WO2005088394A1 - ハロゲン化銀カラー写真感光材料 - Google Patents
ハロゲン化銀カラー写真感光材料 Download PDFInfo
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- WO2005088394A1 WO2005088394A1 PCT/JP2005/004725 JP2005004725W WO2005088394A1 WO 2005088394 A1 WO2005088394 A1 WO 2005088394A1 JP 2005004725 W JP2005004725 W JP 2005004725W WO 2005088394 A1 WO2005088394 A1 WO 2005088394A1
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- halide emulsion
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/08—Sensitivity-increasing substances
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/08—Sensitivity-increasing substances
- G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/3041—Materials with specific sensitometric characteristics, e.g. gamma, density
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/305—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers
- G03C7/30511—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers characterised by the releasing group
- G03C7/30517—2-equivalent couplers, i.e. with a substitution on the coupling site being compulsory with the exception of halogen-substitution
- G03C7/30535—2-equivalent couplers, i.e. with a substitution on the coupling site being compulsory with the exception of halogen-substitution having the coupling site not in rings of cyclic compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/08—Sensitivity-increasing substances
- G03C1/10—Organic substances
- G03C1/12—Methine and polymethine dyes
- G03C1/14—Methine and polymethine dyes with an odd number of CH groups
- G03C1/16—Methine and polymethine dyes with an odd number of CH groups with one CH group
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/81—Photosensitive materials characterised by the base or auxiliary layers characterised by anticoiling means
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
- G03C2001/03517—Chloride content
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
- G03C2001/03594—Size of the grains
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/08—Sensitivity-increasing substances
- G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
- G03C2001/097—Selenium
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains
- G03C2007/3025—Silver content
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C2200/00—Details
- G03C2200/26—Gamma
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C2200/00—Details
- G03C2200/27—Gelatine content
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/392—Additives
- G03C7/39208—Organic compounds
- G03C7/3924—Heterocyclic
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/392—Additives
- G03C7/39208—Organic compounds
- G03C7/3924—Heterocyclic
- G03C7/39268—Heterocyclic the nucleus containing only oxygen as hetero atoms
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/392—Additives
- G03C7/39208—Organic compounds
- G03C7/3924—Heterocyclic
- G03C7/39272—Heterocyclic the nucleus containing nitrogen and oxygen
Definitions
- the present invention relates to a silver halide color photographic light-sensitive material. More specifically, it relates to a silver halide color photographic light-sensitive material for printing which is high contrast in high-intensity light exposure and is suitable for a digital exposure method, and has a rapid processing suitability and is excellent in white background for printing. About the material.
- the present invention relates to a silver halide color photographic light-sensitive material excellent in rapid processing, and further relates to a silver halide photographic light-sensitive material in which a change in performance due to a change in processing conditions is small.
- the present invention relates to a silver halide color photographic light-sensitive material suitable for digital exposure and rapid processing, and in particular, silver halide silver halide which has high sensitivity, high saturation, can reproduce high gray density, and has less unevenness. It relates to a color photographic light-sensitive material.
- the present invention also relates to a silver halide color photographic light-sensitive material capable of obtaining a high-quality image in rapid processing.
- Silver halide photographic light-sensitive materials have been widely used to date to provide inexpensive, stable and high-quality images.
- digitization has also been progressing in the field of color printing using silver halide color photographic light-sensitive materials.
- digital exposure represented by laser scanning exposure is a conventional process. This shows a dramatic increase in the penetration rate compared to analog exposure in which printing is performed directly from a runner negative film through a color printer.
- Such digital exposure is characterized in that high quality prints can be obtained by performing image processing, and plays an extremely important role in improving the quality of prints using silver halide color photographic materials.
- the ability to easily obtain high-quality color prints from electronic recording media is also an important factor, and these are expected to further expand their use.
- a one-stop service of color printing such as receiving a recording medium of a digital camera at a store and finishing and returning a high-quality print in a short time of several minutes, silver halide color
- the superiority of color prints using photographic light-sensitive materials is increasing.
- the processing speed of silver halide color photographic light-sensitive materials is improved, the processing equipment can be reduced in size, and a small and inexpensive printing equipment with high productivity can be provided.
- the one-stop service for printing will become increasingly popular. In recent years, demands for shortening and speeding up the development process are increasing. This is a color printing paper for other color printing methods such as ink jet method and sublimation method.
- the advantage of the print production method using a printer is to further enhance high productivity, which is one of the advantages.
- silver halide color photographic light-sensitive materials can be used from various viewpoints, such as shortening the exposure time, shortening the so-called latent image time from exposure to the start of development, shortening the processing time, and shortening the drying time after processing. Considerations have been made, and proposals for each have been made in the past.
- the silver halide emulsion used for the silver halide color photographic light-sensitive material for printing needs to satisfy various requirements as described above.
- a silver halide emulsion having a high silver chloride content (also referred to as a high silver chloride emulsion) is used due to a demand for rapid processing. Further, it is known that the development speed can be improved by reducing the size (also referred to as particle size) of emulsion grains contained in a silver halide emulsion, and related techniques have been disclosed (for example, , Journal of the Photographic Society of Japan, Abstracts of the 2004 Autumn Meeting (see pages 20-21)). However, when the size of the emulsion grains is reduced, the sensitivity also decreases, and the sensitivity required for digital exposure cannot be obtained. Therefore, a technique for increasing the sensitivity of a high silver chloride emulsion has been required.
- Japanese Unexamined Patent Publication No. 2003-28873838 discloses an emulsion having high sensitivity, high contrast in high-illuminance exposure and laser-scanning exposure, low capri even after rapid processing, and excellent white background. Are disclosed.
- the effect of capri improvement immediately after the preparation of the silver halide color photographic light-sensitive material is shown, nothing is described about the effect of improving the storage stability assuming the aging of the light-sensitive material.
- the gradation in the exposure for 10 seconds and the exposure for 10 to 4 seconds, it is not expected to be the present invention because the gradation is represented by a relative value with respect to the reference sample.
- JP 4 3 3 5 3 3 6 and JP Hei 4 - 3 but 3 5 3 3 1 0 seconds exposure to 8 discloses gradations and gradations of 1 0 2 sec exposure is described , Each with improved pressure characteristics, latent image preservation This is a technical disclosure concerning the improvement of Capri and does not describe Capri.
- Japanese Unexamined Patent Publication No. Hei 6-380652 discloses a technology for improving the capri over time with respect to the improvement of preservation, but the description of laser scanning exposure is unknown, but the gradation is unknown. In addition, although the description concerning rapid processing is made, it is not disclosed in the examples.
- a silver halide emulsion having a high silver chloride content is used due to a demand for rapid processing.
- photographic materials with a high silver chloride content are particularly advantageous for rapid processing. They have low sensitivity, are difficult to undergo chemical sensitization and spectral sensitization, and the obtained sensitivities are unstable, and capricorn is also produced. Had the disadvantage of being easy. It is also known that the use of a silver halide emulsion having a small grain size further improves the rapid processability.
- the sensitivity of the emulsion is proportional to the surface area of the silver halide grains, and reducing the size of the silver halide grains causes a significant decrease in sensitivity. Therefore, further enhancement of sensitivity is required to improve quick processing.
- Japanese Patent Publication No. 7-314103 discloses a silver bromide-containing silver chloride emulsion. It is disclosed that the problem of the latent image feeling can be solved by providing a highly localized phase and doping it with iridium.
- the silver halide emulsion prepared by this method has high sensitivity and high contrast even at relatively high illuminance exposure of about lZi00 seconds, and does not cause the problem of latent image sensitization.
- the problem became apparent that it was difficult to obtain a high-contrast gradation when trying to maintain high sensitivity up to the required 1 ⁇ s ultra-high illuminance exposure.
- U.S. Pat.Nos. 5,783,373 and U.S. Pat.No. 5,783,387'8 disclose high intensity failure using at least three dopants. A method of reducing and increasing contrast is disclosed. However, a high gradation is obtained because a dopant having a desensitizing high contrast effect is used, which is incompatible with high sensitivity in principle.
- color photographic paper is also required to have higher sensitivity.
- Various improvements such as a chemical sensitization method and a silver halide emulsion grain formation method have been made to enhance the sensitivity of high silver chloride emulsions.
- Typical methods of chemical sensitization in silver halide emulsions include sulfur sensitization, selenium sensitization, tellurium sensitization, noble metal sensitization such as gold, reduction sensitization, and various sensitization methods using combinations of these. It has been.
- selenium sensitization has a larger sensitizing effect than sulfur sensitization performed in the industry, but it is not suitable for color photographic paper because fogging is extremely large and it is easy to soften. .
- the high saturation enables a vivid color tone to be expressed, and the reproduction of a high gray density enables an image with a sense of depth to be expressed. If a color photographic paper has the ability to reproduce highly saturated colors with little color saturation, less saturated colors can be created through image processing using a computer. If a color photographic paper does not have the ability to reproduce highly saturated colors, it will not be possible to reproduce more saturated colors. Since a gray image is obtained by simultaneously developing the yellow, magenta and cyan colors, a higher gray density can be reproduced by the higher color density of each color.
- the present inventors have studied and found that the use of the selenium sensitization in the rapid processing did indeed increase the sensitivity, but when the resulting color prints had streak-like unevenness, when the color saturation was reduced, Alternatively, it was found that the gray density sometimes decreased.
- a silver halide emulsion having a fog as small as possible in order to express white clearly.
- the selenium sensation may show a greater sensitizing effect than the sulfur sensitization performed in the industry, but it is not suitable for color printing paper because fogging is extremely large and it is easy to soften. Met. A remarkable increase in sensitivity can be obtained by using gold sensitization in combination with selenium sensation. / The development of a hard selenium sensation method was strongly desired.
- a difference in sensitivity may occur due to a difference in the emulsion preparation scale (here, the emulsion preparation scale is an index indicating the emulsion preparation amount in terms of the molar amount of silver). .
- the emulsion preparation scale is an index indicating the emulsion preparation amount in terms of the molar amount of silver.
- a silver halide color photographic material having at least one red-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer and at least one blue-sensitive silver halide emulsion layer on a support. Wherein at least one of the silver halide emulsion layers contains a silver halide emulsion having a silver chloride content of 90 mol% or more, and the silver halide emulsion contains at least one selenium compound.
- a silver halide color photographic light-sensitive material characterized in that the characteristic curve of the silver halide emulsion layer containing the silver halide emulsion satisfies the following formula (1).
- Equation (1) 2.0 ⁇ y H / y L ⁇ 0.5
- X D 1 represents a halogen ion.
- L D1 from the X D 1 represents any ligand which is different from.
- n represents 3 4 5 or 6,
- ⁇ 1 is a charge of the metal complex, 4 3 2 1 0 or 1 +.
- a plurality of X D 1 is may be the same or different, when L D1 there are multiple, they may be the same or different from each other.
- the metal complex represented by the general formula (D 1) is Shiano (CN I) No ligand, or only one if yes.)
- X D2 is.
- L D2 represents a halogen ion or a pseudohalogen ion (except death. Ann ion OCN) represents any ligand different from X D2.
- N 2 represents 3 4 or 5
- m 2 represents the charge of the metal complex, and represents 4 ⁇ 32 ⁇ 1 0 or 1+, and a plurality of X D2 may be the same or different from each other, and L D2 When there are two or more, these may be the same or different from each other.
- a silver halide emulsion layer containing a cyan dye-forming coupler, a silver halide emulsion layer containing a magenta dye-forming coupler, a silver halide emulsion layer containing a yellow dye-forming coupler, and a non-photosensitive hydrophilic colloid A silver halide color photographic light-sensitive material having a photographic constituent layer comprising at least one silver halide layer, wherein the total amount of silver applied in the photographic constituent layer is 0.5 g / m 2 or less; At least one of the silver halide emulsion layers contains a silver halide emulsion containing 90 mol% or more of selenium-sensitized silver chloride, and at least one of the silver halide emulsion layers containing the yellow dye-forming coupler has the following structure.
- a silver halide photographic material comprising at least one coupler represented by the general formula (Y). PT / JP2005 / 004725
- R 2 represents an alkyl group, a cycloalkyl group, an acyl group, or an aryl group
- R 3 represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group.
- R A , R B , R c , and R D independently represent hydrogen or a substituent.
- a silver halide emulsion layer containing a cyan dye-forming coupler, a silver halide emulsion layer containing a magenta dye-forming coupler, a silver halide emulsion layer containing a yellow dye-forming coupler, a non-photosensitive hydrophilic layer on a support A silver halide color photographic light-sensitive material having a photographic constituent layer composed of at least one colloid layer, wherein the total amount of applied silver in the photographic constituent layer is 0.5 g / m 2 or less; (1) 90 moles of selenium-sensitized silver chloride. /.
- a silver halide emulsion layer containing a cyan dye-forming coupler, a silver halide emulsion layer containing a magenta dye-forming coupler, a silver halide emulsion layer containing a yellow dye-forming coupler, and a non-photosensitive tfe hydrophilic colloid on a support A silver halide color photographic light-sensitive material having a photographic constituent layer composed of at least one layer, wherein the total amount of silver applied in the photographic constituent layer is 0.5 g / m 2 or less; (1) 90 moles of selenium-sensitized silver chloride in at least one of the silver gemide emulsion layers.
- / 0 contains a silver halide emulsion containing more, and (2) contain one or more condensed by crown ethers from aromatic ring, further said I E port one dye-forming coupler-containing C port Gen halide emulsion A silver halide color photographic material, wherein at least one of the layers contains at least one kind of coupler represented by formula (Y).
- a silver halide color photographic material having at least one emulsion layer, wherein at least one of the silver halide emulsion layers containing a color-forming coupler has a silver chloride-sensitive silver chloride content of 90 mol%. containing more silver halide emulsion, wherein the yellow dye-forming coupler-containing layer the silver halide emulsion only the 1 X 1 0- 4 seconds yellow maximum color density obtained by color development processing after the exposure time of (DYmax ) Is 1.90 to 2.30, the maximum magenta color density obtained by subjecting only the silver halide emulsion layer of the magenta dye-forming coupler containing layer to color development after exposure for 1 X 10 to 4 seconds ( DMmax) is 1.95 to 2.30.Maximum cyan color density obtained by subjecting only the silver halide emulsion of the cyan dye-forming coupler-containing layer to color development after exposure for 1 X 10 to 4 seconds.
- DCmax 1.85 to 2.40
- the dye-forming coupler Chromatography containing halogen I all emissions halide emulsion layers were exposed at 1 X 1 0- 4 seconds time obtained by the photosensitive after color development processing
- the maximum cyan color density (DGCmax) is 2.10 to 2.40, 2.30—2.70 and 2.10—2.45, respectively, and curl at 25 ° C and 20% relative humidity
- a silver halide color photographic material having a degree of from 115 to 115.
- the selenium-sensitized silver halide emulsion is chemically sensitized with a selenium-sensitizer represented by the following general formula (SE 1) (13) or (1).
- SE1 selenium-sensitizer represented by the following general formula (SE 1) (13) or (1).
- SE1 The silver halide power photographic material according to the above item.
- M 1 and M 2 represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group, an amino group, an alkoxy group, a hydroxy group, represents Rubamoiru group
- Q is an alkyl group, an alkenyl group, an alkynyl group, Ariru group, a heterocyclic group, an OM 3 or NM 4 M 5
- M 3 ⁇ M 5 is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group , Ariru group, a heterocyclic group.
- 1, M 2 and Q may be bonded to each other to form a ring structure.
- the selenium-sensitized silver halide emulsion is chemically sensitized with a selenium sensitizer represented by the following general formula (SE2) (13) or (14).
- SE2 selenium sensitizer represented by the following general formula (SE2)
- X 1, X 2 and X 3 is an alkyl group, an alkenyl group, an alkynyl group, Ariru group, a heterocyclic group, OJ 1 or NJ 2 J represents a 3 1 ⁇ J 3 is Represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group.
- the selenium-sensitized silver halide emulsion is chemically sensitized with a selenium sensitizer represented by the following general formula (SE3) (13) or (14).
- SE3 selenium sensitizer represented by the following general formula (SE3) (13) or (14).
- SE3 selenium sensitizer represented by the following general formula (SE3) (13) or (14).
- SE3 silver halide color photographic light-sensitive material according to the above item.
- E 1 and E 2 represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, or a carbamoyl group.
- E 1 and E 2 may be the same or different.
- the selenium-sensitized silver halide emulsion is chemically sensitized with a selenium-sensitizer represented by any of the following formulas (PF1) to (PF6). 1 3) or
- 21 represents a compound capable of coordinating to gold via a ⁇ atom, an S atom, a Se atom, a Te atom, or a P atom.
- N 21 represents 0 or 1.
- a 21 Represents 0 S or NR 24 , and R 21 to R 24 represent a hydrogen atom or a substituent, and R 23 may form a 57-membered ring together with R 21 or R 22 .
- L 21 represents a compound capable of coordinating to gold via an N atom, S atom, Se atom, Te atom or P atom.
- n 21 represents 0 or 1.
- 21 to display the 0 S or NR 25 Y 21 represents an alkyl group, an alkenyl group, an alkynyl group, Ariru group, a heterocyclic group, an OR 26 SR 27 N (R 28 ) R 29.
- R 25 and R 29 each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group.
- X 21 and Y 21 may combine with each other to form a ring.
- L 21 represents a compound capable of coordinating to gold via an N atom, an S atom, a Se atom, a Te atom or a P atom.
- n 21 represents 0 or 1.
- R 21 ° R 211 and R 212 each independently represent a hydrogen atom or a substituent, but at least one of R 21 Q and R 211 represents an electron-withdrawing group.
- 21 represents a compound capable of coordinating to gold via an atom, S atom, Se atom, Te atom or P atom.
- n 21 represents 0 or 1.
- W 21 represents an electron-withdrawing group, and R 213 and R 215 each represent a hydrogen atom or a substituent. W 21 and R 213 are joined together 4725
- An annular structure may be formed.
- L 21 represents a compound capable of coordinating to gold via an N atom, S atom, Se atom, Te atom or P atom.
- n 21 represents 0 or 1.
- a 22 represents 0, S, Se, Te or NR 219 .
- R 216 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group or an acyl group
- R 217 to R 219 represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or Represents a heterocyclic group.
- Z 21 represents a substituent, and n 22 represents an integer of 0 to 4. When n 22 is 2 or more, Z 21 may be the same or different.
- Q 21 and Q 22 represent a compound selected from the general formulas (SE 1) to (SE 3), and the Se atoms in Q 21 and Q 22 are coordinated to Au. . 11 23 represents 0 or 1, and J 21 represents anion. When n 23 is 1, Q 21 and Q 22 may be the same or different. However, the compound represented by the formula (PF6) does not include a compound represented by any of the general formulas (PF1) to (PF5). )
- a silver halide having at least one silver halide emulsion layer containing a cyan dye-forming coupler, a silver halide emulsion layer containing a magenta dye-forming coupler, and a silver halide emulsion layer containing a yellow dye-forming coupler on a support.
- a color photographic light-sensitive material wherein at least one of the silver halide emulsion layers containing the yellow dye-forming coupler is (1) a silver halide emulsion containing 90 mol% or more of selenium-sensitive silver chloride.
- Y A silver halide color photographic light-sensitive material containing a seed, wherein the silver halide color photographic light-sensitive material satisfies the following condition (a):
- R represents an alkyl group or a cycloalkyl group
- R 2 represents an alkyl group, a cycloalkyl group, an acyl group, or an aryl group
- R 3 represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group.
- Z! Represents one O—, one NR A —, and Z 2 represents one NR B _ or one C (R c ) R D —.
- At least one peak in the spectral sensitivity distribution is in the range of 450 to 49 O nm, and the difference between the long wavelength and short wavelength exposure wavelengths that gives 70% sensitivity of the peak in the spectral sensitivity distribution is 20 nm. Not less than 100 nm.
- ⁇ 1, ⁇ 2, and j 31 to 4 represent a hydrogen atom, an alkyl group, an alkenyl group, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an amino group, an alkoxy group, a hydroxy group, Or Lumbamoyl tomb, and these groups may be substituted.
- the silver halide color photographic light-sensitive material is 25 ° C, 20 ° /.
- At least one layer of the silver halide emulsion layer containing the cyan dye-forming coupler and / or at least one layer of the silver halide emulsion layer containing the magenta dye-forming coupler contains 90% by mole or more of the silver chloride that has been sensitized.
- the silver halide emulsion contains a silver halide emulsion containing silver halide emulsion containing silver halide emulsion having an average sphere equivalent diameter of 0.50 m or less.
- the silver halide color photographic light-sensitive material described in the above items (7) to (12) is referred to as a second embodiment.
- the silver halide color photographic light-sensitive material described in the above items (1.3) to (20) is referred to as a third embodiment.
- the silver halide color photographic light-sensitive material described in the above items (21) to (24) is referred to as a fourth embodiment.
- ⁇ represents the gradation of the characteristic curve, and is defined as follows.
- each color-sensitive silver halide emulsion layer is subjected to color separation exposure, and after 30 minutes, color development processing is performed, and the density is measured in a spectral region corresponding to the color hue of the layer. Obtain a characteristic curve. .
- the yellow image corresponds to the characteristic curve of the blue photosensitive emulsion layer
- the magenta image corresponds to the characteristic curve of the green photosensitive emulsion layer
- the cyan image corresponds to the characteristic curve of the red photosensitive emulsion layer.
- the minimum density (Dmin) corresponding to the unexposed portion is defined as capri. Further, the reciprocal of the exposure amount at the point A where the density 0.5 is given is defined as the sensitivity S. Further, a point giving the density 1.5 is defined as B, and a gradient of a straight line connecting the points A and B is defined as a gradation ⁇ . Exposure performs a 100 seconds exposure and 1x10 one 6 seconds exposure, the resulting gamma and S for each, and Y L and S L and gamma Eta Toyopi S H.
- the silver halide color photographic light-sensitive material of the present invention preferably the first embodiment, is characterized in that at least one of the silver halide emulsion layers contains a silver halide emulsion having a silver chloride content of 90 mol% or more;
- the silver halide emulsion preferably contains at least one selenium compound, and the characteristic curve of the silver halide emulsion layer containing the silver halide emulsion preferably satisfies the following formula (1).
- Equation (1) 2.0 ⁇ 7H / YL ⁇ 0.5
- ⁇ ⁇ / ⁇ _ is preferably 0.75 or more, more preferably 0.95 or more, and particularly preferably 1.05 or more. Also, preferably the ⁇ ⁇ / ⁇ _ 1. 8 or less, and more preferably 1. 6 or less.
- the silver halide grains contained in the silver halide emulsion used in the light-sensitive material are not particularly limited in grain shape, but are substantially cubes having ⁇ 100 ⁇ faces. , Tetradecahedral crystal grains (these may have rounded vertices and higher-order faces), octahedral crystal grains, ⁇ 100 ⁇ face or ⁇ 111 ⁇ It is preferable that the particles be composed of tabular grains having an aspect ratio of 3 or more. The aspect ratio is the value obtained by dividing the diameter of the circle corresponding to the projected area by the thickness of the particle.
- cubic and tetradecahedral crystal grains having substantially ⁇ 100 ⁇ planes are preferred.
- the silver halide color photographic material of the first embodiment of the present invention it is necessary that at least one of the silver halide emulsion layers contains a specific emulsion.
- the specific emulsion is a silver halide emulsion having a silver chloride content of 90 mol% or more and containing at least one selenium compound.
- the silver chloride content in the specific silver halide emulsion in the first embodiment of the present invention needs to be 90 mol% or more, and from the viewpoint of rapid processing, the silver chloride content is more preferably 94 mol% or more. preferable.
- the silver bromide content is preferably from 0.1 to 8 mol%, more preferably from 0.5 to 6 mol%, because of high sensitivity and high contrast.
- the silver iodide content is 0.02 to 1 mol because of high sensitivity and high contrast at high illuminance exposure. / Is preferably 0, more preferably 0.05 to 0.50 mol 0/0, 0.07 to 0.40 mol% is most preferred.
- the specific silver halide grains in one embodiment are preferably silver iodochlorochloride grains, and more preferably silver iodobromochloride grains having the above-mentioned halogen composition.
- the silver halide particles contained in the specific silver halide emulsion in the first embodiment of the present invention preferably have a silver bromide-containing phase and / or a silver iodide-containing phase.
- the phase containing silver bromide or silver iodide means a site where the concentration of silver bromide or silver iodide is higher than the surroundings.
- the halogen composition of the silver bromide-containing phase or silver iodide-containing phase and its surroundings may change continuously or may change steeply.
- Such a phase containing silver bromide or silver iodide may form a layer having a substantially constant width in a certain portion in the grain, or may have a maximum point without spreading.
- Local silver bromide content in the silver bromide-containing phase lay preferred that at least 5 mol%, more preferably 1 0-8 0 mole 0/0, 1 5-5 0 mol% Is most preferred.
- the local silver iodide content of the silver iodide-containing phase is preferably at least 0.3 mol%, more preferably 0.5 to 8 mol%, and more preferably 1 to 5 mol%. Is most preferred.
- a plurality of such silver bromide or silver iodide-containing phases may be present in layers in each grain, and the silver bromide or silver iodide content may be different. Must be contained.
- the silver bromide-containing phase or the silver iodide-containing phase of the silver halide particles contained in the specific silver halide emulsion according to the first embodiment of the present invention be in a layered form so as to surround each of the grains. It is.
- the silver bromide-containing phase or silver iodide-containing phase formed in a layer shape so as to surround the grains preferably has a uniform concentration distribution in the circumferential direction of the grains in each phase. It is an aspect. However, in the silver bromide-containing phase or silver iodide-containing phase that is layered so as to surround the grains, silver bromide has a maximum point or a minimum point of the silver iodide concentration in the orbital direction of the grains.
- the concentration of silver bromide or silver iodide in the grain corner or edge is different from that of the main surface. There are cases.
- apart from the silver bromide-containing phase and the silver iodide-containing phase which are layered so as to surround the grains they are completely isolated at specific portions of the grain surface and do not surround the grains.
- Phase or silver iodide-containing phase is formed in a layered manner so as to surround the grain near the grain surface.
- the silver halide grains contained in the specific silver halide emulsion according to the first embodiment of the present invention contain a silver bromide-containing phase
- the silver bromide-containing phase contains odor inside the grains. It is preferable to form the layer so as to have the maximum silver halide concentration.
- the silver iodide-containing phase is formed in a layered manner so as to have a maximum silver iodide concentration on the surface of the grain.
- Such a silver bromide-containing phase or a silver iodide-containing phase has a silver content of 3% or more and 30% or less of the grain volume in order to increase the local concentration with a smaller silver bromide or silver iodide content. , And more preferably 3% or more and 15% or less.
- the silver halide particles contained in the specific silver halide emulsion in the first embodiment of the present invention preferably contain both a silver bromide-containing phase and a silver iodide-containing phase.
- the silver bromide-containing phase and the silver iodide-containing phase may be in the same part of the grain or in different places, but it is preferable to be in different places in order to facilitate control of grain formation.
- the silver bromide-containing phase may contain silver iodide, and the silver iodide-containing phase may contain silver bromide.
- the iodide added during the formation of high silver chloride grains is more likely to be formed on the grain surface than the bromide, so that the silver iodide-containing phase is easily formed near the grain surface. Therefore, when the silver bromide-containing phase and the silver iodide-containing phase are located at different positions in the grain, the silver bromide-containing phase is preferably formed inside the silver iodide-containing phase. Good. In such a case, another silver bromide-containing phase may be provided further outside the silver iodide-containing phase near the grain surface.
- the silver bromide content or silver iodide content required to exhibit the effects of the present invention such as high sensitivity and high contrast is such that the silver bromide-containing phase or silver iodide-containing phase is formed inside the grains.
- the silver bromide-containing phase and the silver iodide-containing phase are adjacent to each other in order to consolidate these functions for controlling the photographic action near the surface of the grain. From these points, the silver bromide-containing phase forms anywhere from 50% to 100% of the grain volume, as measured from the inside, and the silver iodide-containing phase forms 85% to 100% of the grain volume.
- the silver bromide-containing phase may be formed at any position of 70% to 100% of the grain volume, and the silver iodide-containing phase may be formed at any position of 90% to 100% of the grain volume. More preferred.
- the introduction of bromide or iodide ions for containing silver bromide or silver iodide in a specific silver halide emulsion is performed by adding a solution of a bromide salt or an iodide salt alone.
- a bromide salt or an iodide salt solution may be added together with the addition of the silver salt solution and the high chloride salt solution.
- the bromide salt or iodide salt solution and the high chloride salt solution may be added separately or as a mixed solution of the bromide salt or iodide salt and the high chloride salt.
- the bromide or iodide salt is added in the form of a soluble salt such as an alkali or alkaline earth bromide salt or an iodide salt. Alternatively, they can be introduced by cleaving bromide or iodide ions from organic molecules described in US Pat. No. 5,389,508. Further, as another bromide or iodide ion source, fine silver bromide particles or fine silver iodide particles can be used.
- the particle shape of the silver halide grains contained in the silver halide emulsion contained in the silver halide color photographic light-sensitive material of the second, third or fourth embodiment of the present invention Cubes with substantially ⁇ 100 ⁇ planes, 14-sided crystal grains (these may have rounded peaks and higher-order planes), 8-sided crystal grains, and ⁇ It is preferable that the grains are composed of tabular grains having an aspect ratio of 3 or more and composed of ⁇ 100 ⁇ faces or ⁇ 111 ⁇ faces. The aspect ratio is the value obtained by dividing the diameter of the circle corresponding to the projected area by the thickness of the particle.
- the silver halide color photographic light-sensitive material of the present invention is more preferably cubic or tetradecahedral.
- the silver halide emulsion of the second embodiment of the present invention contains silver chloride, and the content of the silver chloride is 100 mol based on the total amount of silver halide. / 0 is at least 90 mol%, and from the viewpoint of rapid processing, the silver chloride content is preferably at least 93 mol%, more preferably at least 95 mol%.
- Silver chloride is produced by selenium sensitizers such as selenium compounds represented by the general formulas (SE1) to (SE3) and gold selenium compounds represented by the general formulas (PF1) to (PF6). It is preferable that the silver chloride is felt.
- silver chloride contained in at least one of the silver halide emulsion layers is selenium-sensitized, and it is more preferable that silver chloride contained in all silver halide emulsion layers is selenium-sensitized. preferable.
- the silver halide emulsion preferably contains silver bromide and Z or silver iodide.
- the silver bromide content and a this is excellent in latent image stability in contrast, is preferably from 0.1 to 7 mol%, it is good preferable more is 0.5 to 5 mole 0/0 .
- the silver iodide content is preferably from 0.02 to 1 mol%, more preferably from 0.05 to 0.50 mol%, and more preferably from 0.07 to 0.5 mol%, because of high sensitivity and high contrast at high illuminance exposure.
- the silver halide emulsion is preferably a silver iodobromochloride emulsion, and more preferably a silver iodobromochloride emulsion having the above-mentioned halogen composition.
- the silver halide emulsion contained in the silver halide color photographic light-sensitive material according to the third embodiment of the present invention must have a silver chloride content of 90 mol% or more for rapid processing. It is preferably at least 3 mol%, and 95 mol. /. The above is more preferred.
- the silver bromide content is preferably from 0.1 to 7 mol%, more preferably from 0.5 to 5 mol%.
- the silver iodide content is preferably from 0.02 to 1 mol%, and more preferably from 0.05 to 0.5 mol, because of high sensitivity and high contrast at high illuminance exposure. /. Is more preferably 0.07 to 0.40 mol. / 0 is most preferred.
- the specific silver halide grains in the third embodiment of the present invention are preferably silver iodobromochloride grains, and more preferably silver iodobromochloride grains having the above-mentioned halogen composition.
- the silver halide emulsion is 100 mol of the whole silver halide from the viewpoint of rapid processing.
- / 0 as is the silver chloride content of 9 0 mole 0/0 or more, more preferably 9 3 mole 0/0 or more, 9 5 mole 0/0 or more is particularly preferable.
- the composition of the silver halide may be pure silver chloride, but preferably contains a small amount of a different halogen for the purpose of sensitization, and preferably contains a small amount of silver bromide and Z or silver iodide.
- the silver halide emulsion preferably has a phase containing silver bromide and / or a phase containing silver iodide. If the silver halide emulsion has a silver bromide-containing phase, the silver bromide content 0.1 consequent preferred that to 6. mol%, 0., More preferably from 5 to 5 mol 0/0, 1-4 moles are particularly preferred.
- the silver iodide content is preferably from 0.01 to 1 mol%, more preferably from 0.05 to 0.5 mol%. 0.1 to 0.4 mol% is particularly preferred.
- the silver halide grains preferably have a silver bromide-containing phase and / or a silver iodide-containing phase.
- the phase containing silver bromide or silver iodide means a site where the concentration of silver bromide or silver iodide is higher than that of the surroundings.
- the halogen composition between the silver bromide-containing phase or silver iodide-containing phase and its surroundings may change continuously or may change steeply.
- Such a phase containing silver bromide or silver iodide may form a layer having a substantially constant width in a certain part of the grain, or may be a maximum point having no spread.
- the local silver bromide content of the silver bromide-containing phase is 5 mol 0 /.
- the local silver iodide content of the silver iodide-containing phase is preferably at least 0.3 mol%, and 0.5 to 8 mol 0 /. More preferably, it is 1 to 5 mol. /. Is most preferred.
- a plurality of such silver bromide or silver iodide-containing phases may be present in layers in each grain, and the silver bromide or silver iodide content may be different from each other. It must have one contained phase, preferably at least one even phase each.
- the emulsion when a silver bromide-containing phase or a silver iodide-containing phase is provided in a silver halide emulsion, the emulsion is preferably in a layered form so as to surround each grain. It is a very preferable embodiment that the silver bromide-containing phase or silver iodide-containing phase formed in a layer so as to surround the grains has a uniform concentration distribution in the circumferential direction of the grains in each phase. However, in the silver bromide-containing phase or silver iodide-containing phase which is layered so as to surround the grain, a maximum point or a minimum point of the silver bromide or silver iodide concentration exists in the circumferential direction of the grain. It may have a distribution.
- the concentration of silver bromide or silver iodide at the corners or edges of the grain is different from that of the main surface. There are cases.
- the silver bromide-containing phases which are completely isolated at specific portions of the grain surface and do not surround the grains are provided. Phase or a phase containing silver iodide.
- the silver bromide-containing phase when the silver halide emulsion contains a silver bromide-containing phase, the silver bromide-containing phase is preferably formed in a layer form so as to have a maximum silver bromide concentration inside the grains. Further, when the silver halide emulsion of the present invention contains a silver iodide-containing phase, the silver iodide-containing phase may be formed in a layered form so as to have a maximum silver iodide concentration on the surface of the grains. preferable.
- Such a phase containing silver bromide or silver iodide is composed of a silver content of 3% to 30% of the grain volume in order to increase the local concentration with a smaller silver bromide or silver iodide content.
- the silver content is 3% or more and 15% or less.
- the silver halide emulsion preferably contains both a silver bromide-containing phase and a silver iodide-containing phase.
- the silver bromide-containing phase and the silver iodide-containing phase may be located at the same part of the grain or at different places, but being located at different places is preferable in that the control of grain formation becomes easier. Good.
- the silver bromide-containing phase may contain silver iodide, and conversely, the silver iodide-containing phase may contain silver bromide.
- the iodide added during the formation of high silver chloride grains oozes out on the grain surface rather than the bromide, so the silver iodide-containing phase is easily formed near the grain surface! /. Therefore, when the silver bromide-containing phase and the silver iodide-containing phase are located at different positions in the grain, the silver bromide-containing phase is preferably formed inside the silver iodide-containing phase. In such a case, another silver bromide-containing phase may be provided further outside the silver iodide-containing phase near the grain surface.
- the silver bromide content or silver iodide content required to exhibit effects such as high sensitivity and high contrast increase as the silver bromide or silver iodide-containing phase is formed inside the grains.
- the silver chloride content may be unnecessarily reduced, resulting in impaired rapid processing. Therefore, it is preferable to consolidate the functions of the silver bromide-containing phase and the silver iodide-containing phase for controlling the photographic action near the surface in the grain. Therefore, the silver bromide-containing phase and the silver iodide-containing phase are preferably adjacent to each other.
- the silver bromide-containing phase forms anywhere from 50% to 100% of the grain volume measured from the inside, and the silver iodide-containing phase forms from 85% to 10% of the grain volume. It is preferably formed at any of the 0% positions.
- the silver bromide-containing phase is formed at any of the positions 70% to 95% of the grain volume, and the silver iodide-containing phase is formed at any of the positions 90% to 100% of the grain volume. It is more preferable to form.
- the silver halide emulsion when the silver halide emulsion has a silver bromide-containing phase, another preferred embodiment of the silver bromide-containing phase is within 20 nm from the grain surface.
- This is a silver halide emulsion having a region having a silver bromide content of 0.5 to 20 mol% at a depth. It is preferable to have a silver bromide-containing phase within 10 nm from the grain surface.
- the silver bromide content is 0.5 to 10 mol 0 /. It preferably has a silver bromide-containing phase of 0.5 to 5 mol 0 /. More preferably, it has a silver bromide-containing phase.
- the silver bromide-containing phase does not necessarily need to be formed in a layered form.
- a silver bromide-containing phase is formed in a layer so as to surround the grains.
- the addition of bromide or iodide ions for containing silver bromide or silver iodide in the silver halide emulsion may be performed by adding a solution of a bromide salt or an iodide salt alone, Alternatively, a bromide salt or iodide salt solution may be added together with the addition of the silver salt solution and the high chloride salt solution. In the latter case, the bromide or iodide salt solution and the high chloride salt solution may be added separately or as a mixed solution of the bromide or iodide salt and the high chloride salt.
- the bromide or iodide salt is added in the form of a soluble salt, such as an alkaline or alkaline earth bromide or iodide salt. Alternatively, it can be introduced by cleaving a bromide ion or an iodide ion from an organic molecule described in US Pat. No. 5,389,508. Further, as another bromide or iodide ion source, fine silver bromide grains or fine silver iodide grains can be used. 'The addition of the bromide salt or iodide salt solution may be performed intensively at one stage of particle formation, or may be performed over a certain period of time.
- the location of iodide ion introduction into the high chloride emulsion is limited to obtain a high sensitivity and low fogging emulsion.
- the addition of the iodide salt solution is preferably performed outside 50% of the particle volume, more preferably from outside 70%, and most preferably from outside 85%. Further, the addition of the iodide salt solution is preferably terminated at a lower side of 98% of the particle volume, most preferably at an inner side of 96%.
- the addition of the bromide salt solution is preferably performed outside 50% of the particle volume, more preferably outside 70%.
- the distribution of the concentration of bromide or iodide ions in the depth direction within the particle is determined by etching / TOF-SIMS (Time of Flight-Secondary Ion Mass Spectrometry) method, for example, using FFPII Evans's TRIF TII TOF-SIMS Can be measured.
- TOF-SIMS Time of Flight-Secondary Ion Mass Spectrometry
- the TOF-SIMS method is specifically described in “Surface Analysis Technology Selection Secondary Ion Mass Spectrometry” edited by The Surface Science Society of Japan, Maruzen Co., Ltd. (1999).
- the emulsion grains are analyzed by the etching ZTOF-SIMSS method, it can be analyzed that even if the addition of the iodide salt solution is completed inside the grains, the iodide ions are seeping out toward the grain surface.
- the silver halide emulsion used in the present invention is preferably analyzed by etching / TOF-SIMS to find that the iodide ion has a concentration maximum on the grain surface and the iodide ion concentration is attenuated inward.
- the bromide ion preferably has a maximum concentration inside the particle.
- the local concentration of silver bromide is X if the silver bromide content is somewhat high.
- the emulsion of the silver halide photographic light-sensitive material of the present invention preferably comprises monodispersed grains having a grain size distribution.
- the variation coefficient of the equivalent spherical diameter of all the grains is preferably 20% or less, and more preferably 15% or less. Is more preferable, and particularly preferably 10% or less.
- the coefficient of variation of the equivalent sphere diameter is expressed as a percentage of the standard deviation of the equivalent sphere diameter of each particle with respect to the average value of the equivalent sphere diameter. At this time, in order to obtain a wide latitude, it is preferable to use the above monodispersed emulsion by blending it in the same layer, or to carry out multilayer coating.
- the particle size of the silver halide grains means the average equivalent sphere size unless otherwise specified.
- the sphere equivalent diameter is a value represented by the diameter of a sphere having a volume equal to the volume of each particle.
- the particle size has a length equal to the length of one side (also referred to as a side length) of a cube having a volume equal to the volume of an individual particle, or a volume equal to the volume of an individual particle.
- the emulsion used in the color photographic light-sensitive material of the first embodiment of the present invention is preferably a so-called monodisperse emulsion comprising particles having a monodisperse particle size distribution.
- the variation coefficient of the grain size of all grains contained in each silver halide emulsion is preferably 20% or less, more preferably 15% or less, and even more preferably 10% or less. .
- the coefficient of variation of the particle size is expressed as a percentage obtained by dividing the standard deviation of the side length or sphere equivalent diameter of each particle by the average value of the side length or sphere equivalent diameter. At this time, in order to obtain a wide latitude, it is preferable to use the above monodispersed emulsion by blending it in the same layer, or to perform multi-layer coating as the same color-sensitive layer.
- the sphere equivalent diameter of the grains contained in the silver halide emulsion containing the selenium compound is preferably 0.65 ⁇ or less, more preferably 0.6 ⁇ or less. It is more preferably not more than 0.5 ⁇ , and particularly preferably not more than 0.4 ⁇ ⁇ ⁇ .
- the lower limit of the equivalent sphere diameter of the silver halide grains is preferably 0.05 ⁇ , and more preferably 0.1 ⁇ .
- a particle with an equivalent sphere diameter of 0.6 ⁇ corresponds to a cubic particle with a side length of approximately 0.48 ⁇
- a particle with an equivalent sphere diameter of 0.5 ⁇ corresponds to a cubic particle with a side length of approximately 0.4 ⁇ , equivalent to a sphere.
- a particle having a diameter of 0.4 ⁇ corresponds to a cubic particle having a side length of about 0.32 ⁇ .
- the equivalent spherical diameter of the grains contained in the silver halide emulsion is preferably 0.6 ⁇ or less, preferably 0.5 ⁇ or less, and 0.4 ⁇ or less. More preferably, it is not more than m.
- the lower limit of the equivalent sphere diameter of the silver halide grains is preferably 0.05 m, more preferably 0.1 / m.
- the equivalent spherical diameter of the particles contained in the silver halide emulsion of the silver halide emulsion layer containing the yellow dye-forming coupler is preferably 0.6 ⁇ m or less, It is more preferably 5 m or less, most preferably 0.4 ⁇ or less.
- the equivalent spherical diameter of the particles contained in the silver halide emulsion of the silver halide emulsion layer containing the magenta dye-forming blur and the silver halide emulsion layer containing the cyan dye-forming blur is 0.5 m or less. It is more preferably at most 0.4 ⁇ , most preferably at most 0.3 ⁇ .
- the lower limit of the equivalent spherical diameter of the grains contained in any of these silver halide emulsions is preferably at least 0.05, more preferably 0.1, and even more preferably 0.2 ⁇ . ⁇
- a silver halide emulsion layer containing a yellow dye forming power, a silver halide emulsion layer containing a magenta dye forming coupler, a silver halide emulsion layer containing a magenta dye forming coupler, and a cyan dye forming material according to a fourth embodiment of the present invention are described below. It has at least one coupler-containing silver halide emulsion layer.
- the average sphere-equivalent diameter of the silver halide grains contained in the silver halide emulsion layer containing the yellow dye-forming coupler is 0.75 ⁇ or less (up to the upper limit), and may be 0.68 ⁇ or less.
- the average equivalent spherical diameter of the silver halide grains contained in the silver halide emulsion layer containing the magenta dye-forming coupler or the silver halide emulsion layer containing the cyan dye-forming coupler should be 0.50 ⁇ or less (up to the upper limit). It is more preferably not more than 0.30 ⁇ , particularly preferably not more than 0.32 / m. In any of the silver halide emulsions, the lower limit of the average equivalent spherical diameter of the silver halide grains is preferably 0.05 ⁇ m, more preferably 0.1 m.
- Particles with a spherical equivalent diameter of 0.60 ⁇ m correspond to cubic particles with a side length of about 0.48 m
- particles with a spherical equivalent diameter of 0.50 ⁇ correspond to cubic particles with a side length of about 0.40 zm
- a particle with an equivalent sphere diameter of 0.40 ⁇ m corresponds to a cubic particle with a side length of about 0.32 m
- a particle with an equivalent sphere diameter of 0.30 ⁇ m has a side length of about 0. Five
- the silver halide emulsion of the silver halide photographic light-sensitive material of the present invention may contain silver halide grains having a sphere equivalent diameter exceeding the upper limit of each layer.
- silver halide grains that are not more than the upper limit of each layer and are not less than the lower limit (usually 0.05 m or more in sphere equivalent diameter) (hereinafter, also referred to as silver halide grains in the upper and lower limits).
- 50% or more of the silver halide grains are preferably silver halide grains within the upper and lower limits, more preferably 80% or more, and particularly preferably 90% or more.
- the equivalent sphere diameter of a silver halide grain can be determined from its electron micrograph, and can be calculated from the side length of a cube having the same volume as the silver halide grain.
- the equivalent sphere diameter can be obtained by measuring the side length of a silver halide grain having a statistically significant value (for example, 600 or more) and calculating the average value as the average equivalent sphere diameter.
- the selenium compound As the selenium compound, the following general formulas (SE1), (SE2) or (SE3) can be preferably used.
- M 1 and M 2 represent a hydrogen atom, an alkyl group, an alkenyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an amino group, an alkoxy group, a hydroxy group, or represents Rubamoiru group
- Q is an alkyl group, an alkenyl group, an alkynyl group
- Ariru group, a heterocyclic group an OM 3 or NM 4 M
- M 3 ⁇ M 5 is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group Represents an aryl group or a heterocyclic group.
- M 1 M 2 and Q may combine to form a ring structure.
- X 1 , X 2 and X 3 represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, OJ 1 or NJ 2 J 3 .
- 1 to J 3 represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group.
- E 1 and E 2 are an alkyl group, an alkyl group, an alkyl group, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group or Represents a rubamoyl group.
- E 1 and E 2 may be the same or different.
- the alkyl group represented by M 1 ⁇ ! 5 and Q represents a linear, branched, or cyclic substituted or unsubstituted alkyl group.
- a substituted or unsubstituted linear or branched alkyl group having 1 to 30 carbon atoms eg, a methyl group, an ethyl group, an isopropyl group, an n-propyl group, an n-butyl group, a t-butyl group
- 2-pentyl group n-hexyl group, n_octyl group, t-octyl group, 2-ethylhexyl group, 1,5-dimethylhexyl group, n-decyl group, n-dodecyl group, n- Tetradecyl group, n-hexadecyl group, hydroxyethyl group, hydroxypropyl group, 2,3
- alkenyl group represented by M i to M 5 and Q represents an alkenyl group having 2 to 16 carbon atoms (eg, an aryl group, a 2-butenyl group, a 3-pentyl group, etc.),
- the alkynyl group represented by M 5 and Q represents an alkynyl group having 2 to 10 carbon atoms (for example, a propargyl group, a 3 -pentulle group and the like).
- the aryl groups represented by M 1 ! ⁇ 5 and Q include a substituted or unsubstituted phenyl group and a naphthyl group having 6 to 20 carbon atoms (eg, an unsubstituted phenyl group, an unsubstituted naphthyl group, 3, 5-dimethylphenyl, 4-butoxyphenyl group, 4-dimethylaminophenyl group, etc.), and the heterocyclic group includes, for example, a pyridyl group, a furyl group, an imidazolyl group, a piperidyl group, a morpholyl group, and the like. .
- Examples of the acetyl group represented by M 1 and M 2 in the general formula (SE 1) include an acetyl group, a formyl group, a benzoyl group, a bivaloyl group, a propyl group, an n-nonanoyl group, and an amino group.
- Examples thereof include an unsubstituted amino group, a methylamino group, a hydroxyxethylamino group, an n-octylamino group, a dibenzylamino group, a dimethylamino group, a getylamino group, and the like.
- Examples of the alkoxy group include a methoxy group and an ethoxy group.
- N-butyloxy group cyclohexyloxy group, n-octyloxy group, n-decyloxy group and the like.
- rubamoyl group examples include unsubstituted rubamoyl group, N, N-getylcarbamoyl group, and N-phenyl group. And a benzylcarbamoyl group.
- MM 5 and Q in the general formula (SE 1) may have a substituent as much as possible.
- substituents include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom).
- alkyl group (a linear, branched, or cyclic alkyl group including a bicycloalkyl group and an active methine group), an alkenyl group, an alkynyl group, an aryl group, and a heterocyclic group (regardless of the position of substitution), Acyl group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic carbonyl group, carbamoyl group, N-hydroxycarbamoyl group, N-acyl carbamoyl group, N-sulfonylcarbamoyl group, N-carbamoylcarbamoyl, thiocarbamoyl, N-sulfamoylcarbamoyl, carbazoyl, carboxy or a salt thereof, Salil group, Okisamoiru group, Shiano grave, Karubon'imi Doyle based on
- Carbonimidoyl group formyl group, hydroxy group, alkoxy group (including groups containing repeating ethyleneoxy or propyleneoxy group units), aryloxy group, heterocyclic oxy group, acryloxy group, (alkoxy or aryloxy) Roxy) carbonyloxy group, carbamoyloxy group, sulfo-loxy group, amino group, (alkyl, aryl, or heterocycle) amino group, acylamino group, sulfonamide group, perido group, thioperido group, 2005/004725
- N-hydroxyperido group imido group, (alkoxy or aryloxy) carbonyl diamino group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrozino group, ammoeo group, oxamoylamino group, N — (Alkyl or aryl) sulfonyl peridode, N-acyl peridolide, N-acylsulfamoylamino, hydroxyxamino, nitro, heterocyclic groups containing quaternized nitrogen atoms (eg Pyridinio, 'imidazolio, quinolinio, isoquinolino), isocyano, imino, mercapto, (alkyl, aryl, or heterocycle) thio, (alkyl, aryl, or heterocycle) dithio, (Alkyl or aryl) sulfonyl group
- the active methine group means a methine group substituted with two electron-withdrawing groups
- the electron-withdrawing group here is an acyl group, an alkoxycarboxy group, or an aryloxycarbo group.
- the two electron-withdrawing groups may be bonded to each other to form a cyclic structure.
- the salt means a cation such as an alkali metal, an alkaline earth metal, or a heavy metal, and an organic cation such as an ammonium ion or a phosphonium ion. These substituents may be further substituted with these substituents.
- M 1 and M 2 are each a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 6 carbon atoms, Is a substituted or unsubstituted cyclic alkyl group, an alkenyl group having 2 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, a heterocyclic group, and an acyl group, and Q is A substituted or unsubstituted linear or branched alkyl group having 1 to 6 carbon atoms; a substituted or unsubstituted cyclic alkyl group having 3 to 6 carbon atoms; an alkenyl group having 2 to 6 carbon atoms; substituted or unsubstituted Ariru group or a NM 4 M 5,, M 4 and M 5 is a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 6 carbon atoms, Is
- More preferred compounds represented by the general formula (SE 1) include: M 1 and M 2 each being a hydrogen atom, a carbon; a substituted or unsubstituted linear or branched alkyl group having 1 to 6 carbon atoms; A substituted or unsubstituted aryl group having 6 to 10 carbon atoms, wherein Q is a substituted or unsubstituted linear or branched alkyl group having 1 to 6 carbon atoms, and a carbon atom having 6 to 1 carbon atoms.
- M 4 and M 5 is a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 6 carbon atoms, carbon atoms This is a case of a 2-6 alkenyl group or a substituted or unsubstituted aryl group having 6-10 carbon atoms.
- Q is NM 4 M 5
- M 4 and M 5 are a hydrogen atom, a substituted or unsubstituted straight-chain or branched-chain having 1 to 6 carbon atoms. It is an alkynole group, an alkenyl group having 2 to 6 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms.
- the compounds represented by the general formula (SE 1) include, for example, Chemical 'Reviews (Chem. Rev.) 55, 18 1—2 28 (1955), Journal of Organic 'Chemist Lee (J. Org. Chem.) 24, 470—473 (1959), Journal of Heterocyclic Chemistry (J. Heterocycl. Chem.) 4, 605-609 (19667), Pharmaceutical Journal, 82, 36-45 (1962), JP-B-39-26203, JP-A-63-229449, OLS-2, 043, 944. .
- the alkyl group, alkenyl group, alkynyl group, aryl group and heterocyclic group represented by Xi X 3 and J to J 3 are each represented by M 1 M 5 and It has the same meaning as the alkyl group, alkenyl group, alkynyl group, aryl group and heterocyclic group represented by Q.
- to 3 and J to J 3 may have a substituent as much as possible, and examples of the substituent include the same specific examples as the substituent described above.
- X to X 3 are preferably a substituted or unsubstituted linear or branched alkyl group having 1 to 6 carbon atoms, and a substituted or unsubstituted alkyl group having 6 to 10 carbon atoms. It is a case where it represents an aryl group or a heterocyclic group, more preferably a case where Xi X 3 represents a substituted or unsubstituted aryl group having 6 to 10 carbon atoms.
- Compounds represented by the general formula (SE 2) include, for example, Organic Phosphorus Compounds (4, pp. 1-73), Journal 'Chemical' Society B (J. Chem. Soc. (B), 141, p. 6, 196), Journal Organik 'Chemistry (J. Org. Chem. 32, 1717, 1967) Y.), Journal Organic 'Chemistry (J.
- Formula (SE 3) alkyl group represented by E 1 and E 2 in, Aruke - group, Al Kiniru group, Ariru heterocyclic group group and to each of the general formulas (SE 1)! ⁇ 1 to ⁇ 5 have the same meanings as the alkyl group, alkenyl group, alkynyl group, aryl group and heterocyclic group represented by Q and Q.
- E 1 and E Ashiru group as the example Asechiru group represented by 2, formyl group, Benzoiru group, pivaloyl group, force Puroiru group, .eta. Nonanoiru group and the like, alkoxy.
- Examples of the carbonyl group include main butoxy force Carbonyl group, ethoxycarbonyl group, ⁇ -butyloxycarbonyl group, cyclohexyloxycarbonyl group, ⁇ -octyloxycarbonyl group, ⁇ -decyloxycarbonyl group and the like.
- Examples of the phenyl group include a phenoxycarbonyl group and a naphthoxycarbonyl group
- examples of the rubamoyl group include an unsubstituted rubamoyl group, ⁇ , ⁇ -getylcarbamoyl group, and ⁇ -phenylcarbamoyl group.
- the E 1 and E 2 may have as much possible substituents, the same specific examples include et al is a substituent described above as examples of the substituent.
- Preferred compounds of the general formula (SE 3) is selected from groups E 1 and E 2 is represented by the following general formula (T 1) ⁇ ( ⁇ 4) .
- ⁇ 1 and ⁇ 2 may be the same or different.
- -General formula (Tl) General formula (T2) — General formula ( ⁇ 3) — General formula ( ⁇ 4)
- Upsilon 11 represents an alkyl group, an alkenyl group, an alkynyl group, ⁇ Li one group, a heterocyclic group, an ⁇ _R 11 or NR 12 R 13, R 11 ⁇ R 13 is an alkyl group, Represents an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group.
- L 11 represents a divalent linking group
- EWG represents an electron-withdrawing group.
- a 11 represents an oxygen atom, a sulfur atom or NR 17, and a rule 14 to!
- ⁇ 17 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group.
- a 12 represents an oxygen atom, sulfur C CCR yellow I— atom or NR 111
- R 18 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group or an acyl group.
- R 19 , R 110 and R 111 represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group.
- Z 11 represents a substituent, and n 11 represents an integer of 0 to 4. When n 11 is 2 or more, Z 11 may be the same or different.
- Y 11 represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group
- OR 11 or NR 12 R 13 and 11 to! ⁇ 13 represents an alkyl group, an alkenyl group, an alkynyl Represents an alkyl group, an aryl / alkyl group, or a heterocyclic group.
- the alkyl group referred to herein has the same meaning as the alkyl group represented by Mi M 5 and Q in Formula (SE 1), and the preferred range is also the same.
- alkenyl group, alkynyl group, aryl group and heterocyclic group have the same meaning as the alkenyl group, alkynyl group, aryl group and heterocyclic group represented by IV M 5 and Q, respectively, and the preferred range is also the same.
- Y 11 is preferably an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and more preferably an alkyl group or an aryl group.
- G 1 G 2 , G 3 , and G 4 are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and an aryl group having 6 to 20 carbon atoms. Alternatively, it represents a heterocyclic group having 1 to 10 carbon atoms, and GG 2 and G 3 may be linked to form a ring.
- G 4 is preferably a hydrogen atom, an alkyl group or an aryl group, and is preferably a hydrogen atom or 5 004725
- EWG represents an electron-withdrawing group.
- the electron-withdrawing group referred to herein is a substituent having a positive Hammett's substituent constant a m value (or ⁇ ⁇ value), and preferably has a (j m value of 0.12 or more (or ⁇ ⁇ value is 0.2 or more), and the upper limit is a substituent of 1.0 or less a Specific electron withdrawing group having a positive m value (or a ⁇ ⁇ value of 0.2 or more)
- Examples include an alkoxy group (preferably an alkoxy group substituted with at least two or more halogen atoms), an aryloxy group (preferably an aryloxy group substituted with at least two or more halogen atoms), an alkylthio group ( Preferably, an alkylthio group substituted with at least two or more halogen atoms), an arylthio group, an acyl group, a formyl group, an acyloxy group, an
- Rubonyl group cyano group, nitro group, dialkylphosphono group, diarylphosphono group, dianolequinolephosphinyl group, diarylphosphinyl group, phosphoryl group, alkylsulfinyl group, arylusnorefininole Group, alkylsnolephoninole group, arylinolenohoninole group, sulfoninoleoxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, imino group, imino group substituted with ⁇ atom, carboxy group ( or a salt thereof) of at least two or more halogen atoms-substituted alkyl group, Ashiruamino group, at least two or more alkyl amino group substituted with a halogen atom, a m value is positive (or sigma [rho value 0.
- EWG is preferably an alkoxy group, an acyl group, a formyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, a dialkylphosphono group, or the like.
- Diarylphosphono group dialkylphosphinyl group, diarylphosphininole group, alkylsulfiel group, arylsulfininole group, alkynolesnolehoninole group, arylsulfonyl group, sulfamoyl group, thiocarbonyl group, imino A group, an imino group substituted with a ⁇ atom, a phosphoryl group, a carboxy group (or a salt thereof), and an alkyl group substituted with at least two or more halogen atoms.
- a substituted alkyl group more preferably an alkoxy group, an acyl group, a formyl group, a cyano group, a nitro group, an alkyl sulfonyl group, an aryl sulfo group, or an alkyl substituted with at least two or more halogen atoms.
- the Hammett's rule is an empirical rule proposed by LP Hammett in 1935 to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives.
- the Hammett's substituent constant is ⁇ p
- cm values There are values and cm values, and these values are found in many common books. For example, JA Dean ed., "Lange's Handbook of Chemistry J, 12th Edition, 1979 (McGraw-Hill)" and “Chemical Domain Special Issue", 122, 96-103, 197 9 (Nankodo) or Cihemical Reviews, Vol. 91, pp. 165-195, 1991.
- the substituent specified by the substituent constant according to the Hammett rule is not limited to only those substituents having a known value in the literature described in these books, but the value is described in the literature. Of course, even unknown ones are included as long as they are within the range when measured based on the Hammett's rule.
- L 11 is represented by the general formula (L 1)
- GG 3 is a hydrogen atom or an alkyl group
- EWG is an alkoxy group, an acyl group, a formyl group, or carbamoyl.
- L 11 is represented by the general formula (L 1), GG 3 represents a hydrogen atom or an alkyl group, and EWG represents an alkoxy group, an acyl group, a formyl group, a cyano group, a nitro group, an alkylsulfonyl group, An arylsulfonyl group is an alkyl group substituted with at least two or more halogen atoms.
- R 14 to R 17 each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group.
- R 14 to R 17 has the same meaning as the alkyl group represented by M! M 5 and Q, and the preferred range is also the same.
- alkenyl group, alkynyl group, Ariru group, respectively it also heterocyclic group M ⁇ ⁇ M 5 and Q represents an alkenyl group, an alkynyl group, Ariru group has the same meaning as the heterocyclic group, preferred ranges are also the same It is.
- R 14 is preferably an alkyl group.
- R 15 and R 16 are preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group, and most preferably one is a hydrogen atom and the other is a hydrogen atom or an alkyl group.
- R 17 is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group, and most preferably an alkyl group.
- a 11 represents an oxygen atom, a sulfur atom or NR 17 , but is preferably an oxygen atom or a sulfur atom, more preferably an oxygen atom.
- a 11 is preferably an oxygen atom or a sulfur atom
- R 14 is an alkyl group
- R 15 and R 16 are a hydrogen atom, an alkyl group or an aryl group. More preferably, A 11 is an oxygen atom, R 14 is an alkyl group, and R 15 and R 16 are a hydrogen atom or an alkyl group.
- the alkyl groups represented by R 18 , R 19 , R 110 , and R 111 have the same meaning as the alkyl groups represented by Mi M 5 and Q in formula (SE 1), and the preferred range is also the same. It is.
- alkenyl group, alkynyl group, Ariru group, an alkenyl group each represented by Mi ⁇ M 5 and Q also heterocyclic group, an alkynyl group, Ariru group, a heterocyclic group as defined.
- a preferred range thereof is also the same .
- the acryl group represented by R 18 include an acetyl group, a formyl group, a benzoyl group, a bivaloyl group, a propyl group, and an n-nonanoyl group.
- Z 11 represents a substituent, and examples thereof include the same specific examples as the substituent described above.
- a halogen atom an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an N-acynolelbamoyl group, an N-sulfonylcarbamoyl group Group, N-carbamoylcarbamoyl group, thiocarbamoyl group, N-sulfamoylcarbamoyl group, carbazole group, carboxy group (and salts thereof), cyano group, formyl group, hydroxy group, alkoxy group, Aryloxy group, heterocyclic group, acyloxy group, nitro group, amino group, (alkyl, aryl or hetero ring) amino group, acylamino group, sulfonamide group, ureido group, A thioureido group, an alkylthio
- a halogen atom an alkyl group, an aryl group, a heterocyclic group, a carboxy group (and a salt thereof), a hydroxy group, an alkoxy group, an aryloxy group, a heterocyclicoxy group, an acyloxy group, an amino group, Amino, acylyl, ureido, thioureido, alkylthio, arylthio, heterocyclic thio, sulfo (and salts thereof), and more preferably alkyl.
- n 11 represents an integer of 0 to 4. n 11 preferably represents 0 to 2, and more preferably 0 or 1.
- a 12 in the general formula (T4) an oxygen atom, a sulfur atom or NR 11 1, preferably if it represents an oxygen atom or sulfur atom, may represent an oxygen atom is more preferable.
- a 12 is preferably an oxygen atom or a sulfur atom
- R 18 is a hydrogen atom, an alkyl group, or an acyl 'group
- R 19 and R 11 G are a hydrogen atom, an alkyl group, a Ariru group, 3 ⁇ 4 11 0-2 Deari
- Z 11 is an alkyl group, Ariru grave, (including and salts thereof) carboxy group, arsenate Dorokishi group, an alkoxy group, Ariruokishi group, (alkyl, Ariru or, (Hetero ring)
- a 12 is an oxygen atom
- a R 18 is a hydrogen atom or an alkyl group
- R 19 and R 110 are Eimoto atom or an alkyl group
- Z 11 Is an alkyl group, an aryl group, a carboxy group (including a salt thereof), an alkoxy group, a ureido group, a sulfo group (including a salt thereof).
- Still more preferably from A 12 is oxygen atoms
- R 18 is a alkyl group
- R 19 and R 11 ° is a hydrogen atom
- Z 11 is an alkyl group, carboxy Group (and its salt), alkoxy group, and sulfo group (and its salt).
- E 1 is the general formula (T 1), E 2 is the general formula (T l), and E 1 is the general formula (T 1)
- E 2 is the general formula (T2)
- E 1 is the general formula (T 1)
- E 2 is the general formula (T3)
- E 1 is the general formula (T 1)
- E 2 is the general formula (T 4)
- E 1 is E 2 is the formula by the formula (T 2) (T 3)
- E 2 is the formula by E 1 general formula (T 2) (T4)
- E 1 is the E 2 in the general formula (T3)
- E 1 is the general formula (T 3)
- E 2 is the general formula (T4)
- E 1 is the general formula (T4)
- E 1 is the general formula (T4)
- E 2 is the general formula (T4)
- E 1 is the general formula (T4)
- E 2 is the general formula (T4)
- E 1 is the general formula (T4)
- E 2 is the general formula (T4)
- E 1 is the general formula (T4)
- E 1 is the general formula (T 1)
- E 2 is the general formula (T l)
- E 1 is the general formula (T1)
- E 2 is the general formula (T2)
- E 1 is the general formula (T 1)
- E 2 is the general formula (T4)
- E 1 is the general formula (T 2)
- E 2 is the general formula (T3)
- E 1 is the general formula (T4)
- E 2 is a case of the general formula (T4), more preferably E 2 is the formula by the formula (T 1)
- E 1 is (T2)
- E 1 is the general formula (T 1)
- E 2 is the general formula (T4)
- E 1 is the general formula (T 2)
- E 2 is the general formula (T 3)
- E 1 is the general formula (T3 )
- E 2 is the general formula (T4)
- E 1 is the general formula (T 3)
- E 1 is the general formula (T3 )
- preferred compounds of the E 1 and E 2 when at least one is selected from the general formula (T1), or at least hand the general formula (.tau.4) It is a case where it is chosen from. More preferably, when one of ⁇ 1 and ⁇ 2 is selected from the general formula (T 1) and the other is selected from the general formulas (Tl), ( ⁇ 2) and ( ⁇ 4), or one of the general formula ( In the case of ⁇ 4), the other is selected from the general formula ( ⁇ 3) and the general formula ( ⁇ '4).
- ⁇ 1 and ⁇ 2 are selected from general formula (T 1) and the other is selected from general ⁇ ( ⁇ 2) or ( ⁇ 4), or both ⁇ 1 and ⁇ 2 are selected from general formula ( ⁇ 4) It is a case where it is chosen from.
- E 1 and E 2 is when one is selected from when the other by the general formula (T 1) is selected from the general formula (.tau.2), or E 1 and E 2 both formula (.tau.4) .
- the compounds used in the silver halide photographic material of the present invention are not limited to these. Further, for a compound in which a plurality of stereoisomers can exist, the stereostructure is not limited.
- Examples of other selenium compounds used in the silver halide color photographic light-sensitive material of the present invention include JP-B Nos. 439-13489 and 44-15748, and JP-A-4-125832; 4-1 0 9 240, 4-1 2 7 1 34 1, 5-40 3 24, 5-1 1 385, 6-5 1 4 1 5, 6-1 7 5 No. 25, No. 6-1 80478, No. 6-208 186, No. 6-208 184, No. 6-3 178, 67 No. 7, No. 9 259, No. 9 7- 9 848 3, 7- 140 5 7 9, 7- 30 18 79, 7- 30 18 80, 8-11 48 8 2, 9-13 Selenium compounds described in Nos.
- colloidal metal selenium for example, selenobenzone) Phenone
- isoselenosocyanates for example, selenocarboxylic acids, and the like.
- non-labile selenium compounds described in JP-B-46-4553 and JP-B-52-34492 such as selenous acid, selenocyanic acids (for example, potassium selenocyanate), selenazoles, and selenide Can also be used. Of these, selenocyanic acids are particularly preferred.
- the selenium compound used in the silver halide color photographic light-sensitive material of the present invention is not limited to the selenium compound described above.
- the selenium compound used in the silver halide color photographic light-sensitive material of the present invention has a binding energy of 3d orbital electron of selenium atom measured by an X-ray photoelectron spectrometer of 54. O eV or more and 65.0 eV. The following are preferred in terms of high contrast and low capri.
- the amount of the selenium sensitizer used in the silver halide photographic light-sensitive material of the present invention varies depending on the selenium compound used, silver halide grains, chemical ripening conditions and the like, but is generally 1 X per mole of silver halide. 1 0- 8 ⁇ 1 X 1 0 one 4 moles, preferably 1 X 1 0 - 7 ⁇ 1 X 1 0- 5 moles used.
- the conditions of chemical sensitization in the silver halide color photographic light-sensitive material of the present invention are not particularly limited, but pC1 is preferably 0 to 7, more preferably 0 to 5, and further preferably 1 to 3. preferable.
- the temperature is preferably from 40 to 95 ° C, more preferably from 50 to 85 ° C.
- the temperature is preferably from 40 to 80 ° C, more preferably from 50 to 70 ° C.
- the compounds represented by the general formulas (SE1) to (SE3) may be used singly or as a mixture of two or more kinds. Also, it may be added simultaneously with another selenium increasing agent.
- the selenium compound used in the silver halide color photographic light-sensitive material of the present invention can be added at any stage from immediately after grain formation to immediately before the end of chemical exposure.
- the preferred time of addition is between the time of desalting and the time of chemical sensitization.
- the compounds represented by the general formulas (SE1) to (SE3) may be used singly or as a mixture of two or more kinds in the same layer or a plurality of layers. Moreover, you may add simultaneously with another selenium increasing agent.
- PF1 gold selenium compound that can be used in the present invention
- PF2 a compound represented by any of the following general formulas (PF1) to (PF6) can be preferably used.
- PF1 General formula (PF2)
- 21 represents a compound capable of coordinating to gold via> 1, S, Se, Te, or P atom.
- n 21 represents 0 or 1.
- a 21 represents 0, S or NR 24 , and R 21 to R 24 represent a hydrogen atom or a substituent.
- R 23 may form a 5- to 7-membered ring with R 21 or R 22 .
- L 21 represents a compound capable of coordinating to gold via an N atom, an S atom, a Se atom, a Te atom or a P atom.
- n 21 represents 0 or 1.
- X 21 represents 0, S or NR 25 .
- Y 21 represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, OR 26 , SR 27 , N (R 28 ) R 29 .
- R 25 to R 29 each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group.
- Y 21 may combine with each other to form a ring.
- L 21 represents a compound capable of coordinating to gold via an N atom, an S atom, a Se atom, a Te atom or a P atom.
- n 21 represents 0 or 1.
- R 21 (3 , R 211 and R 212 each independently represent a hydrogen atom or a substituent, and at least one of 2113 and 1 ⁇ 211 represents an electron-withdrawing group.
- L 21 represents a compound which can coordinate to gold via an N atom, an S atom, a Se atom, a Te atom or a P atom.
- n 21 represents 0 or 1.
- W 21 represents an electron-withdrawing group R 213 to R 215 each represent a hydrogen atom or a substituent. W 21 and R 213 may combine with each other to form a cyclic structure.
- 21 represents a compound capable of coordinating to gold via a ⁇ atom, S atom, Se atom, Te atom or P atom.
- n 21 represents 0 or 1.
- Item 22 represents ⁇ , S, Se, Te or NR 219 .
- R 216 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group or an acyl group; and R 217 to R 219 represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a hetero ring.
- Z 21 represents a substituent, and n 22 represents an integer of 0 to 4. When n 22 is 2 or more, Z 21 may be the same or different.
- Q 21 and Q 22 are compounds selected from the general formulas (SE 1) to (SE 3) described above, and the Se atom in Q 21 and Q 22 is Au Coordinate to n 23 represents 0 or 1, and J 21 represents anion. When n 23 is 1, Q 21 and Q 22 may be the same or different. However, the compound represented by the formula (PF6) does not include the compounds represented by the general formulas (PF1) to (PF5).
- R 21 and R 22 are preferably a hydrogen atom, an alkyl group, an alkyl group, a heterocyclic group, a hydroxyl group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an amino group, a mercapto group.
- R 23 is preferably a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, more preferably an alkyl group, an aryl group, or a heterocyclic group, and most preferably an alkyl group or an aryl group.
- R 24 is preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an amino group, an acylamino group, an alkyl or arylsulfonylamino group, an alkyl or arylaryl group, an acyl group, an aryloxy group.
- R 23 is good to form a ring structure of five to seven membered with R 21 or R 22 les.
- the ring structure formed is a non-aromatic oxygen-, sulfur-, or nitrogen-containing heterocycle. Further, this ring structure may form a condensed ring with an aromatic or non-aromatic carbon ring or a hetero ring.
- Contact to the present invention • Itewa R 23 is not more preferable to form a cyclic structure 5-7 membered with R 21 or R 22.
- a 21 is preferably 0, S or NR 24
- R 21 and R 22 are each a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic ring.
- R 23 is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group
- R 24 is a hydrogen atom, an alkyl group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, or a heterocyclic thio group.
- a 21 is O or S
- R 21 and R 22 are each a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group
- R 23 is an alkyl group, an aryl group, or a heterocyclic group. is there.
- a 21 represents O or S
- R 21 and R 22 are each a hydrogen atom, an alkyl group, or a aryl group
- R 23 is an alkyl group, It is a reel group.
- the cyclic structure formed by R 23 with R 21 or R 22 is gnorecose, mannose, galactose, growth, xylose, lyxose, arabinose, ribose, fucose, idose, talose, arose.
- a 21 in the general formula (PF 1) Is an oxygen atom ( ⁇ )) and its sulfur analog (when A 21 in the general formula (PF 1) is S).
- the sugar derivative means a hydroxyl group, an amino group, or a carboxy group in the sugar structure is an alkoxy group (including a group containing a repeating ethyleneoxy or propyleneoxy unit), an aryloxy group, a heterocyclic oxy group, an acryloxy group, Alkoxycarbonyloxy, aryloxycarbonyloxy, carbamoyloxy, sulfonyloxy, silyloxy, (alkyl, aryl, or heterocycle) amino, acylamino, sulfonamide, perylene, Choprad group,
- N-hydroxyureido group alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, oxamoylamino group, N- (alkyl or aryl) sulfonyl Ureido group, N-acyl-delay group, N-acylsulfamoylamino group, hydroxyamino group, acetyl group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, alkamoyl And N-hydroxycarbamoyl, N-acylcarbamoyl, N-snolephoninolecarbamoyl, N-carbamoylcarbamoyl, N-sulfamoylcarbamoyl and the like.
- preferred compounds include, for example, selenognorecose gold (I) salts, selenomannose gold (I) salts, selenogalactose gold (I) salts, selenolyxose gold (I) salts, and sugar derivatives thereof.
- X 21 is preferably ⁇ or S, and more preferably ⁇ .
- Upsilon 21 is preferably an alkyl group having 1 to 30 carbon atoms,. Alkenyl group, an alkynyl group, Ariru group or ⁇ atom, Omicron atom, 5- to 7-membered heterocyclic group containing at least one S atom, OR 26 , SR 27 , or N (R 28 ) R 29 , preferably an alkyl group, an aryl group, a heterocyclic group, OR 26 , SR 27 , or N (R 28 ) R 29 , more preferably. It is an alkyl group, aryl group, heterocyclic group or N (R 28 ) R 29 , more preferably an alkyl group, aryl group or heterocyclic group.
- R 25 to R 29 represent a hydrogen atom, an alkyl group, an alkenyl group, an alkyl group, an aryl group or a heterocyclic group, preferably a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group; Preferably it is an alkyl group or an aryl group.
- X 21 and Y 21 may be bonded to each other to form a ring.
- the ring formed in this case is a 3- to 7-membered nitrogen-containing hetero ring, for example, pyrroles, indoles, imidazoles, benzimidazoles, thiazols, benzothiazoles, isooxazoles, oxazoles , Benzoxazoles, indazoles, purines, pyridines, pyrazines, pyrimidines, quinolines, quinazolines.
- X 21 is preferably O or S, and Y 21 is an alkyl group, an aryl group, a heterocyclic group, OR 26 , SR 27 , N (R 28 ) R 29 And R 26 to R 29 are an alkyl group, an aryl group or a heterocyclic group. More preferably, X 21 is O, and Y 21 is an alkyl group, aryl group, or heterocyclic group. Most preferably, X 21 is O, and Y 21 is an alkyl group, aryl group, or heterocyclic group.
- At least one of R 21 ′ ° and R 211 represents an electron-withdrawing group, and the electron-withdrawing group referred to herein is a Hammett's substituent constant ⁇ p value.
- the electron-withdrawing group having a ⁇ ⁇ value of 0.2 or more include an acyl group, a formyl group, an acyloxy group, an acylthio group, a carbamoyl group, an alkoxycarbonyl group, an aryloxy carbonyl group, a cyano group, Nitro group, dialkylphosphono group, diarylphosphono group, dialkylphosphinyl group, diarylphosphinyl group, phosphoryl group, alkylsulfiel group, arylinolenorefininole group, anolequinolenolehoninole At least one group selected from the group consisting of a group, an arylesnolephoninole group, a snolephoninoleoxy group, an acylthio group, a sulfamoyl group, a thiosinate group, a thiocarbonyl group, an imino group, an imide,
- an acyl group preferably, an acyl group, a formyl group, a carbamoyl group, an alkoxycarbyl group, an aryloxycarbyl group, a cyano group, a dialkylphosphono group, a diarylphosphono group, and a dialkylphosphine Nore group, diarynophosphinino group, alkylsulfinyl group, arylsulfiel group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, thiocarbyl group, imino group, imino substituted with ⁇ atom Group, phosphoryl group, carboxy group (or salt thereof), alkyl group substituted with at least two or more halogen atoms, aryl substituted with another electron withdrawing group having a ⁇ ⁇ value of 0.2 or more A heterocyclic group or a halogen atom, more preferably an acyl group
- both R 21 ° and R 211 preferably represent an electron-withdrawing group.
- R 212 is preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an amino group, an acylamino group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkyl or 7 "reelsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbyl group and carbamoyl group, more preferably hydrogen atom, alkyl group, aryl group, heterocyclic group, alkoxy group, An aryloxy group, a heterocyclic oxy group, an amino group, and an acylamino group.
- R 210 , R 211 and R 212 are bonded to each other to form a ring.
- the ring formed is a non-aromatic carbocyclic or heterocyclic ring, preferably a 5- to 7-membered ring.
- R 21 ° forming a ring is preferably an acyl group, a carbamoyl group, an oxycarbonyl group, a thiocarbonyl group, or a sulfonyl group
- R 211 is an acyl group, a carbamoyl group, an oxypropyl group, a thiocarbonyl group, or a sulfonyl group.
- Group, imino group, imino group substituted by N atom, An acylamino group and a carbthio group are preferred.
- R 21 ° and R 211 are electron-withdrawing groups
- R 212 is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, Ryloxy group, heterocyclic oxy group, amino group, and acylamino group. More preferably, R 210 and R 211 are electron withdrawing groups, and R 212 is a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. Most preferably, R 210 and R 211 are electron withdrawing groups, and R 212 is a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.
- R 212 is a hydrogen atom
- R 212 is a hydrogen atom, an alkyl group, Ariru group, a heterocyclic group.
- R 210 and R 211 form a non-aromatic 5- to 7-membered ring
- R 212 is a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.
- the electron-withdrawing group represented by W 21 has the same meaning as the aforementioned electron-withdrawing group represented by R 21 (5 and R 211) , and the preferred range is also the same.
- R 213 to R 215 are preferably a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a carboxy group, a sulfamoinole group, a snorejo group, Anolequinole or arylsulfol group, asinole group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, etc., and more preferably hydrogen atom, halogen atom, alkyl group, alkenyl group, alkynyl group, a A leyl group, a heterocyclic group, a cyano group, a carboxy group, a sulfo group, an alkyl or arylaryl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group
- W 21 and R 213 may combine with each other to form a ring.
- the ring formed is a non-aromatic carbon ring or a hetero ring, preferably a 5- to 7-membered ring.
- W 21 forming a ring is preferably an acyl group, a carbamoyl group, an oxycarbonyl group, a thiocarbonyl group, or a sulfol group
- R 213 is an alkyl group, an alkenyl group, an aryl group, or a heterocyclic tomb. preferable.
- W 21 is preferably an electron-withdrawing group
- R 213 to R. 215 are each a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkyl group, An aryl group, a heterocyclic group, a cyano group, a carboxy group, a sulfo group, an alkyl or arylsulfol group, an acyl group, an aryloxycarbonyl group, an alkoxycarbyl group, and a carbamoyl group.
- W 21 is an electron-withdrawing group
- R 213 to R 215 are each a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, a carboxy group, a sulfo group, or an alkyl group.
- R 213 to R 215 are each a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, a carboxy group, a sulfo group, or an alkyl group.
- an arylsulfonyl group an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, or a carbamoyl group.
- W 21 is an electron-withdrawing group
- R 213 to R 215 are a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a carboxy group, a sulfo group.
- W 21 and R 213 are bonded to each other.
- a non-aromatic 5- to 7-membered ring is also preferable, in which case R 213 is an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, etc.
- R 214 and R 215 are a hydrogen atom, Halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, carboxy group, sulfo group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxy And a carboyl group and a carbamoyl group.
- W 21 and R 213 are bonded to each other to form a non-aromatic 5- to 7-membered ring
- R 214 and R 215 are hydrogen, halogen, alkyl, alkenyl, alkynyl Group, aryl group, heterocyclic group, cyano group, carboxy group, sulfo group, 'alkyl or arylsulfonyl group, acyl group, arylino ethoxy group, alkanol carboxy group, carbamoyl group, most
- W 21 and R 213 are bonded to each other to form a non-aromatic 5- to 7-membered ring
- R 214 and R 215 are a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group.
- R 216 is preferably a hydrogen atom, an alkyl group, an aryl group or an acyl group, more preferably a hydrogen atom, an alkyl group or an acyl group, and most preferably an alkyl group.
- R 217 and R 218 are preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group, and most preferably one is a hydrogen atom and the other is a hydrogen atom or an alkyl group.
- R 219 is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group, and most preferably an alkyl group.
- a 22 represents S, S, Se, Te or NR 219 , but is preferably 0, S or NR 219 in the present invention, more preferably O or S. , O is most preferred.
- Z 21 represents a substituent.
- substituents include the same groups as those described above.
- Z 21 is preferably a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an N-acylcarbamoyl group, an N-sulfonyl group.
- Rucarbamoyl carbamoylcarbamoyl, thiocarbamoyl, N-snorrefamoylcarbamoyl, carbazoyl, carboxy (and its salts), cyano, formyl, hydroxy, alkoxy Group, aryloxy group, heterocyclic oxy group, acyloxy group, nitro group, amino group, (alkyl, aryl or hetero ring) amino group, acylamino group, sulfonamide group, peridode group, thioperido group, alkylthio group , Aryl thio group, heterocyclic thio group, ( Alkyl or aryl) sulfonyl group, (alkyl or aryl) sulfier group, sulfo group (including its salt), sulfamoyl group, etc., more preferably halogen atom, alkyl group, aryl group, heterocyclic group, carb
- n 22 represents an integer of 0 to 4, but in the present invention, n 22 preferably represents 0 to 2, and more preferably 0 or 1.
- a 22 represents 0, S or NR 219 ;
- R 2 is represents a hydrogen atom, an alkyl group, an aryl group, or an acyl group
- R 217 and R 218 represent a hydrogen atom, an alkyl group, or an aryl group
- R 219 represents a hydrogen atom, an alkyl group, or an aryl group.
- Z 21 is an alkyl group, Ariru group, a carboxy group (including a salt ⁇ Piso), human Dorokishi group, an alkoxy group, Ariruokishi group, (alkyl, ⁇ Li Lumpur or to, Terrorist ring) It represents an amino group, a peridot group, an alkylthio group, an arylthio group, a sulfo group (and its salts).
- a 22 represents 0, S or NR 219 ;
- R 216 represents an alkyl group;
- R 217 and R 218 represent a hydrogen atom or an alkyl group;
- R 219 represents an alkyl group or an aryl group;
- n 22 represents 0 to 2
- Z 21 represents an alkyl group, an aryl group, a carboxy group (including a salt thereof), a hydroxy group, an alkoxy group, an aryloxy group, an (alkyl, aryl, or heterocyclic) amino group , Ureido group, alkylthio group, arylthio group, and sulfo group (and their salts).
- a 22 represents 0, S or NR 219
- R 216 represents an alkyl group
- R 217 and R 218 represent a hydrogen atom or an alkyl group
- R 219 represents an alkyl group
- n 22 represents 0 to represents 2
- Z 21 is an alkyl group, Ariru group (including a salt of ⁇ Piso) carboxy group, arsenate Dorokishi group, an alkoxy group, Ariruokishi group, (alkyl, Ariru or heterocyclic) amino group, Ulei de Group, alkylthio group, arylthio group, and sulfo group (including salts thereof).
- a 22 represents ⁇ , represents R 216 Gaa alkyl group, one of R 217 and R 218 represents other is a hydrogen atom or an alkyl Le group a hydrogen atom, 11 2 2 represents 0-1 , Z 21 is an alkyl group, aryl group, carboxy group (including its salt), hydroxy group, alkoxy group, aryloxy group, (alkyl, aryl, or hetero ring) amino group, perylene group , An alkylthio group, an arylthio group, and a sulfo group (including salts thereof). '
- n 21 represents 0 or 1, but when 1 2 1 represents 1 , 21 represents 1 ⁇ atom, 3 atom, Se atom, Te atom or Represents a compound that can coordinate to gold via a P atom.
- substituted or unsubstituted amines preferably mean primary, secondary or tertiary alkylamines or arylamines having 1 to 30 carbon atoms
- 5- to 6-membered nitrogen-containing heterocycles Class refer to a 5- or 6-membered nitrogen-containing heterocyclic ring composed of a combination of N, ⁇ , S and C, which may have a substituent.
- a substituent May be coordinated to gold via a substituent, or may be coordinated to gold via a substituent, such as benzotriazole, triazole, tetrazole, indazole, benzimidazole, imidazole, benzothiazole, thiazole, thiazoline, Benzoxazole, benzoxazoline, oxazole, thiadiazole, oxaziazole, triazine, pyrrole, pyrrolidine, imidazolidine, morpholine ), Meso-ions (here, meso-ion compounds are 5- or 6-membered heterocyclic compounds that can be satisfactorily represented by a single covalent or localized structural formula.
- benzotriazole triazole, tetrazole, indazole, benzimidazole, imidazole, benzothiazole, thiazole, thiazoline, Benzoxazole, benzoxazoline, oxazole,
- Compound, and the mesoionic ring is an imidazolyme ring, Ring, oxazolym ring, thiazolium ring, triazolium ring, tetrazolium ring, thiadiazolium ring, oxaziazolium ring, thiatriazolium ring, oxatriazolium ring and the like.
- Thiols preferably alkylthiols having 1 to 30 carbon atoms, or arylthiols having 6 to 30 carbon atoms or at least one of N, O and S atoms
- thioethers preferably alkyl groups having 1 to 30 carbon atoms, aryl groups, or 5- to 7-membered rings containing at least one of N, ⁇ , and S atoms
- a compound in which each heterocyclic group is bonded to an S atom and may be symmetric or asymmetric, such as dialkylthioethers, diarylthioethers, diheterocyclic thioethers, alkylarylthioethers, and alkyl-heterocyclic thioate.
- diaryls preferably an alkyl group having 1 to 30 carbon atoms, an aryl group or an aryl group.
- Useful thioamides include, for example, US Pat. , 030,925, 4,031,127, 4,080,207, 4,245,037, 4,255,511 and 4,266,031 And 276, 364 Research Disclosure Vol. 151, Jan. 1976, Jan. 1, pp. 162, and 176, Vol. 176, Jan. 1978, Feb.
- thiourea thiourethane, dithiocarbamic acid ester
- 4-thiazoline-12-thione thiazolidine-12-thione
- 4-oxazoline-12-thione oxazolidine-12-thione
- 2-pyrazolinone 5-thione 4-imidazoline-12-thione, 2-thiohydantoin, rhodanine, isorodine, 2-thio-1,4-oxazolidinedione, thiobarbituric acid, tetrazoline-5-thione, 1,2 1,4-triazoline-1 3-thione, 1,3,4-thiadiazoline-1 2-thione, 1,3,4-oxadiazoline-1 2-thione, benzimidazoline 1-2-thione, benzo Sazorin is 2-thione and base Nzochiazorin 2-thione, which may be substitution.
- Selenols preferably alkyl selenols having 1 to 30 carbon atoms, arylselenols, or 5- to 7-membered heterocyclic selenol containing at least one of N, O, and S atoms
- Selenoethers preferably, selenoether compounds in which an alkyl group, aryl group, or heterocyclic group having 1 to 30 carbon atoms is bonded to a Se atom; It may be asymmetrical substitution, for example, dialkyl selenoethers, diaryl selenoethers, diheterocyclic selenoethers, alkylaryl selenoethers, alkylheterocyclic selenoethers, arylylheterocyclic seleno Preferred are dialkylselenoethers, diarylselenoethers and alkylaryls.
- Diselenides preferably diselenide compounds in which an alkyl group, aryl group or heterocyclic group having 1 to 30 carbon atoms is bonded to a Se atom, whether symmetric or asymmetric with respect to the diselenide group.
- dialkyl diselides and diaryl diselenides are also alkylaryl diselenides.
- L 21 is preferably 5 to heterocyclic compounds to 6-membered nitrogen-containing, meso, thiols, Ji Oeteru acids, Chioami earth, selenol compound, selenoethers, Serenoami earths al kills phosphines or ⁇ reel phosphine And more preferably a 5- or 6-membered nitrogen-containing heterocyclic ring, mesoions, thiols, thioethers, thioamides, selenols, alkylphosphines or arylphosphines, most preferably Mesions, thiols, thioethers, thioamides, selenols, alkylphosphines or arylphosphines.
- Particularly preferred L 21 is selected from compounds represented by any of the following formulas (PL 1) to (PL 5).
- Ch is S, represents Se or Te, M 21 represents a counter cation to neutralize the charge of the hydrogen atom or compound.
- a 2 2 3 3 represents the ' ⁇ + 0, S or NR 223, R 220, R 221 , R 222, R 223 are respectively synonymous with the aforementioned R 21, R 22, R 23 , R 24, The same applies to the preferred range.
- X 22 represents 0, S or NR 224
- Y 22 represents H, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, OR 225 , SR 226 ,
- N (R 227 ) represents R 228 .
- R 224, R 22 5, R 2 26, R 22 7, R 22 8 is described above, respectively
- R 25 , R 26 , R 27 , R 28 and R 29 have the same meanings and preferred ranges are also the same.
- R 229 , R 23 °, and R 231 are respectively the aforementioned R 210 , It has the same meaning as R211 and R212, and the preferred range is also the same.
- W 22 , R 232 , R 233 , and R 234 have the same meanings as W 21 , R 213 , R 214 , and R 215 , respectively, and the preferable range is also the same.
- a 24 represents 0, S, Se, Te or NR 238 .
- R 235 , R 236 , R 237 , R 238 , Z 22 , and ⁇ 23 have the same meanings as R 216 , R 217 , R 218 , R 219 , Z 21 , and n 22 , respectively, and the preferred ranges are also the same. .
- L 21 is selected from the compounds represented by any one of General Formulas (PL 1) ⁇ (PL 5 ), the general formula (PF 1) ⁇ compound represented by any one of (PF 5) gold ( It can be a symmetric or asymmetric complex with respect to I). In the present invention, both are preferred, but the case of a symmetric complex with respect to gold (I) is more preferred.
- Ch represents S, Se or Te.
- S or Se is preferable, and S is more preferable.
- M 21 represents a counter cation to neutralize the charge of the hydrogen atom or compound.
- M 21 represents a counter cation, specifically, an inorganic cation such as an alkali metal such as Li, Na, K, Rb, or Cs, or an alkaline earth metal such as Mg, Ca, or Ba, or substituted or unsubstituted And organic cations such as ammonium ion and phosphonium ion.
- M 21 is an inorganic cation, M 21 does not represent an Ag + ion or an Au + ion in the present invention.
- M 21 is preferably a hydrogen atom or an alkali metal cation, an alkaline earth metal cation, a substituted or unsubstituted ammonium ion, and an alkali metal cation, a substituted or unsubstituted ammonium ion. And more preferably an alkali metal cation or a substituted or unsubstituted ammonium ion.
- M 21 is a cation of an alkali metal
- Ch is S or Se
- a 23 is ⁇ or S
- R 220 and R 221 are a hydrogen atom, an alkyl group and an aryl group, respectively
- R 222 is an alkyl group and an aryl group.
- M 21 is a cation of an alkali metal
- Ch is S
- a 23 is O or S
- R 22 Q and R 221 are each a hydrogen atom, an alkyl group, an aryl group, and R In the case where 222 is an alkyl group or aryl group.
- glucose R 222 is formed with R 220, or R 221, manno Ichisu.
- Preferred compounds for example Chiodaruko over scan as L 21, Chioman'nosu, Chiogarata toast, Chiorikisosu, Chiokishirosu, Chioara Binosu, seleno grayed Honoré course, seleno mannose, Serenogaraku toast, seleno Rikiso scan, seleno xylose, seleno arabinose Contact Yopi ether opening glucose And its metal salts, and its sulfur analogs and their derivatives.
- ⁇ 21 is an alkali metal cation
- Ch is S or Se
- X 22 is O or S
- Y 22 is H, alkyl Group, aryl group, heterocyclic group
- M 21 is a cation of an alkali metal
- Ch is S or Se
- X 22 is O
- Y 22 is an alkyl group, aryl group, or heterocyclic group.
- M 21 is a cation of an alkali metal
- Ch is S
- X 22 is O
- Y 22 is an alkyl group, aryl group, or heterocyclic group.
- M 21 is an alkali metal cation
- Ch is S or Se
- R 229 and R 23 Q are electron-withdrawing
- R 231 is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an amino group, or an acylamino group.
- M 21 is an alkali metal cation
- Ch is S or Se
- R 229 and R 23 ° are electron withdrawing groups
- R 23 i is a hydrogen atom, an alkyl group, Aryl group and heterocyclic group.
- M 21 is a cation of an alkali metal
- Ch is S
- R 229 and R 23 ° are electron-withdrawing groups
- R 231 is a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic ring. Group.
- R 229 and R 23Q may form a ring of 5-7 membered non-aromatic, this time M 21 Al-force Ch is S or Se, and R 231 is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an amino group, an acylamino group. is there.
- M 21 is a cation of an alkali metal
- Ch represents S or Se
- R 231 is A hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.
- M 21 is a cation of an alkali metal
- Ch is S
- R 229 and R 23 ° form a non-aromatic 5- to 7-membered ring
- R 231 is a hydrogen atom or an alkyl group.
- An aryl group and a heterocyclic group is preferred.
- M 21 is an alkali metal ion
- Ch is S or Se
- W 22 is an electron-withdrawing group
- 232 to R 234 represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a carboxy group, a sulfo group, an alkyl or aryl sulfol group, an acyl group, and an aryl group
- M 21 is a cation of an alkali metal
- Ch is S or Se
- W 22 is an electron-withdrawing group
- R 232 to R 234 are a hydrogen atom, a halogen atom, an alkyl group, Nyl group, a.
- M 21 is a cation of an alkali metal
- Ch is S or Se
- W 22 is an electron-withdrawing group
- R 232 to R 234 are a hydrogen atom, a nitrogen atom, an alkyl group, Alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, carboxy group, sulfo group, alkyl or arylsulfol group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, and carbamoyl group is there.
- M 21 Is an alkali metal cation
- Ch represents S or Se
- R 26 is an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, etc.
- R 233 and R 234 are a hydrogen atom, a halogen atom, Alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, carboxy group, Those which are a sulfo group, an alkyl or arylsulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group and the like are preferred.
- M 21 is a cation of an alkali metal
- Ch represents S or Se
- W 22 and R 232 combine with each other to form a non-aromatic 5- to 7-membered ring
- R 233 and R 234 are hydrogen atom, halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, carboxy group, sulfo group, alkyl or arylsulfonyl group, acyl Groups, aryloxycarbol groups, alkoxycarbonyl groups, and carbamoyl groups
- M 21 is an alkali metal cation
- Ch represents S
- W 22 and R 232 are Bond to each other to form a non-aromatic 5- to 7-membered ring
- R 233 and R 234 are a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group
- Ch is S or Se
- a 24 represents 0, S or NR 238
- R 235 represents a hydrogen atom, an alkyl group, an aryl group, or an acyl group
- R 236 and R 237 represent a hydrogen atom, an alkyl group, or an aryl group
- R 238 represents a hydrogen atom, an alkyl group or an aryl group, n 23 represents 0 to 2, Z 22 represents an alkyl group, an aryl group, a carbonyl group (including salts thereof), a hydroxy group, an alkoxy group Group, aryloxy group, (alkyl, aryl, or heterocycle) amino group, perylene group, alkylthio group, arylthio group, sulfo group (and salts thereof).
- Ch is S or Se
- a 24 represents ⁇ , S or NR 238
- R 235 represents an alkyl group
- R 236 and R 237 represent a hydrogen atom or an alkyl group
- R 238 There alkyl group or ⁇ Li Ichiru group
- n 23 represents 0 to 2
- Z 22 and Al kill group Ariru group (including a salt of ⁇ Piso) carboxy group, hydroxy group, alkoxy group, Ariruokishi group , (Alkyl, aryl, or heterocyclic ring) This represents an amino group, a ureido group, an alkylthio group, an arylthio group, or a sulfo group (including salts thereof).
- R 235 represents an alkyl group
- R 236 Contact Yopi
- R 237 represents a hydrogen atom or an alkyl group
- R 238 represents an alkyl group
- eta 2 ⁇ 3 represents 0 to 2
- Ch is S
- a 24 represents O
- R 235 represents an alkyl group
- one of R 236 and R 237 represents a hydrogen atom and the other represents a hydrogen atom or an alkyl tomb
- n 23 represents 0
- Z 22 represents an alkyl group, an aryl group, a carboxy group (including a salt thereof), a hydroxy group, an alkoxy group, an aryloxy group, an (alkyl, aryl or hetero ring) amino group, or a ureido group , Alkylthio, arylthio, and sulfo groups (and salts thereof).
- the compound represented by any of formulas (PL1) to (PL5) can be synthesized by the method described in JP-A-2004-4446.
- J 21 represents an ion.
- Anion specifically a halogen ion (e.g. F-, C 1-, B r-, I-), Tetorafuruorobo port sulfonate ion (BF 4 -), the hexa full O Rojo Suho sulfonate ion (PF 6 -) , Hexafluoroantimonate ion (S b F 6 —), arylinosulfonate ion (eg, p-toluenesulfonate ion), alkylsulfonate ion (eg, methanesulfonate ion, trifluoromethanesulfonate ion, etc.), carboxy Ions (eg, acetate ion, trifluoroacetate ion, benzoate ion, etc.).
- These anions are composed of a mercapto group (one
- the compound does not have an adsorptive group to gold, such as (1-Se-) and telluro-teru (1Te-).
- J 21 is preferably a halogen ion, a tetrafluoroborate ion, a hexanoleophosphonate ion, a perinoresnorrefonate ion or an anorex.Rusnorefonate ion, and a halogen ion, a tetrafluoroborate ion or a hexafluorophosphophosphate ion.
- halogen ions are even more preferred.
- halogen ions are even more preferred.
- CI—, Br— or I— is preferred
- C 1— or Br— is more preferred
- C 1— is more preferred.
- Q 21 and Q 22 are selected from the compounds represented by any one formula described in the previous (SE 1) ⁇ (SE 3 ).
- Guarding general formula (SE 1) a compound represented by, preferably, M 1 ⁇ Pi M 2 each are a hydrogen atom, an alkyl group, Aruke - group, Ariru group, a heterocyclic group a ⁇ Pi Ashiru group, Q is an alkyl group, an alkenyl group, an Ariru group or NM 4 M 5,, M 4 Contact Yopi M 5 is a hydrogen atom, an alkyl group, an alkenyl group, Ariru group, a heterocyclic group This is the case where More preferably, M 1 and M 2 are each a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group, Q is an alkyl group, an aryl group, or NM 4 M 5 , and M 4 and M 5 are a hydrogen atom , An alkyl group, an alkenyl group, and an aryl group.
- M 1 and M 2 are a hydrogen atom, an alkyl group, and an aryl group, respectively
- Q is NM 4 M 5
- M 4 and M 5 are a hydrogen atom, an alkyl group, and an aryl group.
- Q 21 or Q 22 is a compound represented by the general formula (SE 2), preferably X ⁇ X 3 represents an alkyl group, an aryl group, or a heterocyclic group, respectively.
- X 1 to X 3 each represent an aryl group.
- E 1 and E 2 are selected from the general formulas (T 2) to (T 4). More preferably, when one of E 1 and E 2 is selected from the general formula (T4), and the other is selected from the general formula (T 2), the general formula (T 3) or the general formula (T 4) More preferably, one of E 1 and E 2 is selected from the general formula (T 4), and the other is selected from the general formula (T 3) or the general formula (T 4), and most preferably. This is the case where E 1 and E 2 are both selected from the general formula (T 4).
- J 21 is a halogen ion, a tetraphenoleroborate ion, a hexafenoleo phosphonate ion, an arylsulfonate ion or an alkylsulfonate ion.
- the n 23 is 0 or 1
- compounds of Q 21 and Q 22 are represented by the general formula (SE 1) or (SE 3) It is the case when selected from the object ', more preferably a hexa full O Rojo Suho sulfonate ion J 21 is a halogen ion, Tetorafuruorobo Lone one Toion or to, 11 2 3 is 0,
- Q 21 is the general formula (SE 3) a case where in selected from the compounds represented by, more preferably J 2 1 is halogen ion, n 23 is 0, if Q 21 is selected from the compounds represented by the general formula (SE 3) It is.
- PF1 to (PF6) preferably used are any of the compounds represented by the general formulas (PF1), ( ⁇ F5) and (PF6). And more preferably a compound represented by the general formula (PF1) or (PF6), and most preferably a compound represented by the general formula (PF6).
- the amount of the compound represented by any of the general formulas (PF1) to (PF6) that can be used in the present invention can vary widely depending on the case, but is usually 1 ⁇ 1 per mol of silver halide. 0-7 a to 5 X 1 0_ 3 mol, preferably 5 X 1 0 _6 ⁇ 5 X 1 0- 4 mol.
- Compounds represented by any of the general formulas (PF1) to (PF6) include water, alcohols (eg, methanol and ethanol), ketones (eg, acetone), and amides (eg, dimethylformamide). ), Glycols (e.g., methylpropylene glycol) and esters (e.g., ethyl acetate) and the like, or may be added as a solid dispersion (microcrystalline dispersion) by a known dispersion method. Good.
- the compound represented by any of the general formulas (PF1) to (PF6) it is preferable to add it during the period from the formation of the silver halide grains to the end of the chemical sensitization step.
- the compounds represented by the general formulas (PF1) to (PF6) one kind thereof may be used, or two or more kinds thereof may be used as a mixture in the same layer or a plurality of layers. It may be used simultaneously with other selenium sensitizers.
- the compound represented by any of the general formulas (PF 1) to (PF 6) can be synthesized by the method described in JP-A-2004-2 & 026.
- SE1-2, SE2-1, SE2-12-2, SE3-16-1, SE3-131 are preferred, and SE3-4, SE3--9.
- SE 3—17, SE 3—29, SE 3—37 are more preferred, PF 2—5, PF 3—6, PF 4—3, PF 5—7 are even more preferred, and PF 1 —1, PF 6-1 is most preferred.
- selenium compounds include eh compounds (SE1-2), (SE2-1), (SE2-1-2), (SE 3—16), (SE 3—31), (SE 3—4), (SE 3—17), or (SE 3—37) are preferred, and for gold selenium compounds, Compound (PF2-5), (PF3-6), (PF4_3), (PF5-7), (SE3-9), (SE3-2 9), (PF1-1 ) Or (PF 6-1) is preferred.
- Silver halide emulsions are usually subjected to chemical sensitization.
- the silver halide emulsion can use the selenium-based sensation together with another chemical sensation.
- a sulfur sensation represented by the addition of an unstable sulfur compound, a noble metal sensation represented by a gold sensation, or a reduction sensation can be used alone or in combination.
- the compounds used for the chemical reaction those described in the lower right column of page 18 to the upper right column of page 22 of JP-A-62-215527 are preferably used. Among them, it is particularly preferable to give a feeling of gold.
- a sulfur sensation, a tellurium sensation, and another gold sensation—a precious metal sensation can also be used.
- colloidal gold sulfide or a gold sensitizer having a complex stability constant of 1 og ⁇ 2 of 21 or more and 35 or less can be preferably used.
- commonly used gold compounds for example, chloroaurate, potassium chloride aurate, auric tric oleide, potassium thioate, potassium oleate, tetrasodium acrylate
- Ammonium nitrate thiocyanate for example, chloroaurate, potassium chloride aurate, auric tric oleide, potassium thioate, potassium oleate, tetrasodium acrylate
- Ammonium nitrate thiocyanate for example, chloroaurate, potassium chloride aurate, auric tric oleide, potassium thioate, potassium oleate, tetrasodium acrylate
- Ammonium nitrate thiocyanate
- a reducing sensitizer in combination, and specific examples include stannous chloride, aminoiminomethansulfinic acid, hydrazine derivatives, borane compounds, silane compounds, polyamine compounds, and the like.
- a selenium compound in the presence of a silver halide solvent.
- thiocyanates for example, potassium thiocyanate, etc.
- thioether compounds for example, U.S. Pat. Nos. 3,021,215 and 3,271,157, Japanese Patent Publication No. 58-30571, and Japanese Patent Application Laid-Open No. — Compounds described in No.
- thiocyanates thioether compounds, tetrasubstituted thiourea compounds and thione compounds can be preferably used.
- the amount used it is possible to use 1x10 one 5 ⁇ 1x10 one 2 moles per mol of silver halide.
- the silver halide emulsion preferably contains iridium.
- Iridium preferably forms an iridium complex, and a six-coordination complex having six ligands and having iridium as a central metal is preferable for uniform incorporation into a silver halide crystal.
- One preferred embodiment of the iridium used in the silver halide color photographic light-sensitive material of the present invention is a iridium atom having a chlorine atom (C 1), a bromine atom (Br), or an iodine atom (I) as a ligand.
- a six-coordinate complex having (I r) as a central metal is preferred, and all six ligands are composed of a chlorine atom (C 1), a bromine atom (B r), or an iodine atom (I).
- a 6-coordinate complex having r) as the central metal is more preferred.
- a chlorine atom (C 1), a bromine atom (Br), or an iodine atom (I) may be mixed in the six-coordinate complex.
- a hexacoordination complex having an iridium atom (Ir) as a central metal having a chlorine atom (C 1), a bromine atom (Br), or an iodine atom (I) as a ligand must be included in the silver bromide-containing phase. However, it is particularly preferable to obtain a hard gradation with high illuminance exposure.
- Another preferred embodiment of the compound containing iridium is a hexacoordination complex having a iridium atom (I r) having at least one ligand other than a halogen atom and cyanide as a central metal, and a water molecule (H 20 ), OH, oxygen atom (O), OCN, thiazole or substituted thia tetrazole, 6-coordinate complex is preferably a central metal I r having a thiadiazole or substituted thiadiazole as ligands, at least one water molecule (H 2 0), An iridium atom (I) comprising OH, oxygen atom (O), ⁇ CN, thiazole or substituted thiazole as ligands and the remaining ligands being chlorine atoms (C 1), bromine atoms (Br), or iodine atoms (I) A 6-coordinate complex having r) as the central metal is more preferred.
- one or two 5-methylenothiazoles, 2-chloro-5-funorothiothiazolone or 2-promo-5-phenolylthiazolazole as ligands and the remaining ligands are C1
- a 6-coordination complex having Br as the central metal with Ir as the central metal is particularly preferred.
- At least one water molecule (H 20 ), OH, oxygen atom (O), OCN, thiazole, or substituted thiazole as a ligand, and the remaining ligands are chlorine atom (C 1), bromine atom
- the silver halide emulsions may contain, in addition to the above iridium complex [F e (CN) 6] 4 -, [F e (CN) 6] 3 one, [Ru (CN) ⁇ ] 4 one, [R e (CN) 6] 4 one, [O s (CN) 6] 4 iron atoms having a first class of CN ligands, ruthenium atom, preferably contains rhenium atom or 6-coordinated complex, of which central metal is osmium atom.
- the silver halide emulsion used in the silver halide color photographic light-sensitive material of the present invention further includes a pentachloroditrosyl complex, a pentachlorothionitrosyl complex having a ruthenium atom, a rhenium atom, or an osmium atom as a central metal, and a chlorine atom. It preferably contains a six-coordination complex having a rhodium atom having a bromine atom or an iodine atom as a ligand as a central metal. These ligands may be partially aqua !!.
- the above-mentioned metal complexes are anions, and when forming a salt with a cation, those which are easily dissolved in water as a counterion are preferable. Specifically, alkali metal ions such as sodium ion, potassium ion, rubidium ion, cesium ion and lithium ion, ammonium ion, and alkyl ammonium ion are preferable. These metal complexes are dissolved in a mixed solvent with water and a suitable organic solvent that can be mixed with water (eg, alcohols, ethers, glycols, ketones, esters, amides, etc.). Can be used.
- a suitable organic solvent that can be mixed with water (eg, alcohols, ethers, glycols, ketones, esters, amides, etc.). Can be used.
- metal complexes can be added directly to the reaction solution when forming silver halide grains, or in an aqueous halide solution for forming silver halide grains, or in other solutions. Is preferably incorporated into the silver halide grains. It is also preferable to carry out physical ripening with fine particles in which a metal complex is previously incorporated in the grains and incorporate them into silver halide grains. Further, these methods can be combined and contained in silver halide grains.
- these complexes When these complexes are incorporated into silver halide grains, they may be uniformly present inside the grains, but are disclosed in JP-A-4-1208936, JP-A-2-125245, and JP-A-3-1888437. As disclosed, it is also preferable that the complex is present only in the surface layer of the particle, or that the complex is present only inside the particle and that a layer containing no complex is added to the surface of the particle. Further, as disclosed in U.S. Pat. Nos. 5,252,451 and 5,256,530, the particle surface phase is obtained by physical ripening with fine particles having a complex incorporated therein.
- halogen composition at the position where the above complex is contained is not particularly limited, but all six ligands are chlorine atoms (C 1), bromine atoms (Br), or iridium atoms (I) consisting of iodine atoms (I). I r) as the central metal It is preferable that the six-coordinate complex be contained in the maximum concentration of silver bromide.
- the specific silver halide emulsion used in the first embodiment of the present invention preferably contains a compound represented by the following general formula (D1).
- M D1 is Cr, Mo, Re, Fe, Rii, Os, Co, Rh,? ⁇ 1 or? 1: represents X D1 represents a halogen ion.
- L D 1 represents an arbitrary ligand different from X D1.
- nl represents 3, 4, 5, or 6, and m 1 represents the charge of the metal complex and represents 4, 1, 3—, 2—, 1—, 0, or 1+.
- a plurality of X D 1 may be the same or different from each other, when the L D1 there are multiple, they may be the same or different from each other.
- the metal complex represented by the general formula (D 1) does not have a cyano (CN-1) ligand, or has only one when it does.
- a metal complex represented by the following general formula (D1A) is preferable.
- MDIA represents Re , Ru, Os, and Rh
- XDIA represents a halogen ion
- L DlA represents NO or NS when M DlA is Re , 1 ⁇ 1 or 03, and represents H 2 ⁇ , OH or O when M DlA is Rh.
- n 3 represents 3, 4, 5 or 6, and m 3 represents the charge of the metal complex and represents 4, 1, 3—, 2—, 11, 0 or 1+.
- X DIA has the same meaning as X D1 in formula (D1), and the preferred range is also the same.
- 3 to 6 XDIAs may be the same or different from each other, and when a plurality of LDIAs are present, the plurality of LDIAs may be the same or different from each other.
- metal complexes are, for example, inorganic compounds and complex dictionaries (Katsutaka Nakahara / author, Kodansha Scientific Co., Ltd., editor, Kodansha Co., Ltd. Z199, June 10, 1997, 1st printing), 4th edition Laboratory Chemistry Course (Maruzen Co., Ltd.) 17 volumes, Gmelin handbook oi inorganic and organometallic cnemistry, Comprehensive chemistry 4 Chemistry Chemistry 4 volumes Chemistry, Volume 4, Middle Transition Elements, Pergamon Press), Chelate Chemistry (1)-(6) Ueno Keihei, Nankodo, etc.
- U.S. Pat. No. 5,360,71.2 Japanese Patent Application Laid-Open No.
- the specific silver halide emulsion used in the first embodiment of the present invention preferably contains a compound represented by the following general formula (D2).
- X D2 represents a halogen ion or a pseudohalogen ion (however, excluding citrate ion OCN—).
- L D 2 represents any ligand different from X D 2 .
- n 2 represents 3, 4, or 5
- m 2 represents the charge of the metal complex, and represents 4—, 3—, 2—, 11, 0, or 1+.
- a plurality of XD2s may be the same or different from each other, and when a plurality of LD2s are present, these may be the same or different from each other.
- pseudo-halogen (halogenoid) ions are ions having properties similar to halogen ions, such as cyanide ion (CN—), thiocyanate ion (SCN-I), selenocyanate ion (S e CN—), Terrocyanate ion
- X D2 is preferably a fluoride ion, a chloride ion, a bromide ion, an iodide ion, a cyanide ion, an isocyanate ion, a thiocyanate ion, a nitrate ion, a nitrite ion, or an azide ion. Particularly preferred are chloride ion and bromide ion.
- LD2 is not particularly limited, and may be an inorganic compound or an organic compound, may be charged or uncharged, but is an uncharged organic compound or an organic compound Is preferred.
- a metal complex represented by the following general formula (D2A) is preferable.
- X D2A represents a pseudo halogen ion other than a halogen ion or a cyanate ion
- L D2A represents any inorganic rooster ligand different from X D2A
- n 4 represents 3, 4 or 5
- m 4 represents the charge of the metal complex, and represents 4_, 3—, 2—, 1, 1, 0 or 1+.
- X D2A has the same meaning as X D2 in formula (D2), and the preferred range is also the same.
- L D2A as good Mashiku water (aqua; H 2 0), OCN, ammonia (NH 3), phosphine (PH 3), a carbonyl (co>, it is preferable in particular water (H 2 0).
- 3-5 pieces of X D2A may be the same or different from each other.
- L D2A there are a plurality a plurality of L D2A may be the same or different from each other.
- a metal complex represented by the following general formula (D2B) is more preferable.
- X D2B represents a pseudohalogen ion other than a halogen ion or a cyanate ion
- L D2B represents a chain or cyclic hydrocarbon as a parent structure or a part of the parent structure.
- n5 represents 3, 4 or 5
- m5 represents the charge of the metal complex, and represents 4—, 3—, 2—, 11, 0 or 1+.
- X D2B general formula (D2) has the same meaning as chi ⁇ of, the preferred range is also the same.
- L D2B represents a ligand in which a chain or cyclic hydrocarbon is a parent structure, or in which a carbon or hydrogen atom is partially replaced by another atom or atomic group. It does not include chloride ions.
- L D2B is preferably a heterocyclic compound. More preferably, it is a complex having a five-membered ring compound as a ligand, and among the five-membered ring compounds, a compound containing at least one nitrogen atom and at least one sulfur atom in a five-membered ring skeleton. It is even more preferred.
- 3-5 pieces of X D2B may be the same or different from each other.
- L D2B there are a plurality a plurality of L D2B may be the same or different from each other.
- a metal complex represented by the following general formula (D2C) is more preferable.
- X D2C represents a pseudohalide other than a halogen ion or a cyanate ion
- L D2C is a 5-membered ring ligand, and at least one nitrogen atom and at least 1 Represents a ligand containing two sulfur atoms.
- n 6 represents 3, 4 or 5
- m 6 represents the charge of the metal complex, and represents 4_, 3—, 2—, 11, 0 or 1+.
- X D2C has the same meaning as X D2 in formula (D2), and the preferred range is also the same.
- the substituent on the carbon atom in the ring skeleton in LD2c is preferably a substituent having a smaller volume than the n-propyl group.
- methyl, ethyl, methoxy, ethoxy, cyano, isocyano, cyanate, isocyanato, thiocyanato, isothiocyanato, honolemil, thioformyl, hydroxy, mercapto, amino, A hydrazino group, an azide group, a nitro group, a nitroso group, a hydroxyamino group, a carboxyl group, a carpamoyl group, a fluoro group, a fluoro group, a bromo group, and an ode group are preferred.
- three to five X D2c may be the same or different from each other.
- L D2C there are a plurality a plurality of L D2C may be the same or different from each other.
- a metal complex represented by the following general formula (D2D) is more preferable.
- X D2D represents a pseudo-halogen ion other than a halogen ion or a cyanate ion
- L D2D is a 5-membered ring ligand, and has at least two nitrogen atoms and at least one nitrogen atom in a ring skeleton.
- n 7 represents 3, 4 or 5
- m 7 represents the charge of the metal complex, and represents 4-1, 3-, 2-, 1-1, 0 or 1+.
- X D2D has the same meaning as X D2 of the general formula (D2), and the preferred range is also the same.
- LD2D is preferably a compound having a thiadiazole skeleton, and a substituent other than hydrogen is preferably bonded to a carbon atom in the compound.
- halogen fluorine, chlorine, bromine, iodine
- n 7 is preferably 4 or 5
- m 7 is preferably 12 or 11.
- three to five .X D2D may be the same or different from each other, and if L D2D is to plurality of the plurality of L D2D may be the same or different from each other.
- the above-mentioned metal complex represented by the general formula (D 1) or (D 2) is an anion or is electrically neutral.
- the counter cation is preferably one which is easily dissolved in water.
- alkali metal ions such as sodium ion, potassium ion, rubidium ion, cesium ion and lithium ion, ammonium ion, and alkyl ammonium ion are preferable.
- These metal complexes are dissolved in a mixed solvent with water and a suitable organic solvent that can be mixed with water (eg, alcohols, ethers, glycols, ketones, esters, imides, etc.). You can use it.
- Metal complex represented by the general formula (D1) is preferably added per mol of silver 1 x 10 one 11 mole ⁇ lx l0- 6 mol during grain formation, 1 x 10 one 10 mol ⁇ 1 x 10 one It is most preferable to add 7 mol.
- Metal complex represented by the general formula (D2) is preferably added per mol of silver 1 x 10 one 1Q mol ⁇ Lx l0 one 3 moles during grain formation, 1 x 10 one 8 mol ⁇ 1 x 10 one It is most preferable to add 5 mol.
- the above-mentioned metal complex is added directly to the reaction solution at the time of silver halide grain formation, in an aqueous halide solution for forming silver halide grains, or in another solution. It is preferable to incorporate into the silver halide grains by adding to the forming reaction solution. It is also preferable to physically ripen the metal complex with fine particles in which the metal complex has been previously incorporated into the silver halide particles. Furthermore, these methods can be combined and contained in silver halide grains.
- these metal complexes When these metal complexes are incorporated into silver halide grains, they may be uniformly present inside the grains. However, JP-A-4-2098936, JP-A-2-12525, As disclosed in JP-A-3-1884337, it is also preferable that the complex is present only in the particle surface layer. Addition is also preferred. Also, as disclosed in U.S. Patent Nos. 5,252,451 and 5,256,530, physical ripening is carried out with fine particles having a complex incorporated therein. To modify the particle surface phase It is also preferable to do so. Further, these methods can be used in combination, and plural kinds of complexes may be incorporated in one silver halide grain.
- the specific silver halide emulsion used in the first embodiment of the present invention is, in addition to the iridium complex represented by the general formula (D2), an iridium in which all six ligands are C1, Br or I. Complexes may be further included. In this case, Cl, Br or I may be mixed in the six-coordinate complex. It is particularly preferable that the iridium complex having Cl, Br or I as a ligand is contained in the silver bromide-containing phase in order to obtain a hard gradation with high illuminance exposure.
- the silver halide particle force S in the silver halide emulsion containing a six-coordination complex having Ir as a central metal having at least two kinds of different ligands is as follows. This is one of preferred embodiments of the present invention.
- the six-coordinate complex having Ir as a central metal include a six-coordinate complex having Ir as a central metal and a halogen ligand or an organic ligand contained in the same complex.
- 6-coordinate complex shall be the central metal I r including Yohi 'the other inorganic ligands halogen in the same complex which preferable. Halogen ligands and organic ligands are contained in the same complex. Six-coordinate complexes with Ir as the central metal and halogen ligands and inorganic ligands other than halogen are included in the same complex. It is more preferred to have both 6-coordination complexes with Ir as the central metal.
- the six-coordinate complex having Ir as a central metal preferably used in the third or fourth embodiment of the present invention is a metal complex represented by the following general formula (I). '
- X 1 represents a halogen ion or a pseudohalogen ion other than a cyanate ion
- L 1 represents an arbitrary ligand different from X 1 .
- n represents 3, 4 or 5
- m represents 4-1, 3-, 2-, 1-1, 0 or 1+.
- three to five of X 1 may be the same or different from each other, and if L ⁇ there are a plurality, a plurality of L 1 may be the same or different from each other.
- pseudo-halogen (halogenide) ions are ions having properties similar to halogen ions, such as cyanide ion (CN—), thiocyanate ion (SCN—), selenocyanate ion ( S CN1), Terrocyanate ion
- T e CN— azidodithiocarbonate ion
- S CSN 3 azidodithiocarbonate ion
- OCN— cyanate ion
- ONC-I thunder acid ion
- N 3 _ azide ion
- X 1 is preferably a fluoride ion, a chloride ion, a bromide ion, an iodide ion, a cyanide ion, an isocyanate ion, a thiocyanate ion, a nitrate ion, a nitrite ion, or an azide ion. Particularly preferred are chloride ion and bromide ion.
- L 1 is not particularly limited, and may be an inorganic compound or an organic compound. It may be charged or uncharged, but is preferably an uncharged inorganic compound or organic compound.
- a metal complex represented by the following general formula (IA) is preferable.
- X 1 A represents a pseudohalogen ion other than a halogen ion or a cyanate ion
- L IA represents an inorganic compound different from X 1 A.
- n represents 3, 4 or 5;
- m represents 4—, 3—, 2—, 1, 0, or 1+.
- X 1 A has the same meaning as X] in formula (I), and the preferred range is also the same.
- LIA is preferably water, OCN, ammonia, phosphine, or carbonyl, and particularly preferably water.
- three to five X IA may be the same or different from each other.
- L IA there are a plurality a plurality of L 1 A may be the same or different from each other.
- a metal complex represented by the following general formula (IB) is more preferable.
- X IB represents a pseudo-halogen ion other than a halogen ion or a cyanate ion
- L IB represents a chain or cyclic hydrocarbon as a parent structure, or a part of the parent structure.
- n represents 3, 4 or 5, and m represents 4-1, 3-, 2-, 1-, 0 or 1+.
- X IB has the same meaning as X 1 in formula (I), and the preferred range is also the same.
- L IB represents a ligand in which a chain or cyclic hydrocarbon has a parent structure or in which some carbon or hydrogen atoms of the parent structure have been replaced by other atoms or atomic groups, Do not include ions.
- L IB is preferably a heterocyclic compound. More preferably, the complex has a five-membered ring compound as a ligand, and among the five-membered ring compounds, a compound containing at least one nitrogen atom and at least one sulfur atom in the five-membered ring skeleton. Is more preferred.
- three to five X IB may be the same or different from each other.
- L IB there are a plurality a plurality of L IB may be the same or different from each other.
- X IC represents a pseudohalogen ion other than a halogen ion or a cyanate ion
- L IC has a five-membered ring ligand, and has at least one nitrogen atom and at least one It is a ligand containing a sulfur atom. Any substituent may be present on a carbon atom in the ring skeleton.
- n represents 3, 4 or 5, and m represents 4-1, 3-, 2_, 1_, 0 or 1+.
- X lc has the same meaning as X 1 in formula (I), and the preferred range is also the same.
- L The substituent on the carbon atoms of the ring skeleton in IC is preferably a substituent having a smaller volume than n- propyl group.
- Substituents such as methyl, ethyl, methoxy, ethoxy, Ano group, isocyano group, cyanate group, isocyanato group, thiocyanato group, isothiocyanato group, formyl group, thioformyl group, hydroxy group, mercapto group, amino group, hydrazino group, azide group, nitro group, nitroso group, Preferred are a hydroxyamino group, a carboxyl group, a carbamoyl group, a fluoro group, a chloro group, a promo group and an oxa group.
- three to five X IC may be the same or different from each other.
- L IC there are a plurality a plurality of L IC may be the same or different from each other.
- the specific silver halide grains in the silver halide emulsion have a hexagonal structure in which all six ligands are composed of C 1, Br or I with Ir as a central metal. It is preferable to have a coordination complex. In this case, C1, Br or I may be mixed in the six-coordinate complex.
- a hexacoordination complex having Cl, Br or I as a ligand and having Ir as a central metal is preferably contained in a silver bromide-containing phase in order to obtain a hard gradation in high-intensity light exposure. No.
- the above-mentioned metal complexes are anions, and when forming a salt with a cation, those which are easily dissolved in water as a counterion are preferable. Specifically, alkali metal ions such as sodium ion, potassium ion, rubidium ion, cesium ion and lithium ion, ammonium ion, and alkyl ammonium ion are preferable. These metal complexes are dissolved in a mixed solvent of water and a suitable organic solvent that can be mixed with water (eg, alcohols, ethers, glycols, ketones, esters, amides, etc.). Can be used.
- a suitable organic solvent that can be mixed with water (eg, alcohols, ethers, glycols, ketones, esters, amides, etc.). Can be used.
- Irijiumu complexes be silver is preferred to moles per 1 X 10- 10 mol ⁇ IX 10 one 3 moles added pressure, IX 10 one 8 mol ⁇ IX 10 one 5 moles added mosquitoes ⁇ during grain formation Most preferred.
- the above-mentioned iridium complex is directly added to the reaction solution at the time of forming silver halide grains, or is added to an aqueous halide solution for forming silver halide grains, or to another solution. It is preferable to incorporate into silver halide grains by adding to a silver halide grain forming reaction solution. It is also preferable to physically ripen the fine particles in which the iridium complex has been incorporated in advance and incorporate them into silver halide grains. Further, these methods can be combined and contained in silver halide grains.
- the halogen composition at the position where the above complex is contained is not particularly limited, but a six-coordination complex in which all six ligands are composed of C 1, Br or I, and the central metal is Ir, It is preferable to include it in the concentration maximum.
- metal ions other than the above-described metal complexes can be doped into the inside and / or the surface of the silver halide grains.
- Transition metal is used as the metal ion Ions are preferred, with iron, ruthenium, osmium, lead, cadmium or zinc being particularly preferred. Further, these metal ions are more preferably used as a hexacoordinate octahedral complex with a ligand.
- an inorganic compound When an inorganic compound is used as a ligand, cyanide ion, halide ion, thiocyanate, hydroxide ion, peroxide ion, azide ion, nitrite ion, water, ammonia, nitrosyl ion, or thionitrosi ion It is preferable to use a metal ion of iron, ruthenium, osmium, lead, cadmium, or zinc, and it is preferable to use a plurality of ligands in one complex molecule. Is also preferred. Further, an organic compound can be used as the ligand.
- organic compound examples include a chain compound having 5 or less carbon atoms in a main chain and / or a 5- or 6-membered heterocyclic compound. I can do it.
- Further preferred organic compounds are compounds having a nitrogen atom, a phosphorus atom, an oxygen atom or a sulfur atom as a coordinating atom to a metal in the molecule, and particularly preferred are furan, thifenphen, oxazole, isoxazole, and the like.
- Thiazole, isothiazole, imidazole, pyrazole, triazole, furazan, pyran, pyridine, pyridazine, pyrimidine, pyrazine, and a compound having these compounds as a basic skeleton and having a substituent introduced therein is also preferable. .
- the combination of a metal ion and a ligand is preferably an iron ion or a combination of a ruthenium ion and a cyanide ion.
- a combination of the iridium and these compounds it is preferable to use a combination of the iridium and these compounds.
- the cyanide ion preferably occupies the majority of the coordination numbers to the central metal iron or ruthenium, and the remaining coordination sites are thiocyanate, ammonia, water, nitrosyl ion, dimethyl sulfoxide, pyridine , Pyrazine or 4,4′-biviridine.
- ruthenium or osmium When ruthenium or osmium is used as the central metal, it is also preferable to use a nitrosyl ion, a thionitrosyl ion, or a water molecule and a chloride ion together as a ligand. More preferably, it forms a pentachloronitrosinole complex, a pentachlorothionitrosyl complex, or a pentachloroaqua complex, and also preferably forms a hexaclo mouth complex. These complexes are preferably added per mol of silver 1 X 10- 1Q mol ⁇ 1 X 10 10 mol during grain formation, more Konomareku is added ⁇ 10- 9 mol ⁇ IX 10- 6 moles That is.
- the silver halide emulsion used in the light-sensitive material is preferably subjected to gold sensitization known in the art. This is because by giving the feeling of gold, the emulsion can be made more sensitive, and the fluctuation in photographic performance when scanning and exposure is performed with laser light or the like can be reduced.
- gold sensitization known in the art.
- Various inorganic gold compounds, gold (I) complexes having an inorganic ligand, and gold (I) compounds having an organic ligand can be used to give a gold sensation.
- examples of the inorganic gold compound include chloroauric acid or a salt thereof, and examples of the gold (I) complex having an inorganic ligand include gold dithiocyanate compounds such as potassium dithiocyanate (I) potassium and gold dithiosulfate (I). 3) A compound such as sodium dithiosulfate such as sodium can be used.
- gold (I) compound having an organic ligand examples include bisgold (I) mesoionic heterocycles described in JP-A-4-267249, for example, bis (1,4,5) —Trimethyl-1,2,4—triazolyl-3-thiolato) aurate (I) tetrafluoroborate, PT / JP2005 / 004725
- an organic ligand and an Au compound may be separately added to the emulsion to generate a gold (I) compound having an organic ligand in the emulsion.
- the addition amount of these compounds may vary widely depending on the case, but 1 mol of silver halide per Ri usually 5 ⁇ 1 0 _ 7 ⁇ 5 1 0- 3 Monore, preferably 5 x 1 0 one 6 ⁇ 5 x 1 0 - 4, which is a mole.
- colloidal gold sulfide It is also possible to use colloidal gold sulfide, and its production method is described in Research Disclosure (37154), Solid State Ionics, Vol. 79, pp. 60-66, 1 Sci. Sect. B, Vol. 263, p. 328, published in 1966, etc., published in 995, Compt. Rend. Hebt. Seances Acad.
- the above-mentioned eserch Disclosure describes a method using thiocyanate ion in the production of colloidal gold sulfide, but a thioether compound such as methionine or thiodiethanol can be used instead.
- colloidal gold sulfide can be used, and those having an average particle size of 50 nm or less are preferably used, the average particle size is preferably 1 Onm or less, more preferably 3 nm or less. This particle size can be measured from a TEM photograph.
- the composition of the colloidal gold sulfide may be AuzS !, or may be a sulfur-excess composition such as Av ⁇ S! AuzSz, and a sulfur-excess composition is preferable. ! ⁇ ! ⁇ Enter! : ⁇ Is more preferred.
- this colloidal gold sulfide for example, gold sulfide particles are taken out, and the content of gold and the content of sulfur can be determined by using an analysis method such as ICP method. If gold ions and sulfur ions (including hydrogen sulfide and its salts) dissolved in the liquid phase are present in the gold sulfide colloid, it will affect the composition analysis of the gold sulfide colloid particles. The analysis is performed after the separation.
- the addition amount of the gold sulfide colloids is obtained over a wide range varying fairly as the case usually 5x1 0- 7 ⁇ 5xl CI- 3 mol silver halide per mole gold atoms, the good Mashiku 5x1 0- 6 ⁇ 5xl 0 — 4 moles.
- chalcogen sensitization other than the selenium sensitization ie, sulfur sensitization, tellurium sensitization, and selenium sensitization other than the selenium sensitization
- Au represents Au (I)
- Ch represents a sulfur atom, a selenium atom, and a tellurium atom.
- the molecule capable of releasing AuCh is, for example, a gold compound represented by AuCh-L.
- L represents an atomic group that forms a molecule by bonding to AuCh.
- one or more ligands may be coordinated with Au together with Ch-L.
- AuCh-L can easily produce AgAuS when Ch is S, AgAuSe when Ch is Se, and AgAuTe when Ch is Te when reacted in a solvent in the presence of silver ions in the presence of silver ions.
- Examples of such compounds include compounds in which L is an acyl group, and other compounds represented by the following formulas (AuCh 1), (AuCh 2), and (AuCh 3) shown below.
- Au represents Au (I)
- Ch represents a sulfur atom, a selenium atom, a tellurium atom
- M represents a substituted or unsubstituted methylene group
- X represents an oxygen atom
- NR 2 Represents an atomic group (for example, an organic group such as an alkyl group, an aryl group, or a heterocyclic group) bonded to X to form a molecule
- R 2 represents a hydrogen atom and a substituent (for example, an alkyl group).
- M may combine with each other to form a ring.
- X is preferably an oxygen atom and a sulfur atom, and is preferably an alkyl group or an aryl group.
- Examples of more specific compounds include Au (I) salts of thiosaccharides (gold thioglucose such as ⁇ -gold thioglucose, gold peracetylthioglucose, gold thiomannose, gold thiogalactose, gold thioarabinose, etc.), Au (I) salts of selenosugars (gold acetyl selenoglucose, gold acetyl selenomannose, etc.), and Au (I) salts of tellucose.
- thiosugar, selenosugar, and tenolose sugar refer to compounds in which the anomeric hydroxyl group of the sugar is replaced by an SH group, a SeH group, or a TeH group, respectively.
- Au represents Au (I)
- Ch represents a sulfur atom, a selenium atom, or a tellurium atom
- R 3 and W 2 represent substituents (for example, a hydrogen atom, a halogen atom, an alkyl group, an aryl group) represents group, an organic group), such heterocyclic groups, represents an electron absorption attractive group is a value substituent constant sigma [rho value positive of Hame' bets.
- R 3 and W !, and W 2 , and Wi and W 2 may combine with each other to form a ring.
- Ch is preferably a sulfur atom and a selenium atom
- R 3 is preferably a hydrogen atom and an alkyl group
- W 2 is a Hammett's substituent constant ⁇
- An electron-withdrawing group having a ⁇ value of 0.2 or more is preferred.
- Au represents Au (I)
- Ch represents a sulfur atom, a selenium atom, or a tellurium atom
- E represents a substituted or unsubstituted ethylene group
- W 3 represents a positive Hammett's substituent constant ⁇ ⁇ value. Represents an electron-withdrawing group.
- Echire down Ch is having a sulfur atom, and preferably has a selenium atom, an electron withdrawing group E substituent constant sigma [rho value of Hammett is a positive value W 3 is preferably an electron-withdrawing group having a Hammett's substituent constant ⁇ value of 0.2 or more.
- Ha port Gen silver 1 mol per Ri usually 5 X 1 0- 7 ⁇ 5 x 1 0 3 Monore, preferably 3 x 1 0 _ 6 ⁇ 3 1 0 4 mol.
- Silver halide emulsions can be used in combination with the above gold sensitization and other sensitization methods, such as sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization, or metal sensitization using other than gold compounds. Is also good. In particular, combination with sulfur sensitization and selenium sensitization is preferable.
- the silver halide emulsion used in the present invention contains various compounds or various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. Precursors such as these can be added. As specific examples of these compounds, those described on page 39 to page 72 of JP-A-62-215272 are preferably used. Further, 5-arylamino-1,2,3,4-thiatriazole compounds described in EP 044 7647 (the aryl residue has at least one electron-withdrawing group) are also preferably used.
- the silver halide emulsion used in the present invention may contain a spectral sensitizing dye for the purpose of imparting a so-called spectral sensitivity exhibiting photosensitivity in a desired light wavelength region.
- a spectral sensitizing dye for the purpose of imparting a so-called spectral sensitivity exhibiting photosensitivity in a desired light wavelength region.
- the spectral sensitizing dyes used for spectral sensitization in the blue, green, and red regions include, for example, Heterocycliccompounds— yan ⁇ nedyesandrelatedcompounds (John Wiley & Sons [New Y ork, London], published in 1964).
- Specific examples of the compounds and the spectral sensitization method are preferably those described in the above-mentioned JP-A-62-215272, from page 22, upper right column to page 38, of JP-A-62-215272. .
- spectral sensitizing dyes described in JP-A-3-123340 are particularly useful as red-sensitive spectral sensitizing dyes for silver halide emulsion grains having a high silver chloride content. It is very preferable from the viewpoint of the temperature dependency of exposure.
- spectral sensitization is performed for the purpose of imparting an arbitrary spectral sensitivity according to the light wavelength range of the light source, and it is preferable to have infrared spectral sensitization if necessary.
- the spectral sensitization method for the purpose of digital exposure is preferably the method described in JP-A-5-142712, and the compounds described in the same publication are preferably used as the infrared spectral dye.
- any known dyes as described above can be used. These dyes include a thiazole nucleus, a selenazole nucleus, an oxazole nucleus, and an imidazole nucleus in which a benzene ring or a naphthalene ring is condensed, two basic mother nuclei, a mouth danin nucleus, a thiohydantoin nucleus, and a 2-thioselenazolidine nucleus.
- Examples include a 2,4-dione nucleus, a merocyanine dye having a barbituric acid nucleus as an acidic nucleus, and a trinuclear complex melocyanin dye having three mother nuclei. Since the effect of reducing residual color contamination is large, it can be preferably used. These dyes may be used in combination with a plurality of dyes in order to obtain a required spectral sensitivity distribution.
- spectral sensitizing dyes In order to incorporate these spectral sensitizing dyes into a silver halide emulsion, they must be added directly to the emulsion. It may be dispersed or dissolved in a solvent such as water, methanol, ethanol, propanol, methylcellosolve, 2,2,3,3-tetrafluoropropanol alone or in a mixed solvent, and added to the emulsion. Good. In addition, acid or base is allowed to coexist as described in JP-B-44-23-389, JP-B-44-27555, JP-B-57-22089, etc. As described in U.S. Pat.No. 3,822,135, and 'U.S. Pat.No. 4,006,025, etc.
- aqueous solution or a colloidal dispersion in the presence of a surfactant May be added to the emulsion.
- a dispersion in water or a hydrophilic colloid may be added to the emulsion.
- a dispersion in water or a hydrophilic colloid may be added to the emulsion.
- directly dispersed in a hydrophilic colloid was added to an emulsion. May be.
- the timing of addition to the emulsion may be at any stage during the preparation of the emulsion which has been known to be useful.
- the coating solution is prepared until the emulsion is cooled and solidified.
- the addition of chemical sensitizers at the same time as chemical sensitization and The addition can be carried out prior to the addition, and the addition can be started before the completion of the formation of silver halide grains to start spectral sensitivity.
- a spectral sensitizing dye is separately added, that is, a part is added prior to chemical sensitization, and the rest is chemically sensitized. It can be added at any time during the formation of silver halide grains, including the method taught in US Pat. No. 4,187,756. Of these, it is particularly preferable to add a ⁇ sensitive dye before the step of washing the emulsion or before the chemical sensitization. Over a wide range depending on the case the addition amount of these spectral sensitizing dyes, the silver halide 1 molar equivalent is, 0 5 1 0 6 Monore ⁇ 1 O x 1 Fei -.. 2 moles ranges Shi favored, . More preferably 1. 0 X 1 0- 6 Monore 1-5. Range of O x 0 one 3 Monore.
- the silver halide color photographic light-sensitive material of the first embodiment of the present invention (hereinafter sometimes simply referred to as "light-sensitive material”) comprises a support, a red-sensitive green-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer. Wherein at least one of the silver halide emulsion layers contains the specific silver halide emulsion referred to in the first embodiment of the present invention, and the formula (1) Is satisfied.
- the light-sensitive material of the first embodiment of the present invention comprises, on a support, a silver halide emulsion layer containing a yellow dye-forming coupler, a silver halide emulsion layer containing a magenta dye-forming coupler, and a cyan dye-forming coupler. It is preferable that each of the silver halide emulsion layers has at least one silver halide emulsion layer.
- the silver halide emulsion layer containing the yellow dye-forming coupler is a yellow color-forming layer
- the silver halide emulsion layer containing the magenta dye-forming coupler is a magenta color-forming layer
- the cyan dye-forming coupler is contained.
- the silver halide emulsion layer functions as a cyan coloring layer.
- the silver halide emulsion contained in each of the yellow, magenta and cyan coloring layers preferably has photosensitivity to light of different wavelength ranges.
- Preferable examples include a halogen containing a light-sensitive emulsion in the blue region in the yellow coloring layer, a light-sensitive emulsion in the green region in the magenta coloring layer, and a light-sensitive emulsion in the red region in the cyan coloring layer.
- Examples include, but are not limited to, silver halide color photographic materials.
- the light-sensitive material of the second embodiment of the present invention comprises, on a support, a light-sensitive silver halide emulsion layer containing a yellow dye-forming coupler, a light-sensitive silver halide emulsion layer containing a magenta dye-forming coupler, and a cyan dye-forming coupler. And a photographic constituent layer comprising at least one of a photosensitive silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer.
- the silver halide emulsion layer containing the yellow dye-forming coupler is a yellow color-forming layer (Y)
- the silver halide emulsion layer containing the magenta dye-forming coupler is a magenta color-forming layer (M)
- the silver halide emulsion layer containing the coupler forming the tint functions as a cyan coloring layer (C).
- the silver halide emulsions contained in each of the Y, M, and C color forming layers are exposed to three different wavelength regions of light (for example, blue, green, and red light in the order of Y, M, and C). On the other hand, it is' preferable to have photosensitivity.
- the above three different spectral sensitivities can be arbitrarily selected from the use of a digital exposure system using a semiconductor laser or LED as a light source.
- the closest spectral sensitivity maximum be at least 30 nm apart.
- the correspondence with the color couplers (Y, ⁇ , C) contained in the photosensitive layers (E1, E2, 13) having at least three different spectral sensitivity maxima can be arbitrarily combined. It is also possible to use a wavelength range other than blue, green, and red light, and it is also preferable that it has infrared spectral sensitivity and can respond to infrared laser exposure.
- the light-sensitive material according to the second embodiment of the present invention may further include, if desired, a non-photosensitive hydrophilic colloid layer described below, in addition to a yellow color-forming layer, a magenta color-forming layer, and a cyan color-forming layer, an antihalation layer, an intermediate It may have a layer and a colored layer.
- a non-photosensitive hydrophilic colloid layer described below, in addition to a yellow color-forming layer, a magenta color-forming layer, and a cyan color-forming layer, an antihalation layer, an intermediate It may have a layer and a colored layer.
- the silver halide emulsion layer of the third embodiment of the present invention comprises a silver halide emulsion layer containing a yellow dye forming coupler, a silver halide emulsion layer containing a magenta dye forming coupler, and a cyan dye. It has at least one silver halide emulsion layer containing a coupler.
- the total amount of the cyan dye-forming coupler, the magenta dye-forming coupler and the yellow dye-forming coupler is preferably 1.1 g / m 2 or less, more preferably 0.4 g / m 2 or more and 1.0 g / m 2 or less. g / m 2 or less is more preferable.
- the silver halide emulsions contained in the silver halide emulsion layers containing each of the power blurs have different color sensitivity.
- a silver halide emulsion layer containing a yellow dye-forming coupler contains a blue-sensitive silver halide emulsion
- a silver halide emulsion containing a magenta dye-forming power blur contains a green photosensitive silver halide emulsion.
- the silver halide emulsion layer containing a cyan dye-forming coupler contains a red-sensitive silver halide emulsion.
- the spectral sensitivity of each silver halide emulsion is preferably The peak is preferably from 400 nm to 500 nm for the blue-sensitive emulsion, and 4200 ⁇ ! 480 nm, more preferably 510 nm to 590 nm, more preferably 520 nm to 580 nm.
- Red light sensitive emulsion is 600 nn! 8800 nm, preferably 620 ⁇ ! More preferably, it is 7720 nm.
- the wavelength difference of the spectral sensitivity peak between the respective photosensitive silver halide emulsions preferably differs by 30 nm or more, more preferably by 50 nm or more.
- the above three different spectral sensitivities can be arbitrarily selected from the use of a digital exposure system using a semiconductor laser or LED as a light source.
- JP2005 / 004725 JP2005 / 004725
- the closest spectral sensitivity maximum is separated by at least 30 nm or more.
- the correspondence with the color couplers (Y, M, C) contained in the photosensitive layers ( ⁇ 1, ⁇ 2, 13) having at least three different spectral sensitivity maxima can be arbitrarily combined. It is also possible to use a wavelength range other than blue, green, and red light, and it is also preferable that it has infrared spectral sensitivity and can respond to infrared laser exposure.
- the light-sensitive material of the present invention has an antihalation layer, an intermediate layer, and a coloring layer as a non-photosensitive hydrophilic colloid layer described later, if desired, in addition to a yellow coloring layer, a magenta coloring layer, and a cyan coloring layer. It may be.
- the composition of the silver halide light-sensitive photographic light-sensitive material comprises, on a support, a silver halide emulsion layer containing a cyan dye-forming coupler, It has at least one layer each of a silver halide emulsion layer containing a magenta dye-forming coupler and a silver halide emulsion layer containing a yellow dye-forming dye.
- the silver halide emulsion contained in each layer is preferably sensitive to light in different wavelength ranges (for example, light in the blue, green, and red regions).
- the use amount of the coupler is ideally 1 equivalent to silver, but is preferably 0.6 equivalent or more, particularly preferably 0.7 equivalent or more.
- 1 equivalent is the amount of coupler that forms a color when reacted with all of the used silver
- 0.5 equivalent is the amount of coupler that forms a color by reacting with half of the used silver.
- the silver halide emulsion layer contains at least two kinds of silver halide emulsions having different silver chloride contents with different sensitivities of 90 mol% or more.
- the number of silver halide emulsions having different sensitivities may be two or more, but it is preferable to use two or three silver halide emulsions in the design of the light-sensitive material.
- a plurality of silver halide emulsions may have different or different grain sizes, halogen compositions and structures, and sensitizing dyes, chemical sensitizers, antifogging agents and the like.
- the silver chloride content of at least two different sensitivities is 90 mol.
- the silver halide emulsions having a ratio of / 0 or more are preferably mixed in the same silver halide emulsion layer, but emulsions having different sensitivities may be separately coated in separate emulsion layers. However, it is necessary that those layers have almost the same color sensitivity and coloring hue.
- the substantially equal color sensitivity means, in the case of a color photographic light-sensitive material, for example, blue sensitivity, green sensitivity or red sensitivity, and even if the spectral sensitivities differ in that range. Good.
- substantially the same color hue means, for example, yellow colors, magenta colors or cyan colors, and the color hues may be different within that range.
- the light-sensitive material of the present invention may have, if desired, a hydrophilic colloid layer, an antihalation layer, an intermediate layer, and a coloring layer described later in addition to the yellow color-forming layer, the magenta color-forming layer, and the cyan color-forming layer. Good.
- Y yellow dye-forming coupler represented by the general formula (Y) which can be used in the silver halide color photographic light-sensitive material of the present invention, preferably in the second or fourth embodiment, (hereinafter simply referred to as yellow It is sometimes called a power plastic.
- R! Represents an alkyl group or a cycloalkyl group
- R 2 represents an alkyl group, Shiguroaruki group, Ashiru group, or Ariru group
- R 3 represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, Ariruokishi Group, alkoxycarbonyl group, alkylsulfonyl group, alkylcarbamoyl group, arylcarbamoyl group, alkylsulfamoyl group, arylinosulfamoyl group, alkylcarbonamide group, alkylsulfonamide group, arylsulfonamide group, Represents a sulfamoyl group or an imido group
- m represents 0 or an integer of 1 to 4.
- Z! Represents one O—, one NR A— , and Z 2 represents one NR B— or —C (R c ) R D —.
- R A , R B , R c , and R D independently represent hydrogen or a substituent.
- alkyl group represented by R! include methyl, ethyl, isopropyl, t-butyl, dodecyl, and the like.
- the alkyl group represented by Ri may further have a substituent.
- substituents include a halogen atom (for example, a chlorine atom and a bromine atom), an aryl group (for example, phenyl, p-t —Octylphenyl, etc.), alkoxy groups (eg, methoxy, etc.), aryloxy groups (eg, 2,4-d-t-amylphenoxy, etc.), sulfonyl groups (eg, methanesulfonyl, etc.), and acylamino groups (eg, acetyl, benzoyl, etc.) ), A sulfonylamino group (eg, n-dodecanesulfonylamino, etc.), and a hydroxy group
- Examples of the cycloalkyl group represented by R include an aryl group having 6 to 14 carbon atoms (eg, phenyl, 1.1-naphthyl, and 9-anthranyl).
- the aryl group represented by R can further have a substituent.
- Examples of the substituent include a nitro group, a cyano group, an amino group (eg, dimethylamino, anilino, etc.), an alkylthio group (eg, methylthio, etc.) And the like.
- Examples of the alkyl group and cycloalkyl group represented by R 2 include the same groups as described above, and examples of the acyl group include acetyl, propionyl, butyryl, hexanol, and benzoyl. Further, examples of aryl groups include phenyl.
- the alkyl group, cycloalkyl group and aryl group represented by R 2 include those having the same substituents as described above.
- R 2 is preferably an alkyl group or an aryl group, and particularly preferably an alkyl group. .
- R 3 is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylsulfonyl group, an alkylsulfamoyl group, an arylsulfamoyl group, an alkylsulfamoyl group, an arylsulfamoyl group , Alkyl carboxamide group, alkyl sulfonamide group, aryl sulfonamide group, sulfamoyl group, Or imido group.
- R 3 is preferably a halogen atom, and a chlorine atom is particularly preferred.
- n 0, 1 to 4, preferably 0, 1, 2, or 3, more preferably 0, 1, or 2, and particularly preferably 1.
- R A represents a hydrogen atom or a substituent, and the substituent preferably represents an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group).
- Z 2 is one NR B — (R B represents a hydrogen atom ′ or a substituent, and the substituent is preferably an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group) or —C (R c ) R D — (R c and R D represent a hydrogen atom or a substituent, preferably a halogen atom (eg, chlorine atom, bromine atom, etc.), an aryl group (eg, phenyl, p-t-octylphenyl, etc.), alkoxy group (for example, methoxy), aryloxy group (for example, 2,4-di-t-amylphenoxy), sulfonyl group (for example, methanesulfonyl), and acylamino Group (eg, acetyl, benzoyl, etc.), sulfonylamino group (eg, n-dode
- yellow couplers represented by the general formula (Y) yellow couplers represented by the following general formula (Y-I) are preferred.
- the yellow coupler represented by the general formula ( ⁇ ) used in the silver halide color photographic light-sensitive material of the present invention, preferably in the second or fourth embodiment, is disclosed in JP-A-63-123473.
- the compound can be easily synthesized by the method described in Japanese Patent Application Laid-Open Publication No. Hei. 3-125141 or a method analogous thereto.
- the yellow couplers represented by the general formula ( ⁇ ) used in the silver halide color photographic light-sensitive material of the present invention can be used alone or in combination of two or more. Can be used together.
- Yellow force plug one used for the silver halide force La one photographic light-sensitive material of the present invention, about 1 X 1 0- 3 mol or more per usual 1 mol of silver halide 1 molar or less, preferably 1 X 1 0- 2 mol it can be used in 8 chi 1 0- 1 mols or more.
- the coupler represented by the general formula (II) is typically preferably added by emulsifying and dispersing with a high-boiling organic solvent.
- the couplers represented by the general formula ( ⁇ ) may be used alone or in combination of two or more, and may be used in combination with other couplers (for example, couplers described later).
- crown ethers fused with at least one or more substituted or unsubstituted aromatic rings.
- substituents include alkyl, aryl, arylino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl, and other groups. , Cycloalkenyl, alkynyl, heterocycle, sulfol, sulfiel, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy and the like.
- the hetero atoms constituting the crown ring may be replaced with nitrogen atoms, sulfur atoms, selenium atoms, etc.
- crown ether preferably used in the silver halide color photographic light-sensitive material of the present invention
- the crown ether used in the silver halide color photographic light-sensitive material of the present invention is not limited thereto. Not.
- the brown ether used in the silver halide color photographic light-sensitive material of the second embodiment is added to a hydrophilic colloid containing silver halide grains forming a silver halide emulsion layer.
- a hydrophilic organic solvent such as water, methanol, ethanol, or fluorinated alcohol.
- the timing of addition may be any timing as long as it is before coating of the emulsion, but is preferably added before the end of chemical sensitization.
- the crown ether is added to at least one of the silver halide emulsion layers, and is preferably added to the silver halide emulsion layer containing the cyan dye-forming power.
- the amount of the crown ether used in the silver halide color photographic light-sensitive material of the present invention varies depending on the crown ether compound used, silver octogenide particles, chemical ripening conditions, etc., but generally silver halide is used. 1 mole per 1 X 10- X 10- 1 mol, preferably using about 1 X 10- 5 ⁇ 1 X 10- 2 mole.
- the conditions for using the compound are not particularly limited, but pC1 is preferably 0 to 7, more preferably 0 to 5, and still more preferably 1 to 3.
- the temperature is preferably from 40 to 95, more preferably from 50 to 85 ° C.
- the crown ether used in the silver halide color photographic light-sensitive material of the present invention, preferably in the second embodiment is preferably used as a supersensitizer of a red-sensitive sensitizing dye.
- the brown ether may be added as one kind or as a mixture of two or more kinds in the same layer or a plurality of layers.
- the compound having an action of oxidizing metallic silver clusters used in the silver halide color photographic light-sensitive material of the present invention is obtained by coating a silver halide emulsion together with a protective film of gelatin. Before development, the coated sample is immersed in, for example, a gold intensifying solution of the following composition at 20 ° C for 3 minutes, washed for 1 minute, and can be used to suppress fogging that occurs during normal development.
- a compound is not particularly limited, examples, hydrogen peroxide, nitric acid, nitrous acid, a halogen element such as bromine or iodine, (such as KMn0 4) permanganate, chromium salts (e.g., K 2 C r O, etc.) oxyacid salts such as perhalogenates (e.g., periodic acid potassium ⁇ beam), high-valent metal salts (e.g. potassium ferricyanide, etc.) oxidizing agent generally has been known such as ⁇ Pochi Sulfonic acid compounds are used.
- a halogen element such as bromine or iodine, (such as KMn0 4) permanganate
- chromium salts e.g., K 2 C r O, etc.
- oxyacid salts such as perhalogenates (e.g., periodic acid potassium ⁇ beam)
- high-valent metal salts e.g. potassium ferricyanide, etc.
- An example of a preferable composition of the gold intensifying solution is as follows.
- a known color mixing inhibitor can be used to reduce color smearing.
- the color mixing inhibitor is a compound that suppresses the diffusion of an oxidized developing agent formed by the reaction of the exposed silver halide emulsion with a color developing solution and the reaction with a coupler in another layer.
- the color mixing inhibitor those described in the following patent documents are preferable.
- the color mixing inhibitor can be contained in any of the photographic constituent layers, but is preferably contained in an intermediate layer provided between the silver halide emulsion-containing layers in order to reduce color smear. It is. Since the color mixture inhibitor reacts with the oxidized form of the developing agent during color development, increasing the content of the color mixture inhibitor may reduce the color density. Therefore, the content of the color mixture inhibitor can affect both the performance of color smearing and color density.
- the content of anti-color mixing agent may vary according to aspects of the C port Gen halide photosensitive material, typically a silver halide photographic material lm 2 per 0. 0 1 g ⁇ l O g are preferred, 0. 04 g to; Ig is more preferred.
- the present invention in a preferred silver halide photographic light-sensitive material of the third embodiment, only the silver halide emulsion of the yellow dye-forming coupler-containing layer and time exposure after color current image processing 1 X 10- 4 sec
- the resulting yellow maximum color density (DYmax) is 1.90 to 2.30
- only the silver halide emulsion layer of the magenta dye-forming coupler-containing layer is exposed for 1 ⁇ 10 4 seconds to color development processing.
- resulting magenta maximum color density (DMmax) is 1.95 to 2.
- (D Ymax) is 1.95 2.25
- (D Mmax) is 2.00 2.25
- (D Cmax) is 1.90 2.35
- (DGYmax) is 2 ⁇ 15 2.35 5 2.25 2.65 and 2.15 2.40, respectively.
- the silver halide color photographic light-sensitive material of the present invention set in the above range, preferably in the third cold embodiment, can reproduce a higher gray density with less color smear even in rapid processing.
- the resulting image may have a low density, resulting in a light-colored image or an image with insufficient depth.
- the gray color density is rather lowered, and the color may increase and the streak-like unevenness may increase. is there.
- composition of each processing solution is as follows.
- Polyethylene dalicol (molecular weight 300) 10.0 g
- Triazinylaminostilbene fluorescent whitening agent Hatsukoru FWA—SF / Showa Chemical Co., trade name
- the spectral sensitivity of a silver halide emulsion has a sensitivity distribution over a certain wavelength range
- the silver halide emulsion contained in the other layer is exposed to light at an exposure amount higher than the exposure amount at which the yellow color develops to a maximum, and there is no problem in determining DYmax.
- Exposure using light of any wavelength over the wavelength range having spectral sensitivity may cause the silver halide emulsion contained in the other layer to be exposed at the exposure amount for obtaining the maximum color density of yellow.
- DYma X is the yellow color density at the maximum exposure light amount at which other layers do not develop color.
- the magenta maximum color density (DMm a Read X). Also, in the same manner as in the method for determining D Ymax, except that the wavelength of light used for exposure is changed to a wavelength at which only the silver halide emulsion contained in the cyan dye-forming blur containing layer is exposed. Read the maximum color density (D Cmax). JP2005 / 004725
- the method for determining the DYmax was the same as that for the image in which all colors were formed, except that the light used for exposure was changed to light that simultaneously exposed the silver halide emulsion in all the dye-forming coupler-containing layers. That is, a characteristic curve corresponding to a gray image is obtained, and from this, yellow maximum color density (DGYmax), magenta maximum color density (DGMmax), and cyan maximum color density (DG Cmax) are obtained.
- DGYmax yellow maximum color density
- DGMmax magenta maximum color density
- DG Cmax cyan maximum color density
- a relative humidity of 20% at 25 ° C. (hereinafter, relative humidity is referred to as RH)
- RH relative humidity
- the curl degree in the present invention can be determined by the following procedure.
- a silver halide photosensitive material without warp at 25 ° C 55% RH is cut into 10cmX10cm and left in a dark place at 25 ° C 20% RH for 24 hours, then 25 ° C 20% Under the environment of RH, the reciprocal (1 / R) of the radius of curvature R (unit: m) is obtained, and this is defined as the degree of curl.
- the state of no warpage at 25 ° C. and 5% RH in the present invention means that the radius of curvature is lm or more in an environment of 25 ° C. and 55% RH.
- One method for keeping the silver halide light-sensitive material having such a habit without warping at 25 ° C and 55% RH is to place the silver halide light-sensitive material on a flat surface, and to set the silver halide light-sensitive material from above. This is to apply a force of about 1 kg per cm 2 and to stand still. When removing warpage with force, it is necessary that the photosensitive material is not scratched or creased.
- a curl degree of + indicates that the surface of the photosensitive material coated with the photosensitive layer is concave
- a curl degree of 1 indicates that the photosensitive material This indicates that the surface on the side provided with the conductive layer is in a convex state.
- the degree of curl of a silver halide color photographic light-sensitive material varies depending on various factors.
- the curl depends on the type and amount of gelatin in the photosensitive layer, the ratio of the oil-soluble compound to gelatin, the salt concentration, the type and amount of the gelatin hardener, and the elapsed time since the preparation of the silver halide photosensitive material.
- the degree changes.
- the curl degree changes depending on the material and thickness of the support and the material and amount of the laminate layer.
- a gelatin layer may be provided on the side of the support on which the photosensitive layer is not coated, or the amount of lamination on the support may be reduced. This can be achieved by making changes.
- one of the preferable embodiments is to appropriately change the amount of lamination on the side of the support on which the photosensitive layer is not coated.
- the silver halide contained in at least one of the color coupler-containing silver halide emulsion layers depends on the type of sensitizing dye and the method of addition. It is preferable that the spectral sensitivity distribution of the emulsion be in the following range.
- at least one peak of the spectral sensitivity distribution is at 450 to 49 nm, and 70% of the maximum sensitivity at the spectral sensitivity peak.
- the difference between the exposure wavelengths of the long wavelength and the short wavelength that gives the sensitivity of 20 nm or more and 100 nm or less more preferably the exposure wavelength difference is 20 nm or more and 80 nm or less, particularly preferably 30 nm or more. 80 nm or less.
- the above “exposure wavelength difference” refers to the long wavelength of the spectral sensitivity peak existing at 450 to 490 nm.
- the absolute value of the difference is from 20 nm to 100 nm.
- the spectral sensitivity distribution of the silver halide color photographic light-sensitive material varies depending on various factors. For example, when spectral sensitization is performed using a plurality of sensitized colors, the timing of addition, the rate of addition, the order of addition, the interval of addition, the stirring state of the added silver halide emulsion, the pH, and the temperature, The spectral sensitivity distribution changes greatly.
- a sensitizing dye is added in the emulsion ripening step after the precipitation and desalting treatment.
- a sensitizing dye before the chemical sensitization treatment during the ripening step, and when adding plural kinds of dyes, a mixed solution containing plural kinds of dyes is added. It is one of the preferable modes to prepare and add the mixed solution, and when adding plural kinds of sensitizing dyes in plural times, set the addition interval of plural kinds of sensitizing dyes. It is also preferable to add the compound by opening it for 30 seconds or more, and it is more preferable to add an interval of 1 minute or more. In addition, vigorous stirring is carried out during addition (preferably, Reynolds number of 20, 000 to 130, 000, more preferably of 20, 000 to: L20, 000, particularly preferred).
- the solution temperature and the pH be controlled as appropriate, so that the solution temperature becomes 20.000 to 100.000.
- the Reynolds number is an amount determined by the rotation speed of the stirring blade, the blade diameter, the liquid viscosity, and the liquid density, and the larger the value, the more intense the state of stirring. 1st edition, 6th printing ", Tokyo Chemical Doujin Co., Ltd., published in 2001, page 2537). If each dye is added separately and simultaneously instead of a mixed solution of dyes, and the stirring state is moderated, the distribution of the dye adsorption between silver halide particles will be formed, resulting in broad spectral sensitivity. The peak (exposure wavelength difference is too large) or a single steep peak (exposure wavelength difference is too small).
- a l, hi 2,] 3 1 ⁇ ! 34 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group, an amino group, an alkoxy group, a hydroxy group, or a labamoyl group, and these groups are substituted.
- al and ⁇ 2 represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group, an amino group, an alkoxy group, a hydroxy group, or a valvamoyl group. And these groups may be substituted.
- the alkyl group represents a linear, branched, or cyclic substituted or unsubstituted alkyl group. Also preferably substituted with 1 to 30 carbon atoms 4725
- an unsubstituted linear or branched alkyl group eg, methyl, ethyl, isopropyl, ⁇ -propyl, ⁇ -butyl, t-butyl, 2-pentyl, n-hexyl, n-hexyl) —Octyl, t-octyl, 2-ethylhexyl, 15-dimethylhexyl, n-decyl, n-dodecyl, n-tetradecyl, n-xadecyl, hydroxyethyl, hydroxy Propyl group, 2,3-dihydroxypropyl group, carboxymethyl group, carboxyethyl group, sulfoethyl group, sulfopropyl group, sulfobutyl group, methyla.minoethyl group, getylaminopropyl group, butoxypropyl group, eth
- a substituted or unsubstituted bicycloalkyl group having 530 carbon atoms that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 530 carbon atoms, for example, bicyclo [1, 2,2] heptane-1-yl, bicyclo [22,2] octane-3-yl), and a tricyclo structure having many ring structures.
- the alkenyl group represented by ⁇ 1 and ⁇ 2 represents an alkenyl group having 2 16 carbon atoms (for example, an aryl group, a 2-butenyl group, a 3-pentyl group, etc.).
- the alkynyl group represented by 1 and ⁇ 2 represents an alkynyl group having 210 carbon atoms (eg, a propargyl group, a 3-pentyl group, etc.).
- the aryl groups represented by a 1 and ⁇ 2 include a substituted or unsubstituted phenyl group having 6 to 20 carbon atoms, a naphthyl group (for example, an unsubstituted phenyl group, an unsubstituted naphthyl group, — Dimethylphenyl, 4-butoxyphenyl group, 4-dimethylaminophenyl group and the like, and the heterocyclic group includes, for example, a pyridyl group, a furyl group, an imidazolyl group, a pyridyl group, a morpholyl group and the like.
- examples of the acetyl group represented by ⁇ 1 and ⁇ 2 include acetyl group, formyl group, benzoyl group, bivaloyl tomb, propyl group, ⁇ -nonanoyl group and the like.
- Examples thereof include an unsubstituted amino group, a methylamino group, a hydroxyxylamino group, an ⁇ -octylamino group, a dibenzylamino group, a dimethylamino group, a ethylamino group, and the like.
- the alkoxy group include a methoxy group, an ethoxy group, ⁇ -butyloxy group, cyclohexyloxy group, ⁇ -octyloxy group, ⁇ -decyloxy group, and the like.
- Examples of the rubamoyl group include unsubstituted rubamoyl group, ,, ⁇ -ethylmethylcarbamoyl group, and ⁇ -phenyl. And a rucarbamoyl group.
- ⁇ 1 and ⁇ 2 may have a substituent as much as possible.
- substituents include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom).
- An alkyl group (linear, branched, or cyclic alkyl group, including a bicycloalkyl group and an active methine group), an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group (regardless of substitution position), Acyl group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, ⁇ -hydroxycarbamoyl group, ⁇ -acylcarbamoinole group, ⁇ -sulfonylcarbamoyl group, ⁇ -force Rubamoylcarbamoyl group, thiocarbamoyl group, —sulfamoylcarbamoyl group, sorbazol group, carboxy group or a salt thereof, Oxalyl group, oxamoyl group, cyano group, carboximidoyl group
- (Carbonimidoyl group) Formyl group, hydroxy group, alkoxy group (including groups containing repeating ethyleneoxy or propyleneoxy group units), aryloxy group, heterocyclic oxy group, acryloxy group, (alkoxy or aryloxy) carbonylo A xyl group, Canolepamoyloxy, sulfonyloxy, amino, (alkyl, aryl, or heterocycle) amino, acylamino, sulfonamide, ureido, thioureido, N-hydroxyperido, imimi Group, (alkoxy or aryloxy) carbinoleamino group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, ammonio group, oxamoylamino group, N- (alkyl or aryl) group Ruphonylureido group, N-acylurei
- the active methine group means a methine group substituted by two electron-withdrawing groups
- the electron-withdrawing group here is an acyl group, an alkoxycarbyl group, or an aryloxy group. It means a carbonyl group, a carbamoyl group, an anolyalkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, a trifluoromethyl group, a cyano group, a nitro group, or a carbonimidoyl group (Carbonimidoyl group).
- the two electron-withdrawing groups may be bonded to each other to form a cyclic structure.
- the salt means a cation such as an alkali metal, an alkaline earth metal, or a heavy metal, and an organic cation such as an ammonium ion or a phosphonium ion. These substituents may be further substituted with these substituents.
- 1 to] 34 are defined in the same manner as ⁇ 1 and a 2. However, a plurality of j31s may be the same or different. Similarly, a plurality of 2, j3 3 and / 34 may be the same or different.
- al, a 2, and 1 to 4 each represent an eternal atom, a substituted alkyl group, an alkenyl group, an aryl group, a heterocyclic group, and This is the case for a sil group.
- ⁇ 1, ⁇ 2, and / 31 to J34 each represent a hydrogen atom, a substituted alkyl group, an alkenyl group, or an aryl group.
- Particularly preferred are ⁇ 1, ⁇ 2, and 1 to! In the case where 34 represents a hydrogen atom, a substituted alkyl group or an aryl group, respectively.
- a compound represented by the following general formula (II) is more preferable. Used.
- the compound represented by the general formula (II) used in the silver halide color photographic light-sensitive material of the present invention preferably in the fourth embodiment, is exemplified by British Patent No. 6,640,08 and U.S. Pat. Nos. 4910-105, or JP-A-50-41227 or "The Cyanine 'Soy' and Related 'Compounds" by Hemmer (Interscience Inc.) ⁇ Publishers, New York, 1969) It can be easily synthesized by the method described on pages 32 to 75 or a method analogous thereto.
- the light-sensitive material of the present invention conventionally known photographic materials and additives can be used.
- a transmission type support or a reflection type support can be used.
- Transparent supports include cellulose triacetate film, transparent films such as cellulose nitrate film and polyethylene terephthalate, and polyesters of 2,61-naphthalene dicarboxylic acid (NDCA) and ethylene glycol (EG) and NDCA.
- NDCA 2,61-naphthalene dicarboxylic acid
- EG ethylene glycol
- a material in which an information recording layer such as a magnetic layer is provided on a polyester of terephthalic acid and EG or the like is preferably used.
- the reflective support is preferably a reflective support that is laminated with a plurality of polyethylene layers or polyester layers, and contains a white pigment such as titanium oxide in at least one of such water-resistant resin layers (laminate layers). Is preferred. In the present invention, a reflective support is preferred. .
- the polyolefin layer may be composed of multiple layers, in which case it is preferred that the polyolefin layer be formed on the silver halide emulsion layer side.
- the polyolefin layer adjacent to the latin layer has no micropores (eg, polypropylene, polyethylene), and is composed of a polyolefin (eg, polypropylene, polyethylene) having micropores on the side close to the paper substrate. .
- the density of the multilayer or single polyolefin layer located between the paper substrate and the photographic component layer is preferably 0.40 to 1.0 OgZml, more preferably 0.50 to 0.70 gZm1.
- the thickness of the multilayer or single polyolefin layer located between the paper substrate and the photographic constituent layer is preferably from 10 to 10 ⁇ m, more preferably from 15 to 7 ⁇ .
- the ratio of the thickness of the polyolefin layer to the thickness of the paper substrate is preferably from 0.05 to 0.2, more preferably from 0.1 to 0.15.
- polyolefin layer on the opposite side (back side) of the photographic constituent layer of the paper substrate from the viewpoint of increasing the rigidity of the reflection support.
- the surface of the polyolefin layer on the back side is matted.
- Polyethylene or polypropylene is preferred, and polypropylene is more preferred.
- the polyolefin layer on the back surface is preferably from 5 to 5 ⁇ , more preferably from 10 to 3 ⁇ , and further preferably from 0.7 to 1.1 g / m 1.
- the water-resistant resin layer contains a fluorescent whitening agent.
- the fluorescent whitening agent may be dispersed in the hydrophilic colloid layer of the light-sensitive material, and the hydrophilic colloid layer containing the fluorescent whitening agent dispersed therein may be formed separately.
- a benzoxazole-based, coumarin-based, or pyrazoline-based fluorescent whitening agent can be used. More preferably, a benzoxoxazolylnaphthalene-based or benzoxazolylstilbene-based fluorescent whitening agent can be used. It is.
- the fluorescent whitening agent contained in the water-resistant resin layer include, for example, 4,4'-bis (benzoxoxolinolene) stinoleben, 4,4'-bis (5-methylinobenzobenzoxazolyl) stinoleben and Examples thereof include a mixture thereof.
- the amount used is not particularly limited, but is preferably 1 to 10 Omg / m 2 .
- a mixing ratio of the water-resistant resin Preferably 0005-3 mass 0/0 0. in pairs in the resin, more preferably from 001 to 0.5% by weight 0.5.
- the reflective support may be a transmissive support or a reflective support as described above, on which a hydrophilic colloid layer containing a white pigment is provided. Further, the reflective support may be a support having a mirror-reflective or second-class diffuse-reflective metal surface.
- the support used in the light-sensitive material of the present invention may be a white polyester-based support for display or a support in which a layer containing a white pigment is provided on a support having a silver halide emulsion layer.
- a body may be used.
- the transmission density of the support is preferably set in the range of 0.35 to 0.8 so that the display can be viewed with both reflected light and transmitted light.
- decolorization is performed on the hydrophilic colloid layer by the processing described in European Patent EP 0,337,490 A2, pp. 27-76, for the purpose of improving image sharpness and the like.
- Possible dyes are added so that the optical reflection density at 680 nm of the light-sensitive material becomes 0.70 or more, or a divalent to tetravalent dye is added to the water-resistant resin layer of the support. It is preferable to contain 12% by mass or more (more preferably 14% by mass or more) of titanium oxide surface-treated with alcohols (for example, trimethylolethane). '.
- the light-sensitive material of the present invention contains a hydrophilic colloid layer in order to prevent irradiation and halation and to improve safety and the like, and to the hydrophilic colloid layer, EP No. EP 337 490 A2, No. 2 of the specification of European Patent. It is preferable to add a dye (for example, an oxonol dye or a cyanine dye) that can be decolorized by the treatment described on pages 7 to 76. Further, the dyes described in European Patent EP 0 819 977 are also preferably added to the light-sensitive material of the present invention. Some of these water-soluble dyes, if used in a small amount, degrade color separation and safety of the sailfish. Dyes that can be used without deteriorating the color separation are described in JP-A-5-127324, JP-A-5-127325, JP-A-5-216185. The water-soluble dyes described are preferred.
- a colored layer that can be decolorized by treatment is used instead of the water-soluble dye, or in combination with the water-soluble dye.
- the colored layer that can be decolorized by the processing used may be in direct contact with the emulsion layer, or is arranged so as to be in contact with an intermediate layer containing a processing color mixture inhibitor such as gelatin or hydroquinone. May be.
- This colored layer is preferably provided below (e.g., on the support side of) the emulsion layer that develops the same primary color as the colored color. It is possible to install all the colored layers corresponding to each primary color individually, or to arbitrarily select only some of them. It is also possible to provide a colored layer that is colored corresponding to a plurality of primary color gamuts.
- the optical reflection density of the colored layer is determined by the wavelength range used for exposure (400 nm ⁇ ! To 700 nm in the normal printer exposure range, and the scanning exposure light source used in the case of scanning exposure). It is preferable that the optical density value at the wavelength having the highest optical density is 0.2 or more and 3.0 or less. More preferably, it is 0.5 or more and 2.5 or less, particularly preferably 0.8 or more and 2.0 or less.
- a conventionally known method can be applied.
- the dyes described on page 3 from the upper right column to page 8 of JP-A No. 2-282244 or the page 3 lower left column on page 11 of page 3 of JP-A-3-7931 are disclosed.
- a method using colloidal silver as described in Japanese Patent Application Laid-Open No. 1-239544.
- a fine powder dye which is substantially water-insoluble at least at pH 6 or less but is substantially water-soluble at least at pH 8 or more is contained.
- the method is described on pages 4 to 13 of JP-A No. 21048/44.
- a method of mordanting an aionic dye into a cationic polymer is described in JP-A-2-84637, pages 18 to 26.
- Methods for preparing colloidal silver as a light absorber are described in U.S. Pat. Nos. 2,688,6.01 and 3,459,566. Among these methods, a method of incorporating a fine powder dye, a method of using colloidal silver, and the like are preferable.
- the photosensitive material of the present invention is used for a color negative film, a color positive film, a color reversal film, a color reversal photographic paper, a color photographic paper, a display photographic material, a digital color proof, a color positive for a movie, a color negative for a movie, etc. It is preferably used as a display photosensitive material, digital color proof, color positive for cinema, color reversal photographic paper, or color photographic paper, particularly preferably as color photographic paper.
- the silver halide color photographic light-sensitive material for example, color photographic paper
- the silver halide color photographic light-sensitive material comprises, on a support, a yellow-colored blue-sensitive silver halide emulsion layer (a silver halide emulsion layer containing a yellow dye-forming coupler), a magenta color-forming layer.
- At least one green-sensitive silver halide emulsion layer (a silver halide emulsion layer containing a magenta dye-forming coupler) and one cyan-colored red photosensitive silver halide emulsion layer (a silver halide emulsion layer containing a cyan dye-forming coupler) It is preferable to have each layer Generally, these silver halide emulsion layers are a yellow color-forming silver halide emulsion layer, a magenta color-forming silver halide emulsion layer, and a cyan color-forming silver halide emulsion layer in the order of distance from the support.
- the silver halide emulsion contained in the blue-sensitive silver halide emulsion layer is a green light-sensitive silver halide emulsion due to the spectral characteristics of the negative yellow mask and the light source used during exposure. It is preferable that the sensitivity is relatively high with respect to silver emulsions and red-sensitive silver halide emulsions. Therefore, the grain side length of the blue-sensitive emulsion is preferably larger than the grain side length of the other layer.
- the molar extinction coefficient of commonly known yellow coupler coloring dyes is lower than that of magenta coupler coloring dyes and cyan coupler coloring dyes, and the amount of blue-sensitive emulsion coating increases with the increase in the amount of yellow coupler coating. Tend to.
- the yellow one-color blue-sensitive silver halide emulsion layer is disadvantageous in comparison with other layers in consideration of the resistance to pressure from the surface of the photosensitive material, such as pulling, and is located on the side closer to the support. It is preferred to be located.
- the silver halide emulsion layer containing the yellow coupler may be arranged at any position on the support. However, when the yellow coupler containing layer contains silver halide tabular grains, the silver halide emulsion containing the magenta coupler may be used. It is preferable that the coating is provided at a position farther from the support than at least one of the emulsion layer and the silver halide emulsion layer containing a cyan coupler. In addition, from the viewpoint of accelerating color development, desilvering, and reducing residual color by a sensitizing dye, the silver halide emulsion layer containing the yellow coupler is the most from the support to the silver halide emulsion layer from the other silver halide emulsion layers.
- the coating is provided at a remote position.
- the cyan coupler-containing silver halide emulsion layer is preferably the center layer of the other silver halide emulsion layers, and from the viewpoint of reducing photobleaching, the cyan coupler-containing halide is preferred.
- the silver emulsion layer is preferably the lowermost layer.
- each of the yellow, magenta and cyan color-forming layers may be composed of two or three layers. For example, as described in JP-A-4-75055, JP-A-11-14035, JP-A-10-246940 and U.S. Pat. No. 5,576,159, silver halide emulsions are used. It is also preferred that a coupler layer not containing is provided adjacent to the silver halide emulsion layer to form a color-forming layer.
- the silver halide emulsion and other materials (additives, etc.) and photographic constituent layers (layer arrangement, etc.) used in the present invention, and the processing methods and processing additives applied for processing this light-sensitive material are described in JP-A-62-215272, JP-A-2-33144, and European Patent EP 0,355,660A2, and especially EP 0,355,66.
- OA No. 2 is preferably used.
- JP-A-5-34889, JP-A-4-1359249, JP-A-31-37553, JP-A-4-270344, JP-A-5-66527, JP-A-4-34548 and JP-A-4-34548 No. 145433, No. 2-854, No. 1-158431, No.
- the silver halide color photographic light-sensitive material described in 7A2 and the like and the processing method thereof are also preferable.
- Line 48 Same Line 20, Same Line 19, Line 19, Column 39, Line 11-Line 44, Line 2-Column 31, Line 38-Layer structure of photosensitive material Line 26, Line 35 Item 32 column 33 line column 72 line 12
- cyan, magenta and yellow couplers that can be used or used in combination in the present invention include, in JP-A-62-215272, page 91, upper right column, line 4 to page 121, upper left column, line 6, JP-A-2-33144, page 3, upper right column, line 14 to page 18, last line in upper left column and page 30, upper right column, line 6 to lower right column, page 35 Line 1 and EP 0,355 , 660 A No. 2, page 4, lines 15 to 27, page 5, lines 30 to 28, line 45. page 29, lines 31 to 47, page 47, lines 23 to 63
- the couplers described on page 50, line 50, are also useful.
- the light-sensitive material of the present invention may be added with compounds represented by general formulas (II) and (III) of W098 / 33760 and general formula (D) of JP-A-10-221825. Well, good.
- cyan dye-forming coupler may be simply referred to as “cyan coupler”
- a pyrrole-triazole-based coupler is preferably used, and the general formula (I) described in JP-A-5-1313324 is preferably used.
- Couplers represented by the general formula (I) of JP-A-7960 and the couplers described in these patent documents are particularly preferred. Further, a phenol-based or naphthol-based cyan coupler is also preferable. For example, a cyan coupler represented by the general formula (ADF) described in JP-A-10-333297 is preferable. Other cyan couplers include European Patent 04
- a pyrroloazole-based cyan coupler represented by the general formula (I) described in JP-A-11-282138 is particularly preferable, and paragraph Nos. 001 2 to 0059 of the patent document. Is applied to the present invention as it is, including the exemplified cyan couplers (1) to (47), and is preferably incorporated as a part of the present specification by reference.
- magenta dye-forming coupler (may be simply referred to as “magenta coupler”) used in the present invention
- magenta coupler examples include 5-pyrazolone-based magenta couplers and pyrazoloazo-magenta-based magenta couplers as described in the known documents in the above table.
- a secondary or tertiary alkyl group as described in JP-A-61-65245 has a secondary or tertiary alkyl group of a pyrazo-opened triazono ring, as described in JP-A-61-65245.
- a pyrazolo triazole coupler directly linked to the 6-position; a pyrazoloazole coupler containing a sulfonamide group in the molecule as described in JP-A-61-65246; and JP-A-61-147254.
- Pyrazoloazole couplers having a lucoxyphenylsulfonamide ballast group and alkoxy groups at the 6-position as described in European Patent Nos. 226,849A and 294,785A.
- Preference is given to the use of pyrazoloazole couplers having a oxy group.
- magenta coupler is preferably a pyrazoloazole coupler represented by the general formula (M-I) described in JP-A No. 8-12984, and paragraphs 0009 to 0026 of the patent document are directly used in the present invention. And incorporated herein by reference.
- pyrazoloazole couplers having a sterically hindered group at both the 3-position and the 6-position described in European Patent Nos. 854384 and 884640 are also preferably used.
- yellow coupler examples include, in addition to the compounds described in the above table, European Patent EP 044796 9A1 Acetylacetoamide-type yellow coupler having a 3- to 5-membered cyclic structure in the acyl group described in the European Patent No. EP 048 2552 A1, a malondianilide-type yellow coupler having a cyclic structure described in European Patent No. 9538 7 0 A1, pyrrole described in 95387 1A1, 953872A1, 953873A1, 953874A1, and 953875A1 in Japanese Patent No.
- an acylacetoamide-type yellow coupler in which the acyl tomb is an 11-alkylcyclopropane-111-carbonyl group a malondianilide-type yellow coupler in which one of the anilides constitutes an indoline ring, or a heterocyclic ring substituted with an acyl group It is preferable to use an acetanilide type yellow coupler. These couplers can be used alone or in combination.
- an acylacetamide-type yellow coupler in which the acyl group is an alkylcyclopropane-111-carbonyl group, a malondienylide-type yellow coupler in which one of the anilide forms an indoline ring, or a heterocyclic ring substituted with the acyl group.
- the use of an acetoanilide yellow coupler is preferred. These couplers can be used alone or in combination.
- dye-forming couplers are added to photographic useful substances and other high-boiling organic solvents, and are emulsified and dispersed together, and incorporated into the light-sensitive material as a dispersion.
- This solution is dispersed in a hydrophilic colloid, preferably in an aqueous gelatin solution, together with a surfactant dispersant, by using any known apparatus such as an ultrasonic wave, a colloid mill, a homogenizer, a Mentongorin, and a high-speed dissolver. It is emulsified and dispersed to obtain a dispersion.
- the high-boiling point organic solvent is not particularly limited, and a conventional one can be used. Examples thereof include those described in US Pat. No. 2,322,027 and JP-A-7-152129.
- an auxiliary solvent can be used together with a high-boiling organic solvent.
- co-solvents include lower alcohol acetates such as ethyl acetate and butyl acetate, ethyl propionate, secondary butynoleate acetate, methyl ethyl ketone, methyl isobutyl ketone, s-ethoxysethyl acetate, methyl acetate solvent acetate, and methyl acetate.
- an organic solvent that is completely miscible with water such as methyl alcohol, ethyl alcohol, acetone, and tetrahydrofuran / dimethylformamide.
- these organic solvents can be used in combination of two or more kinds.
- the emulsified dispersion may be used as necessary. All or part of the auxiliary solvent can be removed by a method such as distillation under reduced pressure, washing with noodles or ultrafiltration.
- the average particle size of the lipophilic fine particle dispersion thus obtained is preferably from 0.04 to 0.50 ⁇ m, more preferably from 0.05 to 0.30 ⁇ , most preferably from 0.06 to 0.30 ⁇ . 0.20 ⁇ !
- the average particle size can be measured using a Coulter Submicron Particle Analyzer-model N4 (Coulter Electronics Co., Ltd.) or the like.
- a tinting pigment may be co-emulsified in the emulsion used for the silver halide color photographic light-sensitive material of the present invention for adjusting the color of a white background.
- the compound may be co-emulsified in an organic solvent in which the useful compound for dissolution is dissolved and co-emulsified to prepare an emulsion.
- the coupler used in the present invention is impregnated with an orifice double latex polymer (for example, U.S. Pat. No. 4,203,716) in the presence (or absence) of the high boiling organic solvent described above, Alternatively, it is preferable to dissolve it in a water-insoluble and organic solvent-soluble polymer and emulsify and disperse it in a hydrophilic colloid aqueous solution.
- Water-insoluble and organic solvent-soluble polymers which can be preferably used are described in U.S. Pat. No. 4,857,449, columns 7 to 15 and International Publication WO 88/00723, pages 12 to 15. Homopolymers or copolymers described on page 30 can be mentioned. More preferably, use of a methacrylate-based or acrylamide-based polymer, particularly an acrylamide-based polymer, is preferred in view of color image stability and the like.
- a compound having a triazine skeleton having a high molar extinction coefficient as the ultraviolet absorber.
- the compounds described in the following patent documents can be used. These are preferably added to the photosensitive layer or / and the non-photosensitive.
- binder hydrophilic binder
- protective colloid that can be used in the light-sensitive material of the present invention
- gelatin but if necessary, other gelatin derivatives
- hydrophilic colloids such as graft polymers of ratine and other polymers, proteins other than gelatin, sugar derivatives, cellulose derivatives, and synthetic hydrophilic macromolecules such as mono- or copolymers, alone or together with gelatin. it can.
- the gelatin used in the silver halide color photographic light-sensitive material of the present invention may be any of lime-processed gelatin and acid-processed gelatin, and may be gelatin produced from any of bovine bone, cow skin, pig skin and the like. Preferably, it is a lime-processed gelatin made from beef bone and pig skin.
- heavy metals contained as impurities such as iron, copper, zinc, and manganese are preferably at most 5 ppm, more preferably at most 3 ppm.
- the amount of calcium contained in the light-sensitive material is preferably 20 mg / m 2 or less, more preferably 1 Omg / m 2 or less, and most preferably 5 mg Zm 2 or less.
- the coating pH of the photosensitive material is preferably from 4.0 to 7.0, more preferably from 4.0 to 6.5.
- the total coated gelatin amount in the photographic constituent layer in the present invention is preferably from 3.O g / m 2 to 7.O gZm 2 , more preferably from 3.O g / m 2 to 6.5 gZm 2 , It is more preferably at least 3. O g / m 2 and at most 6. O gZm 2 , and particularly preferably at least 3 g / m 2 and at most 5 g / m 2 .
- the total amount of gelatin in the photographic component layer of the photographic material is defined as the photosensitivity from the support to the hydrophilic colloid layer farthest from the support on the side where the silver halide emulsion layer is coated.
- the total amount of the hydrophilic binder contained in the silver halide emulsion layer and the non-photosensitive hydrophilic colloid layer If the amount of the hydrophilic binder is too large, the effect will be reduced due to such factors as impairing the speed of color development processing, worsening of the pleat discoloration, impairing the rapid processing property of the rinsing step (washing and Z or stabilizing step). There is. On the other hand, if the amount of the hydrophilic binder is too small, adverse effects due to insufficient membrane strength such as pressure cover streaks are likely to occur. Even in the case of ultra-rapid processing, the film thickness of the entire photographic component layer is 3 ⁇ ! To satisfy the image development, fixing bleaching properties, and residual color.
- the method for evaluating the dry film thickness can be measured by a change in the film thickness before and after peeling off the dry film, or by observing the cross section with an optical microscope or an electron microscope.
- the swelled film thickness is 8 ⁇ ! ⁇ 19 ⁇ , more preferably 9 ⁇ ! 118 ⁇ is preferred.
- the swelled film thickness can be measured by immersing a dried photosensitive material in an aqueous solution at 35 ° C., swelling and reaching a sufficient equilibrium, and using a dot printing method.
- the total coating ⁇ weight in the present onset Ming is preferably 0. 5 gZm is 2 or less, 0. 2g / m 2 ⁇ 0.
- the total amount of applied silver means the total amount of applied silver in all the photographic constituent layers in the light-sensitive material of the present invention.
- a surfactant can be added to the light-sensitive material from the viewpoint of improving the coating stability of the light-sensitive material, preventing the generation of static electricity, and adjusting the charge amount.
- Surfactants include anionic surfactants, cationic surfactants, betaine surfactants, and nonionic surfactants, for example, those described in JP-A-5-333492. Is mentioned.
- a surfactant containing a fluorine atom is preferable.
- a fluorine atom-containing surfactant can be preferably used.
- These fluorine atom-containing surfactants may be used alone or in combination with other conventionally known surfactants. It is a combination with an agent.
- the addition amount of the photosensitive material of the surface active ten raw material is not particularly limited, but generally, 1 x 1 0- 5 ⁇ 1 g Zm 2, preferably LXL 0 one 4 ⁇ 1 x 1 0 one 1 g / m 2, more preferably lxl 0-3 ⁇ : a L xl 0- 2 g / m 2 .
- the photosensitive material of the present invention can form an image by an exposure step of irradiating light according to image information and a development step of developing the light-irradiated photosensitive material.
- the light-sensitive material of the present invention is suitable for a scanning exposure method using a cathode ray (CRT) in addition to being used for a printing system using a normal negative printer.
- CTR cathode ray
- a cathode ray tube exposure apparatus is simpler, more compact, and lower in cost than an apparatus using a laser. It is also easy to adjust the optical axis and color.
- various luminous bodies that emit light in the spectrum area are used as necessary. For example, any one of red, green, and blue light emitters, or a mixture of two or more of them may be used.
- the spectrum region is not limited to the red, green, and blue regions described above, and a phosphor that emits light in a yellow, orange, violet, or infrared region is also used.
- a cathode ray tube which emits white light by mixing these light emitters is often used.
- the photosensitive material has a plurality of photosensitive layers having different spectral sensitivity distributions and the cathode tube also has a phosphor that emits light in a plurality of spectral regions
- a plurality of colors are exposed at a time, that is, a cathode ray.
- a plurality of color image signals may be input to the tube to emit light from the tube surface.
- a method of sequentially inputting image signals for each color to sequentially emit light of each color, and exposing through a film for cutting a color other than that color (plane sequential exposure) may be adopted. It is more preferable to use a high-resolution cathode-ray tube for higher image quality.
- the photosensitive material of the present invention may be a monochromatic light source such as a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser, or a second harmonic emission light source (SHG) combining a solid-state laser using a semiconductor laser as an excitation light source and a nonlinear optical crystal.
- a digital scanning exposure method using high-density light is preferably used.
- SHHG second harmonic generation light source
- it is preferable to use a semiconductor laser in order to design a compact, inexpensive device having a long life and high stability, it is preferable to use a semiconductor laser, and it is preferable to use a semiconductor laser as at least one of the exposure light sources.
- the spectral sensitivity maximum wavelength of the photosensitive material of the present invention can be arbitrarily set according to the wavelength of the scanning exposure light source to be used.
- An SHG light source obtained by combining a solid-state laser using a semiconductor laser as an excitation light source or a combination of a semiconductor laser and a nonlinear optical crystal can halve the laser oscillation wavelength, so that blue light and green light can be obtained. Therefore, the spectral sensitivity maximum of the photosensitive material can be provided in the usual three wavelength regions of blue, green and red.
- the exposure time in such a scanning exposure is defined as the time for exposing a pixel size in a case where the pixel density and 4 0 0 dpi (or 3 0 0 dpi), 1 X 1 0 one four seconds as a preferred exposure time Or less, more preferably 1 ⁇ 10 16 seconds or less.
- the present invention When the present invention is applied to a silver halide color photographic light-sensitive material, it is preferable to perform imagewise exposure with coherent light of a blue laser having an emission wavelength of 420 to 46 O nm. Blue laser Among them, it is particularly preferable to use a blue semiconductor laser.
- a blue semiconductor laser with a wavelength of 43 to 450 nm
- a semiconductor laser (oscillation wavelength of about 940 nm) with a waveguide-like inverted domain structure L i N b 0 3 blue laser of approximately 4 7 0 nm taken out by wavelength conversion by the SHG crystal, a semiconductor laser (originating L i N b 0 3 of S HG green laser of about 530 nm taken out by wavelength conversion by crystallization, red semiconductor laser having a wavelength of about 685 nm having a vibration wavelength of about 1 060 nm) a waveguide-like inverted domain structure (Hitachi type No. HL 6738MG, trade name) and a red semiconductor laser with a wavelength of about 650 nm (Hitachi type No. HL 6501MG, trade name) are preferably used.
- the silver halide photographic light-sensitive material of the present invention can be preferably used in combination with an exposure and development system described in the following known materials.
- the developing system include an automatic printing and developing system described in JP-A-10-333253, a photosensitive material transport device described in JP-A-2000-10206, and a photosensitive material conveying device described in JP-A-11-215312.
- a photo print system including an image recording apparatus described in JP-A-2000-310822.
- Preferred scanning exposure methods applicable to the present invention are described in detail in the patent documents listed in the above table.
- the first embodiment of the present invention is applied as a photosensitive material having rapid processing suitability.
- the color development time is 28 seconds or less, preferably 25 seconds or less 6 seconds or more, and more preferably 20 seconds or less 6 seconds or more.
- the bleach-fixing time is preferably 30 seconds or less, more preferably 25 seconds or less and 6 seconds or more, and more preferably 20 seconds or less and 6 seconds or more.
- the washing or stabilizing time is preferably 60 seconds or less, more preferably 40 seconds or less and 6 seconds or more.
- the silver halide color photographic light-sensitive material of the second embodiment of the present invention is preferably applied to a light-sensitive material having rapid processing suitability.
- the color development time is preferably 60 seconds or less, more preferably 50 seconds or less 6 seconds or more, more preferably 30 seconds or less 6 seconds or more, and most preferably 20 seconds or less 6 seconds or more. is there.
- the bleach-fixing time is preferably 60 seconds or less, more preferably 50 seconds or less and 6 seconds or more, more preferably 30 seconds or less and 6 seconds or more, and most preferably 20 seconds or less and 6 seconds or more.
- the washing or stabilizing time is preferably 150 seconds or less, more preferably 130 seconds or less and 6 seconds or more.
- the silver halide color photographic light-sensitive material of the third embodiment of the present invention is preferably applied to rapid processing.
- the color development time is preferably 40 seconds or less, more preferably 30 seconds or less, 6 seconds or more, and most preferably 20 seconds or less and 6 seconds or more.
- the bleach-fixing time is preferably 40 seconds or less, more preferably 30 seconds or less, 6 seconds or more, and most preferably 20 seconds. Less than 6 seconds.
- the washing or stabilizing time is preferably 100 seconds or less, more preferably 80 seconds or less and 6 seconds or more.
- the photosensitive material of the fourth embodiment of the present invention is preferably applied as a photosensitive material having rapid processing suitability.
- the color development time is preferably 30 seconds or less, more preferably 25 seconds or less 6 seconds or more, and more preferably 20 seconds or less 6 seconds or more.
- the bleaching settling time is preferably 30 seconds or less, more preferably 25 seconds or less 6 seconds, and particularly preferably 20 seconds or less and 6 seconds or more.
- the washing or stabilization time is preferably 60 seconds or less, more preferably 40 seconds or less and 6 seconds or more.
- the color development time refers to the time from when the photosensitive material enters the color developing solution to when it enters the bleaching and fixing solution in the next processing step.
- the time during which the photosensitive material is immersed in the color developing solution (so-called submerged time) and the time when the photosensitive material leaves the color developing solution and is bleached and fixed in the next processing step
- the sum of the time during which it is transported in the air toward the bath (so-called air time) is called the color development time.
- the bleach-fixing time refers to the time from when the photosensitive material enters the bleach-fixing solution to when it enters the next washing or stabilizing bath.
- the term “washing or stabilizing time” refers to the time during which the photosensitive material is in the washing or stabilizing solution and then in the solution for the drying step (so-called liquid time).
- the method of developing the light-sensitive material of the present invention after exposure includes a conventional method of developing with a developing solution containing an alkaline agent and a developing agent (particularly a p-phenylenediamine-based color developing agent), and a developing agent.
- a wet method such as a method of developing with an activator solution such as an alkaline solution containing no developing agent and being incorporated in a photosensitive material
- a thermal developing method using no processing solution can be used.
- the activator method is a preferable method from the viewpoint of environmental preservation because the processing agent is not contained in the processing solution, so that the processing solution can be easily supplied and handled, and the load at the time of processing the waste solution is small.
- a method of developing with a developer containing an alkali agent and a developing agent is preferable.
- examples of the developing agent or its precursor incorporated in the photosensitive material include, for example, JP-A Nos. 8-234388, 9-152686, and 9 — 1 5 2
- a developing method in which the amount of silver applied to the light-sensitive material is reduced and image amplification processing (intensification processing) using hydrogen peroxide is preferably used.
- this method it is preferable to use this method as an activator method.
- an image forming method using an activator solution containing hydrogen peroxide described in JP-A-8-297354 and JP-A-9-152695 is preferably used.
- desilvering is usually performed after processing with an activator solution.
- desilvering processing is omitted, and washing or stabilization is performed. Simple methods such as processing can be performed.
- activator solution desilvering solution (bleaching / fixing solution), washing and stabilizing solution used in the present invention
- known materials and processing methods can be used.
- the silver halide photographic light-sensitive material of the present invention can obtain an excellent white background even when subjected to rapid processing. be able to. It is also highly suitable for digital exposure such as laser scanning exposure. Further, even when the photosensitive material is used after being stored over time, an excellent white background can be provided.
- the silver halide color photographic light-sensitive material of the present invention has high sensitivity and low fog, and has little change in performance such as fog change even when processing conditions are changed.
- the silver halide color photographic light-sensitive material of the present invention has excellent effects such as high sensitivity, high chroma, high gray density, and little unevenness in rapid processing.
- the silver halide color photographic light-sensitive material of the present invention can provide an image with high sensitivity, low fog, and little color blur even in rapid processing after digital exposure. Further, the silver halide color photographic light-sensitive material of the present invention has little sensitivity dependency of the emulsion preparation scale and is excellent in running processing suitability.
- the silver halide photographic light-sensitive material of the present invention has high sensitivity, low fog, excellent gradation characteristics, and small change in performance in the emulsion production process.
- High silver chloride cubic particles were prepared by simultaneously adding and mixing an aqueous solution of silver nitrate and an aqueous solution of sodium chloride to deionized water containing agitated deionized gelatin. During the preparation process, the nucleation portion was added from 0% to 3% of silver nitrate. The addition rate of the silver nitrate aqueous solution and the sodium chloride aqueous solution was accelerated as a linear function of time • from the time when the addition of silver nitrate was 3% to the time when it was 80%. Potassium bromide (4.0 mol% per mol of finished silver halide) was added from the time when the addition of silver nitrate was 80% to the time when the addition was 100%.
- the obtained emulsion grains are silver iodobromochloride grains. According to observation and measurement using a transmission electron micrograph (direct method), monodisperse cubic grains having a side length of 0.50 ⁇ and a variation coefficient of 9.0% were obtained. Met. After the emulsion was subjected to sedimentation by precipitation, deionized gelatin, and the compounds (Ab-1), (Ab-2), (Ab-3), and calcium nitrate were added and redispersed.
- Emulsion B-2 K 2 [IrC 15 (5-methylthiazole)] (3.4 moles per mole of finished silver halide) was added from 82% to 88% of silver nitrate. except that the addition of X 10- 8 mol) in the same manner as emulsion B- 2, and an emulsion B- 3.
- Emulsion B-4 was prepared in the same manner as Emulsion B-3, except that the addition amount of each was increased three-fold while maintaining the ratio of [E].
- Emulsion B-6 K 2 [I r C 1 5 (H 2 0)] and K [I r C 1 4 ( H 2 O) 2] and K 2 [I r C 1 g (5 -me [thylthiazole)], and emulsion B-6 was prepared in the same manner as emulsion B-3, except that the amount of each addition was increased 30-fold.
- Emulsion B- 3 K 2 [I r C 1 5 (H 2 0)] and K [I r C 1 4 ( H 2 O) 2] and K 2 [I r C 1 5 (5- me [thylthiazole)], and emulsion B-17 was prepared in the same manner as emulsion B-3, except that the added amount of each was increased by 100 times while maintaining the ratio. (Preparation of Emulsion B-8 to Emulsion B-14)
- Emulsions B-1 to B-7 K 2 [RuC 15 (NO)] (3 moles per mole of finished silver halide) was added from 0% to 3% of silver nitrate.
- Emulsion B-8 to Emulsion B-14 were prepared in the same manner as Emulsion B-1 to Emulsion B-7 except that 4 ⁇ 10 9 mol) was added.
- the redispersed emulsion B-1 was dissolved at 40 ° C, and sodium benzenethiosulfonate, 1- (5-methylureidophenol) -1,5-mercaptotetrazole (Chemical i
- Emulsion B-1a to Emulsion B-7a in the same manner as Emulsion B-1a except that Emulsion B-1a was used in place of Emulsion B-1 in the preparation of Emulsion B-1a was prepared respectively. (Preparation of emulsion B—lb)
- Emulsion-2b to Emulsion B-7b were prepared in the same manner as Emulsion B-1b, except that Emulsion B-2 to Emulsion B-7 were used instead of Emulsion B-1. Each was prepared.
- Emulsion B—8b to Emulsion B—14 In the same manner as Emulsion B—1b, except that Emulsion B—1b was used instead of Emulsion B—1 in the preparation of Emulsion B—1b. b were each prepared.
- Emulsion B-1 In the preparation of Emulsion B-1, the addition rate of the nucleation part was changed. The amount of potassium iodide added was changed to 0.2 mol% per mol of finished silver halide. Otherwise, Emulsion G-1 was prepared in the same manner as Emulsion B-11. The resulting emulsion grains are silver iodobromochloride grains. According to observation and measurement using a transmission electron micrograph (direct method), monodisperse cubic grains having a side length of 0.40 ⁇ and a variation coefficient of 9.5% were obtained. Met. After subjecting this emulsion to precipitation sedimentation treatment, deionized gelatin, compounds (Ab-1), (Ab-2), (Ab-3) and calcium nitrate were added and redispersed. (Preparation of Emulsion G-2)
- Emulsion G-1 K 2 toward the point of 97% addition of the silver nitrate from 9 2% point [I r C 1 5 ( ⁇ 2 ⁇ )] ( silver halide per mol of the finished 2. 0 X 10- 8 molar) and K [I r C 1 4 ( ⁇ 2 ⁇ ) 2] ( same except that the addition of silver halide per mole of 2. 0 XI 0- 7 moles) of the finished and emulsion G-1
- an emulsion G-2 was prepared.
- Emulsion G-2 K 2 [IrC 15 (5-methylthiazole)] (6.6 mol / mol of finished silver halide) was added from the time when the addition of silver nitrate was 82% to the time when 88% was added. except that the addition of X 10- 8 mol) in the same manner as emulsion G-2, was prepared. emulsion G-3.
- Emulsion G-4 to Emulsion G-7 In the preparation of Emulsion G- 3, K 2 [I r C 1 5 ( ⁇ 2 ⁇ )] and K [I r C 1 4 ( H 2 O) 2] and K 2 [I r C 15 ( 5-me thylthiazole )] While maintaining the ratio of Emulsion G-3 to Emulsion G-4 and Emulsion G-7, respectively, in the same manner as Emulsion G-3, except that the added amount is increased by 3, 10, 30, and 100 times. Prepared.
- Emulsion G-. 1 to Emulsion G-7 the addition of silver nitrate over a time of 3% from the time of 0% K 2 [R u C 15 (NO)] ( silver halide of the finished per mol 6 Emulsion G-8 to Emulsion G-14 were prepared in the same manner as Emulsion G-1 to Emulsion G-7, except that .6 ⁇ 10 19 mol) was added.
- the redispersed emulsion G-1 was dissolved at 40 ° C, and sodium benzenethiosulfonate, p-daltalamide phenyl disulfide, sodium thiosulfate as a sulfur sensitizer, and (bis (1, 4, 5-trimethyl one 1, 2, 4-Toriazoriumu 3 Chio 'alerts) was added Oreto (I) tetrafluoropropoxy O robo rate), so that the tone at 1 X 10- 6 seconds exposure is most contrast After ripening at 65 ° C, the chemical sensitization was optimized.
- Emulsion G-1a use Emulsion G-2 to Emulsion G-7 instead of Emulsion G-1.
- Emulsion G-2a to Emulsion G— 7a was prepared respectively.
- the redispersed emulsion G-1 was dissolved at 40 ° C., and sodium benzenethiosulfonate, p-daltalamide diphenyldisulfide, the above-mentioned exemplified compound (SE3-29) as a selenium sensitizer, and as a gold sensitizer were added (bis (1, 4, 5-trimethyl-1, 2, 4 one Toriazo Riumu one 3-thiolate) Oreto (I) tetrafluoropropoxy O robo les Ichito), 1 X 10- 6 seconds
- the ripening was performed at 65 ° C with the chemical sensation being optimized so that the gradation in the exposure was the highest.
- Emulsion G-2b to Emulsion G-7b Except for using Emulsion G-2 to Emulsion G-7 instead of Emulsion G-1 in the preparation of Emulsion G-1b, was prepared respectively. (Preparation of Emulsion G-8b ⁇ Emulsion G-14b)
- emulsion G-1b was used in the same manner as emulsion G-1b except that emulsion G-8 to emulsion G-14 were used instead of emulsion G-1. Each of 14 b was prepared.
- Emulsion B-1 In the preparation of Emulsion B-1, the addition rate of the nucleation part was changed. The amount of potassium iodide added was changed to 0.1 mol% per mol of the finished silver halide. The addition amount of K 4 [Ru (CN) 6 ] was increased three-fold. Otherwise, Emulsion R-1 was prepared in the same manner as Emulsion B-1.
- the obtained emulsion grains are silver iodobromochloride grains. According to observation and measurement using a transmission electron micrograph (direct method), a monodisperse cube having a side length of 0.40 / im and a variation coefficient of 9.5% was obtained. Particles. After subjecting this emulsion to precipitation sedimentation, deionized gelatin, the compounds Ab-1, Ab-2, Ab-3 and calcium nitrate were added and redispersed. (Preparation of emulsion R-2)-'
- Emulsion R-1 to Emulsion R-7 K 2 [Ru C 15 (NO)] (3 moles per mole of finished silver halide) was added from 0% to 3% of silver nitrate.
- Emulsion R-8 to Emulsion R-14 were prepared in the same manner as Emulsion R-1 to Emulsion R-7, except that (3 ⁇ 10 to 19 mol) was added.
- Redispersed emulsion R- 1 was dissolved in 40 ° C, sodium benzene Chio sulfonate, was added compound one 1 as a sulfur Oyopi gold ⁇ agent, the gradation in 1 X 1 0- 6 seconds exposure Aged at 55 ° C with the best chemical feel to give the highest contrast. Then, one-one (3-Acetamidofue Nyl) 5-mercaptotetrazole, 11- (5-methylureidophenyl) -15-mercaptotetrazole, Compound 12, Compound 14 and potassium bromide (0.35 mol% per mole of finished silver halide) ) was added. Further, spectral sensitization was performed by adding sensitizing dye S-8 and Compound 15 before adding the sensitizer. The emulsion thus obtained was designated as emulsion R-1a.
- Emulsion R—2a to Emulsion R—7 In the same manner as Emulsion R—1a, except that emulsion R—1 to emulsion R—7 are used instead of emulsion R—1 in the preparation of Agent R—1a. a was prepared respectively.
- the redispersed emulsion R-1 was dissolved at 40 ° C, sodium benzenethiosulfate, the exemplified compound (SE3-9) as a selenium sensitizer, and (bis (1,4) as a gold sensitizer. , 5 bets Rimechiru 1, 2, 4-addition of triazolopyrimidines ⁇ mu 3- thiolate) Oreto (I) Tetorafuruo Roboreto), 1 X 1 0 one 6 seconds chemically as gradation in the exposure is most contrast Aged at 55 ° C with optimal feeling.
- emulsion R-1b was used in the same manner as emulsion R-1b except that emulsion R-2 to emulsion R-7 was used instead of emulsion R-1. b were each prepared.
- emulsion R-1b was used in the same manner as emulsion R-1b except that emulsion R-8 to emulsion R-14 was used instead of emulsion R_1. Each of 14 b was prepared.
- the emulsified dispersion A and the emulsion B-1a were mixed in a dissolved state, respectively, to prepare a coating solution for the first layer so as to have a composition described later.
- the emulsion coating amount indicates the coating amount in terms of silver.
- Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer.
- (H-1), (H-2) and (H-3) were used as gelatin hardeners in each layer.
- the total amount of each 1 0. Omg / m 2, 43. 0 mg / m 2, 3. 5mg / m 2 and 7. Om g / m 2 .
- each layer is shown below.
- the numbers represent the coating amount (g / m 2 ).
- the silver halide emulsion represents a silver equivalent coating amount.
- the total amount of coated gelatin was 4.44 g / m 2
- the total amount of coated silver was 0.33 g / m 2
- the film thickness was 6.2 ⁇ m
- the swelling film thickness was 16 .7 ⁇ m
- UV-A Color image stabilizer
- Second layer (intermediate coloring layer)
- UV-A Color image stabilizer
- C pd—4 0.024 Color-mixing inhibitor (Cpd—1 2) 0.005 Color image stabilizer (Cpd—3) 0.005 Color image stabilizer (Cpd— 5) 0.005 color image stabilizer (Cpd-6) 0.024 color image stabilizer (UV-A) 0.024 color image stabilizer (Cpd-7) 0.002 solvent (So 1 V- 1) 0.029 solvent (S o 1 V-2) 0.029 solvent (S o 1 V-5) 0.033 solvent (S o 1 v-8) 0.033 6th layer (green photosensitive emulsion layer) ) Emulsion (G-1a) 0.09 Gelatin 1.10 Magenta coupler (Ex-M) 0, 1 Color image stabilizer (C pd-2) 0.01 Color image stabilizer (C pd-8) 0.
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Description
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EP05720960A EP1726990A4 (en) | 2004-03-11 | 2005-03-10 | PHOTOSENSITIVE MATERIAL FOR SILVER HALIDE COLOR PHOTOGRAPHY |
US10/592,319 US7527922B2 (en) | 2004-03-11 | 2005-03-10 | Silver halide color photographic light-sensitive material |
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JP2005-056468 | 2005-03-01 | ||
JP2005-056707 | 2005-03-01 | ||
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JP2005-056705 | 2005-03-01 | ||
JP2005056707A JP2005292807A (ja) | 2004-03-11 | 2005-03-01 | ハロゲン化銀写真感光材料 |
JP2005056468A JP4528156B2 (ja) | 2004-03-11 | 2005-03-01 | ハロゲン化銀カラー写真感光材料 |
JP2005056712A JP2005292808A (ja) | 2004-03-11 | 2005-03-01 | ハロゲン化銀カラー写真感光材料 |
JP2005056705A JP2005309390A (ja) | 2004-03-25 | 2005-03-01 | ハロゲン化銀カラー写真感光材料 |
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Also Published As
Publication number | Publication date |
---|---|
EP1726990A1 (en) | 2006-11-29 |
US7527922B2 (en) | 2009-05-05 |
US20070202448A1 (en) | 2007-08-30 |
EP1726990A4 (en) | 2008-03-19 |
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