minutes while controlling pAg = 8.0 and pH = 5.5. At this time, pAg was controlled by the method described in JP-A-59-45437, and pH was controlled using sulfuric acid or an aqueous sodium hydroxide solution.
(A ₁ solution)
Sodium chloride 3.42g
Potassium bromide 0.03g
200ml with water
(B ₁ liquid)
Silver nitrate 10g
200ml with water
(C ₁ solution)
Sodium chloride 102.7g
Metal compound (II-1) 2 × 10 ⁻⁸ mol Potassium bromide 1.0 g
600ml with water
(D ₁ solution)
300 g of silver nitrate
600ml with water
After completion of the addition, desalting was performed using a 5% aqueous solution of Demol N made by Kao Atlas and a 20% aqueous solution of magnesium sulfate, and then mixed with an aqueous gelatin solution to obtain an average particle size of 0.40 μm, a coefficient of variation of 0.08, A monodispersed cubic emulsion (EMP-11) having a silver chloride content of 99.5% was obtained.
(Preparation of fine grain silver halide emulsion)
The following (A ₂ solution) and (B ₂ solution) were simultaneously added to 1 liter of 2% gelatin aqueous solution kept at 40 ° C. over 10 minutes while controlling pAg = 7.3 and pH = 2.0.
(A ₂ liquid)
170 g silver nitrate
240ml with water
(B ₂ liquid)
Sodium chloride 58.5g
240ml with water
After completion of the addition, the pH is adjusted to 5.5 with sodium hydroxide, and then the salt is desalted until the conductivity becomes 3 mS / cm or less by circulating through the pipe attached with the ultrafiltration membrane with a pump. The gelatin concentration was adjusted to 2.5% by adding gelatin swollen with water. As a result of observation with an electron microscope, a silver chloride fine grain emulsion (EMX-10) having an average particle diameter of about 0.07 μm was obtained.

A silver chloride fine grain emulsion (EMX-11) was prepared in the same manner as in the preparation of the silver chloride fine grain emulsion EMX-10 except that 1 × 10 ⁻⁴ mol of the metal compound (II-1) was previously added to (B ₂ liquid). Obtained.

Furthermore, similarly, instead of the metal compound (II-1), 1 × 10 ⁻⁴ moles of STAB-1, chloroauric acid, metal compound (III-1) or (II-7) were used, and silver chloride was used. Fine grain emulsions (EMX-12) to (EMX-15) were obtained. Here, the metal compound (III-1) represents K ₂ [Fe (CN) ₆ ].

In the preparation of the silver chloride fine grain emulsion EMX-11, except that 20 mol%, 50 mol%, and all of the sodium chloride of (B ₂ solution) were replaced with the corresponding number of moles of potassium bromide, Silver chlorobromide fine grain emulsions (EMX-16), (EMX-17) and a silver bromide fine grain emulsion (EMX-18) were obtained.

  The above-mentioned host emulsion EMP-11 was optimally chemically and color sensitized at 50 ° C. using the following compounds to obtain a red-sensitive silver halide emulsion (Em-R101).

Triethylthiourea 1.0mg / mol AgX
Chloroauric acid 2.0mg / mol AgX
Stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX
Stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX
Stabilizer STAB-3 3 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye RS-2 1 × 10 ⁻⁴ mol / mol AgX
Supersensitizer SS-1 2 × 10 ⁻³ mol / mol AgX
The sensitizing dyes and supersensitizers used for the color sensitization of each color sensitive emulsion are as follows.

The red-sensitive silver halide was prepared in the same manner as in the preparation of the emulsion Em-R101, except that an aqueous solution of the metal compound (II-1) was added at 50 ° C. at 1 × 10 ⁻⁶ mol per mol of silver halide. An emulsion (Em-R102) was obtained.

  Next, the fine grain emulsions EMX-10 to EMX-18 were added to the host emulsion EMP-11 at 50 ° C., and the ripening was carried out by adding 1% equivalent to the amount of silver halide in the host emulsion. Subsequently, the compound was optimally chemically sensitized at 50 ° C. in the same manner as Em-R101 to obtain red-sensitive silver halide emulsions (Em-R103) to (Em-R111).

  Further, in the preparation of emulsion Em-R101, after optimal chemical sensitization and color sensitization were completed, silver chloride fine grain emulsion EMX-11 was subsequently added and matured at an amount corresponding to 1% per silver halide amount. In the same manner as above, a red-sensitive silver halide emulsion (Em-R112) was obtained.

Further, in the preparation of Emulsion Em-R101, when the addition of (C ₁ solution) and (D ₁ solution) during the preparation of Emulsion EMP-11 was completed 80%, the addition was temporarily stopped, and silver chloride fine grain emulsion EMX- 11 was added in an amount corresponding to 1% per silver halide amount and ripened. After the ripening, the remaining (C ₁ solution) and (D ₁ solution) were added, and thereafter, a silver halide emulsion (EMP-12) was prepared in the same manner. Color sensitization was performed to prepare a red-sensitive silver halide emulsion (Em-R113).

  Samples 102 to 113 having the contents shown in Table 3 were obtained in the same manner as in the preparation of Sample 101 except that Em-R102 to Em-R113 were used instead of emulsion Em-R101.

The samples 101 to 113 thus obtained were evaluated for illuminance change characteristics and long-term sample storage by the following methods. The results are shown in Table 3.
《Illuminance change characteristics》
Under each exposure condition, the light-sensitive material sample was subjected to wedge exposure with an exposure time of 100 seconds and 1 second with a tungsten lamp while appropriately adjusting the illuminance so as to obtain the lowest density to the highest density. Similarly, wedge exposure was performed with a xenon flash lamp at exposure times of 10 ⁻³ seconds and 10 ⁻⁶ seconds. Each exposed sample was color developed according to the following processing steps, and then the R (red) density was measured using a densitometer PDA-65 (manufactured by Konica).

  From the obtained characteristic curve, the maximum density (Dm) and gradation (γ) in the sample at each exposure time were calculated. Here, Dm and γ are defined as follows.

  Dm: Density at an exposure amount 2.0 LogE higher than the exposure amount giving a density higher by 0.1 than the fog density

γ: the average slope of the characteristic curve between 0.7 and 1.7 higher than the fog density.
<Long-term sample storage>
One unexposed sample was stored in a refrigerator for one month, and the other was stored for one month in a high temperature environment of 50 ° C. and 50%. Both were left unexposed and subjected to color development according to the following processing steps, and then the R density was measured under reflection density measurement conditions using an X-Rite 310TR densitometer (manufactured by X-Rite).

  The difference in minimum density of the sample stored in the high temperature environment with respect to the sample stored in the refrigerator was set as ΔFog, and the fog increase during storage of the photosensitive material was evaluated.

The prescription of the development processing step and the processing solution is as follows. The replenishment amount is expressed as the amount per 1 m ² of the photosensitive material. At this time, the Konica color QA paper type A7 was printed and run until the processing solution was replenished with a replenisher twice the tank capacity of the color developer.

Processing step Processing temperature Time Replenishment amount Color development 38.0 ± 0.3 ° C 45 seconds 80ml
Bleach fixing 35.0 ± 0.5 ℃ 45 seconds 120ml
Stabilization 30-34 ° C 60 seconds 150ml
Drying 60 to 80 ° C. 30 seconds (color developer tank solution and replenisher) Tank solution Replenisher Pure water 800 ml 800 ml
Triethylenediamine 2g 3g
Diethylene glycol 10g 10g
Potassium bromide 0.01g −
Potassium chloride 3.5g −
Potassium sulfite 0.25g 0.5g
N-ethyl-N- (β methanesulfonamidoethyl)
-3-Methyl-4-aminoaniline sulfate 6.0 g 10.0 g
N, N-diethylhydroxylamine 6.8 g 6.0 g
Triethanolamine 10.0 g 10.0 g
Diethylenetriaminepentaacetic acid sodium salt 2.0 g 2.0 g
Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 2.0 g 2.5 g
Potassium carbonate 30g 30g
Add water to bring the total volume to 1 liter, adjust the tank solution to pH = 10.10 and the replenisher solution to pH = 10.60.
(Bleaching fixer tank solution and replenisher solution)
65 g of diethylenetriaminepentaacetic acid ferric ammonium dihydrate
Diethylenetriaminepentaacetic acid 3g
Ammonium thiosulfate (70% aqueous solution) 100 ml
2-amino-5-mercapto-1,3,4-thiadiazole 2.0 g
Ammonium sulfite (40% aqueous solution) 27.5 ml
Add water to bring the total volume to 1 liter, and adjust to pH = 5.0 with potassium carbonate or glacial acetic acid.
(Stabilizer liquid and replenisher)
o-Phenylphenol 1.0g
5-Chloro-2-methyl-4-isothiazolin-3-one 0.02 g
2-Methyl-4-isothiazolin-3-one 0.02 g
Diethylene glycol 1.0g
Fluorescent brightener (Chinopearl SFP) 2.0g
1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g
Bismuth chloride (45% aqueous solution) 0.65 g
Magnesium sulfate heptahydrate 0.2g
Polyvinylpyrrolidone 1.0g
Ammonia water (25% ammonium hydroxide aqueous solution) 2.5 g
Nitrilotriacetic acid trisodium salt 1.5g
Water is added to make a total volume of 1 liter, and the pH is adjusted to 7.5 with sulfuric acid or ammonia water.

  A photosensitive material having a conventional structure such as the sample 101 has a low maximum density Dm and is very soft during high-intensity exposure for a very short time, and is not practical. It can be seen from Samples 102 and 103 that adding only the metal compound (II-1) or adding only the silver chloride fine grain emulsion has no effect.

  On the other hand, when a silver chloride fine grain emulsion containing a metal compound (II-1) in advance is added as in sample 104, sufficient stability is obtained over a short period of time from high illuminance to long exposure at low illuminance. Dm and gradation can be obtained. In addition, the effect of suppressing the increase in fog during the long-term storage of the photosensitive material is also observed.

  Further, from Samples 105 to 107, when the silver bromide content exceeds 20 mol% in the halogen composition of the fine grain emulsion, not only the improvement effect of high illumination exposure failure is reduced, but the fog increase during long-term storage becomes remarkable, It turns out that it cannot endure practical use. In particular, the effect of the present invention cannot be obtained when a fine grain emulsion having a high silver bromide content is used.

  As a photographically useful compound previously contained in the silver chloride fine grain emulsion, a compound containing a group 8 metal of the periodic table is advantageous. Particularly, in the case of an iridium compound, it is highly effective, and a bromine atom is particularly used as a ligand. It can be understood from the results of the samples 104 and 108 to 111 that the iridium complex having γ is more preferable.

  It can be seen from Samples 104 and 112 to 113 that the timing of adding the fine grain emulsion to the host emulsion is preferably after the sensitization and further before the sensitization rather than the grain formation of the host emulsion.

From the above, it has been confirmed that only in the embodiment of the present invention, a remarkable illuminance failure improvement effect is recognized.
Example 2
A silver halide emulsion (EMP-201) prepared under the following conditions was mixed with a gelatin aqueous solution on a triacetyl cellulose film having a thickness of 120 μm to prepare a coating solution so that (gelatin / silver) = 0.60. . As a coating aid, a surfactant (SU-2) was added to adjust the surface tension. Using this coating solution, coating was performed such that the coating amount as silver was 1.2 g / m ² to prepare a sample 201 for measuring microwave photoconductivity.
(Preparation of silver halide emulsion)
Below the 2% aqueous solution of gelatin 1 liter kept at 40 ° C. (A ₃ solution) and (B ₃ solution) the pAg = 6.5, were simultaneously added while controlling the pH = 3.0, additionally the following (C ₃ pAg = 7.3 liquid) and (D ₃ solution) were simultaneously added over 120 minutes while controlling the pH = 5.5. At this time, pAg was controlled by the method described in JP-A-59-45437, and pH was controlled using sulfuric acid or an aqueous sodium hydroxide solution.
(A ₃ liquid)
3.45g of sodium chloride
Metal compound (II-1) 5.88 × 10 ⁻¹⁰ mol Water added and 200 ml
(B ₃ liquid)
Silver nitrate 10.0g
200ml with water
(C ₃ liquid)
Sodium chloride 103.2g
Metal compound (II-1) 1.76 × 10 ⁻⁸ mol 600 ml added with water
(D ₃ solution)
300 g of silver nitrate
600ml with water
After completion of addition, desalting was performed using a 5% aqueous solution of Demol N manufactured by Kao Atlas and a 20% aqueous solution of magnesium sulfate, and then mixed with an aqueous gelatin solution to have an average side length of 0.40 μm and a coefficient of variation = 0.07. Monodispersed silver chloride cubic emulsion (EMP-201) was obtained. This emulsion is composed of silver chloride cubic crystals having an average side length of 0.4 μm, in which metal compound (II-1) potassium hexachloroiridium (IV) is uniformly added at 1 × 10 ⁻⁸ mol per mol of silver halide. It is a silver halide emulsion.

Next, an emulsion (EMP-202), which was different in the preparation of the emulsion EMP-201, except that the metal compounds (II-1) of (A ₃ solution) and (C ₃ solution) were sequentially changed to the metal compounds shown in Table 4. ) To (EMP-210) were prepared, and in the preparation of sample 201, emulsion EMP-201 was replaced with EMP-202 to 210 to prepare samples 202 to 210.

  Samples 201 to 210 were measured for microwave photoconductivity by the method described in JP-A-5-45758, pages 2 to 3 (Toshiba Glass Co., Ltd .: UVD-33S filter applied to light source and excited with ultraviolet light). The decay time of the photoconductivity signal in the induced absorption was determined.

  Table 4 shows the measurement results. The decay time of the photoconductivity signal of each sample was expressed as a relative value with the decay time of sample 201 as 100.

As shown in Table 4, metal compounds (I-1), (I-7), (I-9), (I-19), (I-20), selected from the metal compounds exemplified above, The decay time of the photoconductivity signal of the samples 202 to 210 coated with the emulsion added with (I-22) is smaller than that of the comparative sample 201. Therefore, it can be seen that the compound is a metal compound satisfying the condition A. .
Example 3
In the preparation of the host emulsion EMP-11 of Example 1, the metal compound (II-1) was changed sequentially as described in the column of the host emulsion of Samples 301 to 308 shown in Table 5 to thereby change the host emulsion (EMP-31). ~ (EMP-39) was prepared. These host emulsions were subjected to chemical and color sensitization by adding silver chloride fine grain emulsion EMX-11 containing metal compound (II-1) in advance in the same manner as red sensitive emulsion Em-R104. Red sensitive silver halide emulsions (Em-R301) to (Em-R308) were obtained.

  At this time, as a comparative example, the red-sensitive emulsion (Em-R309) to which the silver chloride fine grain emulsion EMX-11 was not added and the metal compound (II-1) were previously contained instead of the silver chloride fine grain emulsion EMX-11. A red-sensitive emulsion (Em-R310) to which silver bromide fine grain emulsion EMX-18 was added was also prepared.

  Samples 301 to 310 were obtained in the same manner as in the preparation of sample 101 except that Em-R301 to R311 were used instead of the red-sensitive emulsion Em-R101.

  The samples 301 to 310 were evaluated for illuminance change characteristics and long-term sample storage by the same method as in Example 1. The data for sample 104 is also shown again.

  In Samples 301 to 308, the metal compound contained in the host emulsion was replaced with a compound satisfying the condition A in Example 2 from (II-1). When the compound satisfying the condition A is contained in the host emulsion, in the embodiment of the present invention, the gradation is particularly stable while maintaining a sufficient hardness from the short exposure with high illuminance to the long exposure with low illuminance. It is preferable. In addition, the fog increase during long-term storage is further suppressed, and a remarkable effect is obtained.

Further, it is clear from the results of samples 309 and 310 that even if a compound satisfying the condition A is contained, there is no effect if the embodiment of the present invention is not taken.
Example 4
In the preparation of the red-sensitive emulsion Em-R104 of Example 1, the addition order of triethylthiourea, sensitizing dye and silver chloride fine grain emulsion EMX-11 was changed in the same manner as shown in Table 6, Red sensitive emulsions (Em-R401) to (Em-R406) were prepared. At this time, the time between the addition of each of triethylthiourea, sensitizing dye, and silver chloride fine grain emulsion was at least 10 minutes. Chloroauric acid was added simultaneously with triethylthiourea. As shown in Table 6, the silver chloride fine grain emulsion was not added during the preparation of the red sensitive emulsion Em-R401.

  Next, in the preparation of the red-sensitive emulsions Em-R401 to Em-R406, the red-sensitive emulsion (Em -R407) to (Em-R412) were prepared.

  Samples 401 to 412 were obtained in the same manner except that Em-R401 to Em-R412 were used in place of the red-sensitive emulsion Em-R101 in the preparation of Sample 101.

  The samples 401 to 412 were evaluated for illuminance change characteristics and long-term sample storage by the same method as in Example 1. The results are shown in Table 6.

  Comparing samples 401 to 406, the present invention is particularly effective when the addition of the fine grain emulsion is first performed with respect to triethylthiourea and chloroauric acid as chemical sensitizers (samples 402 to 404). It is recognized that the effect of.

  In addition, when a similar sample is prepared by replacing the chemical sensitizer with sodium thiosulfate (samples 407 to 412), the effects of samples 408 to 410 to which the fine grain emulsion has been added are clearly significant.

From the above, it can be easily understood that it is more preferable to add the fine grain emulsion before the chemical sensitizer.
Example 5
(Preparation of host emulsion)
In 1 liter of 2% gelatin aqueous solution kept at 40 ° C., the following (A ₄ solution) and (B ₄ solution) were simultaneously added over 30 minutes while controlling pAg = 7.3 and pH = 3.0, Further, the following (C ₄ solution) and (D ₄ solution) were simultaneously added over 120 minutes while controlling pAg = 8.0 and pH = 5.5. At this time, pAg was controlled by the method described in JP-A-59-45437, and pH was controlled using sulfuric acid or an aqueous sodium hydroxide solution.
(A ₄ solution)
Sodium chloride 3.42g
Potassium bromide 0.03g
Metal compound (II-1) 5.88 × 10 ⁻¹⁰ mol Water added and 200 ml
(B ₄ solution)
Silver nitrate 10g
200ml with water
(C ₄ liquid)
Sodium chloride 102.7g
Potassium bromide 1.0g
Metal compound (II-1) 1.76 × 10 ⁻⁸ mol 600 ml added with water
(D ₄ solution)
300 g of silver nitrate
600ml with water
After completion of addition, desalting was performed using a 5% aqueous solution of Demol N manufactured by Kao Atlas and a 20% aqueous solution of magnesium sulfate, and then mixed with an aqueous gelatin solution to have an average side length of 0.40 μm and a coefficient of variation = 0.07. A monodispersed cubic emulsion (EMP-51) was obtained. This emulsion is a silver halide emulsion in which the metal compound (II-1) is uniformly added from the center of the grain to the surface in an amount of 1 × 10 ⁻⁸ mol per mole of silver halide.

Then (A ₄ solution) amounts and metal compound ~ (D ₄ solution) (II-1) by variously changing the addition amount of the distribution and amount are tables in a particle (II-1) 7 Silver halide emulsions (EMP-52) to (EMP-64) were prepared so as to be as follows.

  These emulsions were optimally chemically and color sensitized at 60 ° C. using the following compounds to obtain red sensitive emulsions (Em-R501) to (Em-R514).

Sodium thiosulfate 1.8mg / mol AgX
Chloroauric acid 2.0mg / mol AgX
Stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX
Stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX
Stabilizer STAB-3 3 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye RS-2 1 × 10 ⁻⁴ mol / mol AgX
Supersensitizer SS-1 2 × 10 ^-9 mol / mol AgX
Samples 501 to 514 were obtained in the same manner as in the preparation of sample 101 of Example 1, except that Em-R501 to Em-R514 were used instead of red-sensitive emulsion Em-R101.

  Samples 501 to 514 were evaluated for illuminance change characteristics and long-term sample storage by the same method as in Example 1. The results are shown in Table 7.

As is apparent from the table, a significant improvement effect can be obtained only in the embodiment of the present invention. That is, the iridium compound is contained in 50% of the inside of the grain in terms of volume from the center and in the vicinity of the grain surface on the surface side from 90%, and the content of the iridium compound inside the grain is 10 ⁻⁹ mol per silver mole under halogen. It can be understood that the content of the iridium compound in the vicinity of the surface is 10 to 1000 times that of the inside. In particular, it can be seen that even in the vicinity of the surface, more favorable effects can be obtained in the samples 513 and 514 in which the iridium compound is contained on the surface side from 95% of the particle volume.
Example 6
In the preparation of the sample 104 of Example 1, a green-sensitive emulsion and a blue-sensitive emulsion were prepared by applying the same embodiment of the present invention as that for preparing a red-sensitive emulsion.

  The green and blue sensitive emulsions thus obtained were used for the preparation of Sample 104 to prepare Sample 601 in which the red, green and blue all color sensitive emulsions were an embodiment of the present invention.

  Further, in the sample 111, the sample 308 of the example 3, the sample 410 of the example 4, and the sample 514 of the example 5, the same method as the preparation method of each red sensitive emulsion is applied, and red, green, blue Samples 602 to 605 in which all color-sensitive emulsions of the present invention are embodiments of the present invention were prepared.

  With respect to Samples 601 to 605 and Sample 101, the illuminance change characteristics and long-term sample storability were evaluated for each concentration of B, G, and R in the same manner as in Example 1.

The sample 101 as a comparative example has a low maximum density Dm of each characteristic curve of B, G, and R when the exposure time is changed, particularly in an exposure sample with an ultra-high illuminance such as 10 ⁻³ or 10 ⁻⁶ seconds. In addition, it was extremely soft and could not withstand practical use.

On the other hand, with respect to the samples 601 to 605 serving as the embodiment of the present invention, sufficient Dm and an appropriately hard tone were obtained regardless of the exposure time in any of the characteristic curves of B, G, and R. That is, it is presumed that the change in the shape of the characteristic curve is small even in a wide exposure range from 100 seconds to 10 ⁻⁶ seconds, and a stable tone print can always be obtained regardless of the exposure method. In particular, the samples 602 to 605 are preferable with less fluctuation.

  Further, the fog increase during long-term storage under high-temperature conditions was also preferable because Samples 601 to 605 were smaller than Comparative Sample 101 and the effects of the present invention were obtained.

  Further, for long-term storage, in order to evaluate in accordance with the actual use situation, one of the samples 601 to 605 and the sample 101 was stored in a refrigerator for 6 months at room temperature, and then both samples were used as examples. Color development was performed in the same manner as in Example 1, and the B, G, and R densities of the unexposed areas were measured using an X-RITE densitometer (described above). Also in this evaluation, like the above-mentioned results, the samples 601 to 605 of the present invention were superior to the comparative sample 101 with little fog increase during storage at room temperature.

From the above results, the improvement effect obtained by the practice of the present invention obtained with the red-sensitive emulsion can be similarly obtained with the green and blue-sensitive emulsions, and such an emulsion corresponding to the embodiment of the present invention is used. It was confirmed that the prepared sample exhibited excellent characteristics as a silver halide color photosensitive material.
Example 7
Actually, samples 101 and 601 to 605 were exposed through a general enlarger using a tungsten lamp through a developed negative image of Konica Color JX400, and developed in the same manner as in Example 1. At this time, the enlargement ratio was changed from the same negative image, and prints of each size of the service size, cabinet size, quadrilateral size, and full paper size were created using each sample. However, when creating prints of different sizes for each sample, filter conditions were used that provided an optimal image with cabinet-size prints.

  The entire paper size print obtained from the comparative sample 101 was slightly reddish overall and the contrast of the picture was low, and it was difficult to obtain a print of the same quality as the cabinet or service size. On the other hand, when the samples 601 to 605 were used, there was little change in color balance or change in tone for each print size, and it was possible to efficiently create a print with stable image quality.

As described above, it was confirmed that an excellent color print can be obtained by the photographic light-sensitive material of the present invention even in a method for obtaining an actual color print by a conventional analog surface exposure method.
Example 8
The digital exposure suitability was evaluated as follows for the samples 601 to 605 and the sample 101 produced in Example 6.

  The developed negative image of Konica Color JX400 was converted into digital data using Konica Q-scan, and an environment that can be handled using Adobe's software PHOTO SHOP.

  Characters and fine lines of various sizes were added to the captured image to form one image data, which was manipulated so that it could be exposed by a digital scanning exposure apparatus as described below.

A YAG solid-state laser (oscillation wavelength 946 nm) using a semiconductor laser GaAlAs (oscillation wavelength 808.5 nm) as a light source as a light source was converted by KNbO ₃ SHG crystal and extracted, and a semiconductor laser GaAlAs (oscillation wavelength 808.7 nm). ) Using a YVO ₄ solid-state laser (oscillation wavelength: 1064 nm) with a KTP SHG crystal as the excitation light source and AlGaInP (oscillation wavelength: about 670 nm). An apparatus capable of sequentially scanning and exposing on the color photographic paper by moving the laser beams of the three colors in the direction perpendicular to the scanning direction by the polygon mirror was produced. For the exposure amount, the amount of light of the semiconductor laser was electrically controlled. The scanning exposure was performed at 400 dpi, and the exposure time per pixel at this time was 5 × 10 ⁻⁸ seconds.

  The exposure amount was variously adjusted so that an optimal print image was obtained for each sample, and after scanning exposure, development processing was performed in the same manner as in Example 1 to obtain a cabinet-size print image.

  The print obtained from the comparative sample 101 had insufficient density of each color and no black tightening, was soft overall, and in particular, the tone of the shadow portion was not reproduced at all. In addition, the characters are blurred and the fine lines that should be black appear cyan, and the print quality cannot be practically used no matter how the exposure conditions are adjusted.

  On the other hand, the prints obtained from the samples 601 to 605 can be easily obtained with the same quality as the print quality obtained by the analog surface exposure method of Example 7, which is a high-quality print having no practical problem. there were. Bleeding and color deviation were not observed for letters and fine lines, and prints obtained from samples 602 to 605 were particularly preferred because of high contrast.

  In addition, when the same experiment was performed on the printer processor QDP-1500A of the Konica Digital Minilab System QD-21 using the same image information and sample as described above, the prints obtained from the samples 601 to 605 were similarly obtained. Was a more favorable quality.

  As described above, it was confirmed that an excellent color print can be obtained by the photographic photosensitive material of the present invention even in a method for obtaining an actual color print by the digital scanning exposure method.

Claims (3)

A high silver chloride emulsion having an average silver chloride content of 95 mol% or more, and containing 10 ⁻⁹ to 10 ⁻⁷ mol of iridium compound per mol of silver halide in the interior of the grain between the center and 50% of the emulsion grain volume. And an iridium compound that is 10 to 1000 times the iridium compound content per mole of silver halide between 50% and 50% from the center in the vicinity of the grain surface of 90 to 100% of the grain volume. A characteristic silver halide photographic emulsion. A silver halide photographic light-sensitive material comprising the silver halide photographic emulsion according to claim 1. A method of forming an image, comprising subjecting the silver halide photographic light-sensitive material according to claim 2 to scanning exposure.