JP4528156B2 - Silver halide color photographic light-sensitive material - Google Patents

Description

  The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material for printing suitable for a digital exposure method, which is hard in high-illuminance exposure, and further has rapid processing suitability and has a white background. The present invention relates to a silver halide color photographic material excellent in printing.

  In recent years, digitization has progressed also in the field of color printing using silver halide color photographic light-sensitive materials. For example, digital exposure represented by laser scanning exposure is performed from a processed color negative film which has been conventionally performed. Compared to analog exposure, which uses direct printing through a color printer, it has shown a dramatic increase in the penetration rate. Such digital exposure has a feature that a high-quality print can be obtained by performing image processing, and plays an extremely important role in improving the quality of a print using a silver halide color photographic light-sensitive material. In addition, since high-quality prints can be easily obtained from image information using an electronic recording medium such as a digital camera, further spread is expected in the future.

On the other hand, technologies such as ink jet, sublimation type, and color xerography have been advanced, and they are being recognized as a color printing method. Among these competing printing systems, a printing system combining a silver halide color photographic light-sensitive material and digital exposure is characterized by high image quality, high productivity, and high robustness of the resulting image. It is desired to further extend these features and provide high-quality color prints at low cost and in a short time.
For example, if it becomes possible to provide a one-stop service for color printing, such as receiving a digital camera recording medium at a store, finishing and returning high-quality prints in a short time of several minutes, silver halide color photography The superiority of color printing using photosensitive materials is increasing. In addition, by improving the rapid processability of silver halide color photographic light-sensitive materials, it becomes possible to reduce the size of the processing equipment, and to provide a printing apparatus that is small and inexpensive but has high productivity. The one-stop service can be expected to spread more and more.
For this reason, as a silver halide color photographic light-sensitive material, from various viewpoints such as shortening of exposure time, shortening of so-called latent image time from exposure to start of development, shortening of processing time, shortening of drying time after processing. It is necessary to consider these, and proposals for each have been made.

  The silver halide emulsion used in the silver halide color photographic light-sensitive material for printing needs to satisfy various requirements as described above. In the halogen composition, a silver halide emulsion having a high silver chloride content (also referred to as a high silver chloride emulsion) is used due to the demand for rapid processability. Further, it is known that the development speed is improved by reducing the size (also referred to as particle size) of the emulsion grains contained in the silver halide emulsion, and related techniques are disclosed (for example, non-patent). Reference 1). However, if the emulsion grain size is reduced, the sensitivity also decreases, and there is a problem that the sensitivity required for digital exposure cannot be obtained. Therefore, a technique for increasing the sensitivity of high silver chloride emulsions has been demanded.

2. Description of the Related Art In recent years, color photographic materials for photographing have been widely known and used in a technique for enhancing sensitivity using a selenium (Se) compound for chemical sensitization. The use of a selenium compound is also known to easily cause an increase in fog, and techniques relating to this improvement have been studied.
However, in the case of a color negative film as a recording material, even if the fog of the silver halide emulsion is slightly increased, it can be substantially corrected during printing as a part of the mask density. Further, in a color reversal film that also serves as an appreciation material, the fog of the silver halide emulsion appears as a decrease in the maximum density (Dmax) because of the image forming method.
However, in a color photographic light-sensitive material for printing typified by color paper, an increase in fog of the silver halide emulsion appears as a coloration on a white background portion, which is a serious problem. Even a slight increase in fog will lead to fatal quality degradation. That is, a color photographic light-sensitive material for printing is required to give a good white background not only immediately after production but also after storage over time. Similarly, it is required that fog does not increase even if rapid processing is performed. For this reason, when a selenium compound is used in a high silver chloride emulsion premised on use in a silver halide color photographic light-sensitive material for printing, the requirement for fog suppression is very severe.
In color photographic light-sensitive materials for photography, silver iodobromide emulsions are exclusively used. Therefore, the fog suppression technique when using a selenium compound is limited to the technical disclosure in this emulsion region. Furthermore, it is not sufficient to meet the stringent requirements mentioned above.

Recently, a technique for achieving both digital exposure and rapid processing by using a selenium compound in a high silver chloride emulsion has been studied. Patent Document 1 discloses a technique for providing an emulsion excellent in white background with high sensitivity, high contrast and low fog even when high-intensity exposure and laser scanning exposure are performed. However, although this shows an effect of improving fog immediately after the production of a silver halide color photographic light-sensitive material, nothing is described about the effect of improving storage stability on the assumption that the light-sensitive material changes with time. In addition, although there are gradations in 10 second exposure and 10 ⁻⁴ second exposure, they are expressed as relative values with respect to the reference sample, and thus the present invention is not expected.
Patent Document 2 and Patent Document 3 describe a 10-second exposure gradation and a ^10-2 second-exposure gradation, which are technical disclosures relating to improvement of pressure characteristics and latent image storage stability, respectively. Is not described.
Patent Document 4 discloses a technique for improving fog over time with respect to improvement in storage stability, but there is description of laser scanning exposure, but the gradation is unknown. Moreover, although the description regarding a rapid process is made | formed, it is not disclosed by the Example.

JP 2003-287838 A JP-A-4-335336 JP-A-4-335338 Japanese Patent Laid-Open No. 6-308652 Abstracts of Annual Meeting of the Photographic Society of Japan 2004 (20-21 pages)

  The problem to be solved by the present invention is to provide a silver halide color photographic light-sensitive material that overcomes the above-mentioned problems and has high digital exposure suitability represented by laser scanning exposure, can be processed quickly, and is excellent in white background. In particular, the present invention is to provide a silver halide color photographic light-sensitive material that does not impair the white background even after the light-sensitive material is stored over time.

Means for solving the above-described problems are as follows.
(1) A silver halide color photographic material having at least one red-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer and blue-sensitive silver halide emulsion layer on a support, At least one of the silver 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 and a metal represented by the following general formula (D1) A silver halide color photographic light-sensitive material comprising a silver halide emulsion layer containing at least one complex and wherein the silver halide emulsion layer containing the silver halide emulsion satisfies the following formula (1).
Formula (1) 2.0 ≧ γ _H / γ _L ≧ 0.5
Here, γ represents the gradation of the characteristic curve, γ _H represents the gradation in 1 × 10 ⁻⁶ second exposure, and γ _L represents the gradation in 100 second exposure.

One general formula (D1)
[M ^D1 X ^D1 _n1 L ^D1 _(6-n1) ] ^m1
In the general formula (D1), M ^D1 represents Cr, Mo, Re, Fe, Ru, Os, Co, Rh, Pd, or Pt, and X ^D1 represents a halogen ion. L ^D1 represents an arbitrary ligand different from X ^D1 . n ₁ represents 3, 4, 5, or 6, m ₁ represents the charge of the metal complex and represents 4-, 3-, 2-, 1-, 0, or 1+. Further, a plurality of X ^D1 may be the same or different from each other, and when a plurality of L ^D1 are present, these may be the same or different from each other. However, the metal complex represented by general formula (D1) does not have a cyano (CN < ^- >) ligand, or when it has, it is only one.

(2) the silver halide emulsion containing selenium compound, further silver halide color according to you characterized in that it contains at least one metal complex represented by the following general formula (D2) (1) Photosensitive material.
General formula (D2)
[IrX ^D2 _n2 L ^D2 _(6-n2) ] ^m2
In formula ^{(D2), X D2} is a halogen ion or a pseudohalogen ion (although cyanate ion OCN ^- excluding) representative of. L ^D2 represents an arbitrary ligand different from X ^D2 . n2 represents 3, 4, or 5 and m2 represents the charge of the metal complex and represents 4-, 3-, 2-, 1-, 0, or 1+. In addition, a plurality of X ^D2 may be the same as or different from each other, and when a plurality of L ^D2 are present, these may be the same as or different from each other.
( 3 ) The silver halide color photograph as described in (1) or (2) , wherein an average equivalent sphere diameter of silver halide grains of the silver halide emulsion containing a selenium compound is 0.65 μm or less. Photosensitive material.
( 4 ) The silver halide color photograph as described in any one of (1) to ( 3 ), wherein the total coated silver amount is 0.2 g / m ² or more and 0.5 g / m ² or less. Photosensitive material.
( 5 ) The silver halide color photographic light-sensitive material as described in any one of (1) to ( 4 ), wherein the total coated gelatin amount is 3 g / m ² or more and 6 g / m ² or less.

  The silver halide color photographic light-sensitive material of the present invention can provide an excellent white background even if rapid processing is performed. Further, even when the photosensitive material is used after storage over time, an excellent white background can be provided.

Hereinafter, the present invention will be described in detail.
In the present invention, γ 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 by a conventional method, color development processing is performed after 30 minutes, density measurement is performed in a spectral region corresponding to the color hue of the layer, and a characteristic curve is obtained. Get.
In the case of ordinary color paper, during exposure, so-called blue separation exposure, green color is passed through an SP-1, SP-2, or SP-3 filter (all trade names) manufactured by Fuji Photo Film Co., Ltd. Exposure is given to the blue-sensitive emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion layer by the separation exposure or the red separation exposure, respectively. After being left for 30 minutes after exposure, color development processing is performed, and the yellow, magenta, or cyan image reflection density is measured by an optical densitometer, and the vertical axis: reflection density (D) and horizontal axis: log exposure (log E ) For each color image. In this case, the yellow image corresponds to the characteristic curve of the blue photosensitive emulsion layer, the magenta image corresponds to the green photosensitive emulsion layer, and the cyan image corresponds to the characteristic curve of the red photosensitive emulsion layer.
In the obtained characteristic curve, the minimum density (Dmin) corresponding to the unexposed portion is defined as fog. Also, the reciprocal of the exposure amount at point A giving a density of 0.5 is defined as sensitivity S. Furthermore, the point giving density 1.5 is defined as B, and the slope of the straight line connecting points A and B is defined as gradation γ. Exposure performs a 100 seconds exposure and 1 × ^{10 -6} seconds exposure, the resulting gamma and S for each, and gamma _L and _{S L} and gamma _H and and _{S H.}

In the silver halide color photographic light-sensitive material of the present invention, 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 kind. The characteristic curve of the silver halide emulsion layer containing the selenium compound and containing the silver halide emulsion must satisfy the following formula (1).
Formula (1) 2.0 ≧ γ _H / γ _L ≧ 0.5

If γ _H / γ _L is out of this range, fogging increases, sensitivity decreases, softening, or storage stability deteriorates, and the effects of the present invention cannot be obtained. γ _H / γ _L is preferably 0.75 or more, more preferably 0.95 or more, and particularly preferably 1.05 or more. Further, γ _H / γ _L is preferably 1.8 or less, and more preferably 1.6 or less.

  In the silver halide color photographic light-sensitive material of the present invention, it is necessary that at least one silver halide emulsion layer 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 present invention needs to be 90 mol% or more, and the silver chloride content is more preferably 94 mol% or more from the viewpoint of rapid processability. The silver bromide content is preferably 0.1 to 8 mol%, more preferably 0.5 to 6 mol%, since it has high sensitivity and high contrast. The silver iodide content is preferably 0.02-1 mol%, more preferably 0.05-0.50 mol%, and more preferably 0.07-0. 40 mol% is most preferred. The specific silver halide grains in the invention are preferably silver iodobromochloride grains, and more preferably silver iodobromochloride grains having the above-mentioned halogen composition.

  The silver halide grains contained in the specific silver halide emulsion in the invention preferably have a silver bromide-containing phase and / or a silver iodide-containing phase. Here, the silver bromide or silver iodide-containing phase means a portion 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 sharply. Such a silver bromide or silver iodide-containing phase may form a layer having a substantially constant width at a certain portion in the grain, or may be a maximum point having no spread. The local silver bromide content of the silver bromide-containing phase is preferably 5 mol% or more, more preferably 10 to 80 mol%, and most preferably 15 to 50 mol%. The local silver iodide content of the silver iodide-containing phase is preferably 0.3 mol% or more, more preferably 0.5 to 8 mol%, and more preferably 1 to 5 mol%. Most preferred. Further, a plurality of such silver bromide or silver iodide-containing phases may be formed in layers in each grain, and the silver bromide or silver iodide content may be different, but at least one of each. It is necessary to have a contained phase of

  It is important that the silver bromide-containing phase or the silver iodide-containing phase of the silver halide grains contained in the specific silver halide emulsion in the present invention is layered so as to surround each grain. In one preferred embodiment, the silver bromide-containing phase or the silver iodide-containing phase formed in layers 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 that are layered so as to surround the grain, the maximum or minimum point of the silver bromide or silver iodide concentration exists in the circumferential direction of the grain, and the concentration distribution You may have. For example, when a silver bromide-containing phase or silver iodide-containing phase is formed in a layer so as to surround the grain in the vicinity of the grain surface, the silver bromide or silver iodide concentration at the grain corner or edge is different from the main surface. There is a case. In addition to the silver bromide-containing phase and the silver iodide-containing phase that are layered so as to surround the grain, the silver bromide-containing phase that is completely isolated in a specific part of the surface of the grain and does not surround the grain Alternatively, there may be a silver iodide containing phase.

  When the silver halide grains contained in the specific silver halide emulsion in the present invention contain a silver bromide-containing phase, the silver bromide-containing phase is layered so that the silver bromide concentration maximum is present inside the grains. Preferably it is formed. Further, when the silver halide emulsion of the present invention contains a silver iodide-containing phase, the silver iodide-containing phase is preferably formed in a layered manner so as to have a silver iodide concentration maximum on the surface of the grain. Such a silver bromide-containing phase or silver iodide-containing phase is composed of a silver amount of 3% to 30% of the grain volume in order to increase the local concentration with a smaller silver bromide or silver iodide content. It is preferable that the silver content is 3% or more and 15% or less.

  The silver halide grains contained in the specific silver halide emulsion in the present invention preferably contain both a silver bromide-containing phase and a silver iodide-containing phase. In this case, the silver bromide-containing phase and the silver iodide-containing phase may be at the same place or different places in the grain, but it is preferable that the silver bromide-containing phase and the silver iodide-containing phase are in different places from the viewpoint of facilitating control of grain formation. Further, the silver bromide-containing phase may contain silver iodide, and conversely, the silver iodide-containing phase may contain silver bromide. In general, iodide added during the formation of high silver chloride grains tends to ooze out on the grain surface than bromide, so the silver iodide-containing phase tends to be formed near the grain surface. Therefore, when the silver bromide-containing phase and the silver iodide-containing phase are at different locations 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 necessary for exhibiting 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 grain. There is a risk that the amount of silver chloride may be reduced more than necessary, and the rapid processability may be impaired. Therefore, in order to concentrate these functions for controlling the photographic action near the surface in the grain, the silver bromide-containing phase and the silver iodide-containing phase are preferably adjacent to each other. From these points, the silver bromide-containing phase is formed at any of the positions of 50% to 100% of the grain volume as measured from the inside, and the silver iodide-containing phase is any of the positions at 85% to 100% of the grain volume. It is preferable to form it. Further, the silver bromide-containing phase is formed at any position from 70% to 100% of the grain volume, and the silver iodide-containing phase is further formed at any position from 90% to 100% of the grain volume. preferable.

  In order to incorporate silver bromide or silver iodide into the specific silver halide emulsion in the present invention, bromide or iodide ion can be introduced by adding a bromide salt or iodide salt solution alone, or a silver salt solution. In addition to the addition of a high chloride salt solution, a bromide salt or iodide salt solution may be added. In the latter case, bromide salt or iodide salt solution and high chloride salt solution may be added separately or as a mixed solution of bromide salt or iodide salt and high chloride salt. The bromide salt or iodide salt is added in the form of a soluble salt such as an alkali or alkaline earth bromide salt or iodide salt. Alternatively, it can be introduced by cleaving bromide ions or iodide ions from organic molecules described in US Pat. No. 5,389,508. As another bromide or iodide ion source, fine silver bromide grains or fine silver iodide grains can also be used.

The addition of the bromide salt or iodide salt solution may be concentrated during a period of grain formation or may be performed over a certain period. The position of introduction of iodide ions into the high chloride emulsion is limited in obtaining a high sensitivity and low fog emulsion. Iodide ions are introduced more into the emulsion grains and the increase in sensitivity is smaller. Therefore, the iodide salt solution is preferably added outside 50% of the grain volume, more preferably outside 70%, and most preferably outside 85%. Further, the addition of the iodide salt solution is preferably completed within 98% of the grain volume, and most preferably within 96%. The addition of the iodide salt solution is completed slightly inside from the grain surface, whereby an emulsion with higher sensitivity and lower fog can be obtained.
On the other hand, the addition of the bromide salt solution is preferably outside 50% of the particle volume, more preferably outside 70%.

  Distribution of bromide or iodide ion concentration in the depth direction in the particle is measured by etching / TOF-SIMS (Time of Flight-Secondary Ion Mass Spectrometry) method, for example, using TRIFT II type TOF-SIMS manufactured by Phi Evans. it can. The TOF-SIMS method is specifically described in “Surface Analysis Technology Selection Secondary Ion Mass Spectrometry” Maruzen Co., Ltd. (1999), edited by the Surface Science Society of Japan. When the emulsion grains are analyzed by the etching / TOF-SIMS method, it is possible to analyze that iodide ions ooze out toward the grain surface even when the addition of the iodide salt solution is finished inside the grains. The emulsion of the present invention is analyzed by etching / TOF-SIMS method, and it is preferable that iodide ions have a maximum concentration on the grain surface, and the iodide ion concentration is attenuated toward the inside. It is preferable to have a concentration maximum inside. The local concentration of silver bromide can also be measured by X-ray diffraction if the silver bromide content is somewhat high.

  The selenium compound used in the present invention will be described. As the selenium compound, the following general formula (SE1), (SE2) or (SE3) can be preferably used.

In General Formula (SE1), 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, or a carbamoyl group, Q represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, OM ³ or NM ⁴ M ⁵ , and M ^{3 to} M ⁵ are a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a hetero group Represents a cyclic group. M ¹ , M ² and Q may be bonded to form a ring structure.

In the general formula (SE2), 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 . J ¹ through J ³ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group.

In General Formula (SE3), E ¹ and E ^{2 each} represents 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.

Next, the selenium compound represented by the general formula (SE1) will be described.
In general formula (SE1), the alkyl group represented by M ^{1 to} M ⁵ and Q represents a linear, branched, or cyclic substituted or unsubstituted alkyl group. Preferably, it is a substituted or unsubstituted linear or branched alkyl group having 1 to 30 carbon atoms (for example, methyl group, ethyl group, isopropyl group, n-propyl group, n-butyl group, 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, hydroxy Ethyl group, hydroxypropyl group, 2,3-dihydroxypropyl group, carboxymethyl group, carboxyethyl group, sodium sulfoethyl group, diethylaminoethyl group, diethylaminopropyl group, butoxypropyl group, ethoxyethoxyethyl group, n-hexyloxypropyl Group), a substituted or unsubstituted cyclic alkyl group having 3 to 18 carbon atoms ( Example, if a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, cyclooctyl group, adamantyl group, a cyclododecyl group). In addition, a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms (that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms, for example, bicyclo [1,2,2 Heptan-2-yl, bicyclo [2,2,2] octane-3-yl), and tricyclo structures having many ring structures. The alkenyl group represented by M ^{1 to} M ⁵ and Q represents an alkenyl group having 2 to 16 carbon atoms (for example, an allyl group, a 2-butenyl group, a 3-pentenyl group, etc.), and M ^{1 to} M ⁵ and The alkynyl group represented by Q represents an alkynyl group having 2 to 10 carbon atoms (eg, propargyl group, 3-pentynyl group, etc.).

Examples of the aryl group represented by M ^{1 to} M ⁵ and Q include a substituted or unsubstituted phenyl group and naphthyl group having 6 to 20 carbon atoms (for example, an unsubstituted phenyl group, an unsubstituted naphthyl group, 3,5-dimethylphenyl). , 4-butoxyphenyl group, 4-dimethylaminophenyl group, etc.), and examples of the heterocyclic group include pyridyl group, furyl group, imidazolyl group, piperidyl group, morpholyl group and the like.

In the general formula (SE1), examples of the acyl group represented by M ¹ and M ² include an acetyl group, a formyl group, a benzoyl group, a pivaloyl group, a caproyl group, and an n-nonanoyl group. For example, an unsubstituted amino group, a methylamino group, a hydroxyethylamino group, an n-octylamino group, a dibenzylamino group, a dimethylamino group, a diethylamino group and the like can be mentioned. Examples of the alkoxy group include a methoxy group, an ethoxy group, and n -Butyloxy group, cyclohexyloxy group, n-octyloxy group, n-decyloxy group, and the like. Examples of the carbamoyl group include unsubstituted carbamoyl group, N, N-diethylcarbamoyl group, and N-phenylcarbamoyl group. It is done.

If the general formula ^{M 1} and ^M 2 in (SE1), Q and ^{M 1} or Q and ^{M 2,} may be bonded together to form a ring structure, further Q represents ^NM 4 ^{M 5,} and ^{M 4} M ⁵ may be bonded to each other to form a ring structure.

M ^{1 to} M ⁵ and Q in the general formula (SE1) may have a substituent as much as possible. Examples of the substituent include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom). Atoms), alkyl groups (straight chain, branched, cyclic alkyl groups, including bicycloalkyl groups and active methine groups), alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups (regardless of where they are substituted), acyl Group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, N-hydroxycarbamoyl group, N-acylcarbamoyl group, N-sulfonylcarbamoyl group, N-carbamoylcarbamoyl group, thiocarbamoyl group, N- Sulfamoylcarbamoyl group, carbazoyl group, carboxy group or salt thereof, oxali Group, oxamoyl group, cyano group, carbonimidoyl group (Carbonimidoyl group), formyl group, hydroxy group, alkoxy group (including groups containing ethyleneoxy group or propyleneoxy group unit), aryloxy group, heterocyclic oxy group , Acyloxy group, (alkoxy or aryloxy) carbonyloxy group, carbamoyloxy group, sulfonyloxy group, amino group, (alkyl, aryl, or heterocyclic) amino group, acylamino group, sulfonamide group, ureido group, thioureido group, N-hydroxyureido group, imide group, (alkoxy or aryloxy) carbonylamino group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, ammonio group, oxamoylamino group, N- (al Or aryl) sulfonylureido group, N-acylureido group, N-acylsulfamoylamino group, hydroxyamino group, nitro group, heterocyclic group containing a quaternized nitrogen atom (eg pyridinio group, imidazolio group, quinolinio) Group, isoquinolinio group), isocyano group, imino group, mercapto group, (alkyl, aryl, or heterocyclic) thio group, (alkyl, aryl, or heterocyclic) dithio group, (alkyl or aryl) sulfonyl group, (alkyl or Aryl) sulfinyl group, sulfo group or salt thereof, sulfamoyl group, N-acylsulfamoyl group, N-sulfonylsulfamoyl group or salt thereof, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group And a silyl group. Here, the active methine group means a methine group substituted with two electron-withdrawing groups, and the electron-withdrawing group here means an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, An alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, a trifluoromethyl group, a cyano group, a nitro group, and a carbonimidoyl group (Carbonimidoyl group) are meant. Here, the two electron withdrawing groups may be bonded to each other to form a cyclic structure. The salt means a cation such as alkali metal, alkaline earth metal or heavy metal, or an organic cation such as ammonium ion or phosphonium ion. These substituents may be further substituted with these substituents.

As preferable compounds represented by the general formula (SE1), 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, and a substituted group having 3 to 6 carbon atoms. Or an unsubstituted cyclic alkyl group, an alkenyl group having 2 to 6 carbon atoms, a substituted or unsubstituted phenyl group having 6 to 10 carbon atoms, a heterocyclic group, and an acyl group, and Q is 1 to 6 carbon atoms. Substituted or unsubstituted linear or branched alkyl group, substituted or unsubstituted cyclic alkyl group having 3 to 6 carbon atoms, alkenyl group having 2 to 6 carbon atoms, substituted or unsubstituted phenyl having 6 to 10 carbon atoms Or NM ⁴ M ⁵ , where M ⁴ and M ⁵ are a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted cyclic group having 3 to 6 carbon atoms Alkyl group, charcoal This is a case where a alkenyl group having 2 to 6 primes, a substituted or unsubstituted phenyl group having 6 to 10 carbon atoms, or a heterocyclic group is represented.

As a more preferable compound represented by the general formula (SE1), 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, and a ² to 6 carbon atoms. An alkenyl group, a substituted or unsubstituted phenyl group having 6 to 10 carbon atoms, and Q is a substituted or unsubstituted linear or branched alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted group having 6 to 10 carbon atoms A phenyl group, or NM ⁴ M ⁵ , wherein M ⁴ and M ⁵ are a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, carbon This is a case of a substituted or unsubstituted phenyl group of formula 6-10.

As a more preferable compound represented by the general formula (SE1), Q is NM ⁴ M ⁵ , M ⁴ and M ⁵ are hydrogen atoms, substituted or unsubstituted linear or branched alkyl having 1 to 6 carbon atoms Group, an alkenyl group having 2 to 6 carbon atoms, and a substituted or unsubstituted phenyl group having 6 to 10 carbon atoms. Specific examples of the compound represented by the general formula (SE1) are shown below, but the present invention is not limited thereto.

  The compound represented by the general formula (SE1) of the present invention can be obtained by a known method such as Chemical Reviews (Chem. Rev.) 55, 181-228 (1955), Journal of Organic Chemistry (J. Org). Chem.) 24, 470-473 (1959), Journal of Heterocyclic Chemistry (J. Heterocycl. Chem.) 4, 605-609 (1967), "Drugs" 82, 36-45 (1962). ), JP-B-39-262203, JP-A-63-229449, and OLS-2,043,944.

Next, the general formula (SE2) will be described in detail.
In General Formula (SE2), the alkyl group, alkenyl group, alkynyl group, aryl group, and heterocyclic group represented by X ^{1 to} X ³ and J ^{1 to} J ³ are each represented by M ^{1 to} M ⁵ in Formula (SE1). And Q have the same meaning as the alkyl group, alkenyl group, alkynyl group, aryl group and heterocyclic group. X ^{1 to} X ³ and J ^{1 to} J ³ may have a substituent as much as possible, and examples of the substituent may include M ^{1 to} M ⁵ and Q in General Formula (SE1). Synonymous with good substituents.

As the compound represented by the general formula (SE2), preferably X ^{1 to} X ³ are each a substituted or unsubstituted linear or branched alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted group having 6 to 10 carbon atoms. a case where a phenyl group or a heterocyclic group, and more preferably is the case where X ¹ to X ³ each represent a substituted or unsubstituted phenyl group having 6 to 10 carbon atoms.
Although the specific example of a compound represented by general formula (SE2) below is given, this invention is not limited to these.

  The compound represented by the general formula (SE2) of the present invention can be obtained by a known method, for example, Organic Phosphorus Compounds (Vol. 4, pages 1 to 73), Journal Chemical Society B (J. Chem.). Soc. (B), 1416, 1968), Journal Organic Chemistry (J. Org. Chem. 32, 1717, 1967), Journal Organic Chemistry (J. Org. Chem. 32, 2999, 1967), tetrahedron (20, 449, 1964), Journal American Chemical Society (J. Am. Chem. Soc., 91, 2915, 1969). Etc. with reference to It can be formed.

Next, the compound represented by general formula (SE3) is demonstrated.
The alkyl group, alkenyl group, alkynyl group, aryl group and heterocyclic group represented by E ¹ and E ² in the general formula (SE3) are each an alkyl group represented by M ^{1 to} M ⁵ and Q in the general formula (SE1). , Alkenyl group, alkynyl group, aryl group and heterocyclic group. Examples of the acyl group represented by E ¹ and E ² include an acetyl group, a formyl group, a benzoyl group, a pivaloyl group, a caproyl group, and an n-nonanoyl group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group. Group, n-butyloxycarbonyl group, cyclohexyloxycarbonyl group, n-octyloxycarbonyl group, n-decyloxycarbonyl group and the like. Examples of the aryloxycarbonyl group include phenoxycarbonyl group and naphthoxycarbonyl group. Examples of the carbamoyl group include an unsubstituted carbamoyl group, an N, N-diethylcarbamoyl group, and an N-phenylcarbamoyl group. E ¹ and E ² may have a substituent as much as possible, and examples of the substituent are the same as the substituents that M ^{1 to} M ⁵ and Q may have in the general formula (SE1). is there.

In the present invention, preferred compounds represented by the general formula (SE3) are selected from the groups in which E ¹ and E ² are represented by the following general formulas (T1) to (T4). In this case, E ¹ and E ² may be the same or different.

In General Formula (T1), Y represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, OR ¹ or NR ² R ³ , and R ^{1 to} R ³ represent an alkyl group, an alkenyl group, an alkynyl group, Represents an aryl group or a heterocyclic group. In the general formula (T2), L represents a divalent linking group, and EWG represents an electron withdrawing group. In General Formula (T3), A ¹ represents an oxygen atom, a sulfur atom, or NR ⁷ , and R ^{4 to} R ⁷ represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group. In General Formula (T4), A ² represents an oxygen atom, a sulfur atom, or NR ¹¹ , R ⁸ 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 ⁹ to R ¹¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. Z represents a substituent, and n represents an integer of 0 to 4. When n is 2 or more, Z may be the same or different.

In General Formula (T1), Y represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, OR ¹ or NR ² R ³ , and R ^{1 to} R ³ represent an alkyl group, an alkenyl group, an alkynyl group, an aryl A group or a heterocyclic group is represented, and the alkyl group here is synonymous with the alkyl group represented by M ^{1 to} M ⁵ and Q in General Formula (SE1), and the preferred range is also the same. Similarly, the alkenyl group, alkynyl group, aryl group and heterocyclic group are the same as the alkenyl group, alkynyl group, aryl group and heterocyclic group represented by M ^{1 to} M ⁵ and Q, respectively, and the preferred ranges are also the same. .

  In the general formula (T1), in the present invention, Y 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.

  In the general formula (T2), the divalent linking group represented by L represents an alkylene group having 2 to 20 carbon atoms, an alkenylene group or an alkynylene group, and particularly a linear, branched or cyclic group having 2 to 10 carbon atoms. An alkylene group (for example, ethylene, propylene, cyclopentylene, cyclohexylene), an alkenylene group (for example, vinylene), and an alkynylene group (for example, propynylene) are represented. Preferred examples of L include those represented by general formula (L1) and general formula (L2).

In General Formula (L1) and General Formula (L2), G ¹ , G ² , G ³ , and G ⁴ are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 1 to 1 carbon atoms. Represents 10 heterocyclic groups, and G ¹ , G ² and G ³ may be linked to form a ring. G ¹ , G ² , G ³ and G ⁴ are preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group.

In the general formula (T2), EWG represents an electron withdrawing group. The electron withdrawing group here is a substituent having a positive Hammett's substituent constant σ _p value, preferably σ _p value is 0.2 or more, and the upper limit is 1.0 or less. Represents a substituent. Specific examples of the electron withdrawing group having a σ _p 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 aryloxycarbonyl group, a cyano group, a nitro group, and a dialkyl. Phosphono group, diarylphosphono group, dialkylphosphinyl group, diarylphosphinyl group, phosphoryl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, A thiocyanate group, a thiocarbonyl group, an imino group, an imino group substituted with an N atom, a carboxy group (or a salt thereof), an alkyl group substituted with at least two or more halogen atoms, and substituted with at least two or more halogen atoms An alkoxy group, at least Two or more aryloxy groups substituted with a halogen atom, an acylamino group, at least two or more alkyl amino group substituted with a halogen atom, at least two or more alkylthio groups substituted with a halogen atom, sigma _p value Examples include aryl groups, heterocyclic groups, halogen atoms, azo groups, and selenocyanate groups substituted with 0.2 or more other electron-withdrawing groups. In the present invention, EWG is preferably an acyl group, formyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, dialkylphosphono group, diarylphosphono group, dialkylphosphinyl group, diarylphosphine group. Finyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, thiocarbonyl group, imino group, imino group substituted with N atom, phosphoryl group, carboxy group (or salt thereof), at least An alkyl group substituted with two or more halogen atoms, an aryl group substituted with another electron-withdrawing group having a σ _p value of 0.2 or more, a heterocyclic group, or a halogen atom, more preferably an acyl group Group, formyl group, carbamoyl group, alkoxy group Bonyl group, aryloxycarbonyl group, cyano group, nitro group, alkylsulfonyl group, arylsulfonyl group, carboxy group, alkyl group substituted with at least two halogen atoms, more preferably acyl group, formyl group, A cyano group, a nitro group, an alkylsulfonyl group, an arylsulfonyl group, or an alkyl group substituted with at least two halogen atoms.

In General Formula (T3), R ^{4 to} R ^{7 each} represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, and the alkyl group referred to here is M ¹ to M ¹ in General Formula (SE1). M ⁵ and Q have the same meaning as the alkyl group represented by, and preferred ranges are also the same. Similarly, the alkenyl group, alkynyl group, aryl group and heterocyclic group are the same as the alkenyl group, alkynyl group, aryl group and heterocyclic group represented by M ^{1 to} M ⁵ and Q, respectively, and the preferred ranges are also the same. .

In the present invention, R ⁴ is preferably an alkyl group. R ⁵ and R ⁶ 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 ⁷ 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.

In the general formula (T3), A ¹ represents an oxygen atom, a sulfur atom or NR ^{7. In} the present invention, A ¹ is preferably an oxygen atom or a sulfur atom, and most preferably an oxygen atom.

Next, general formula (T4) will be described.
The alkyl group represented by R ^{8 to} R ¹¹ in General Formula (T4) has the same meaning as the alkyl group represented by R ^{1 to} R ⁵ and Q in General Formula (SE1), and the preferred range is also the same. Similarly, the alkenyl group, alkynyl group, aryl group and heterocyclic group are the same as the alkenyl group, alkynyl group, aryl group and heterocyclic group represented by R ^{1 to} R ⁵ and Q, respectively, and the preferred ranges are also the same. . Examples of the acyl group represented by R ⁸ include an acetyl group, a formyl group, a benzoyl group, a pivaloyl group, a caproyl group, and an n-nonanoyl group.

In General Formula (T4), Z represents a substituent, and examples thereof include the same substituents that M ^{1 to} M ⁵ and Q may have in General Formula (SE1).

  In the present invention, Z is preferably a halogen atom, alkyl group, aryl group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-acylcarbamoyl group, N-sulfonylcarbamoyl group, N- Carbamoylcarbamoyl group, thiocarbamoyl group, N-sulfamoylcarbamoyl group, carbazoyl group, carboxy group (including its salt), cyano group, formyl group, hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, Acyloxy group, nitro group, amino group, (alkyl, aryl, or heterocyclic) amino group, acylamino group, sulfonamide group, ureido group, thioureido group, alkylthio group, arylthio group, heterocyclic thio group, (alkyl or aryl) Sulfo Group, (alkyl or aryl) sulfinyl group, sulfo group (including salts thereof), sulfamoyl group, etc., more preferably halogen atom, alkyl group, aryl group, heterocyclic group, carboxy group (and salts thereof). Including), hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group, amino group, (alkyl, aryl, or heterocyclic) amino group, acylamino group, ureido group, thioureido group, alkylthio group, arylthio group , A heterocyclic thio group, a sulfo group (including a salt thereof) and the like, more preferably an alkyl group, an aryl group, a carboxy group (including a salt thereof), a hydroxy group, an alkoxy group, an aryloxy group, (alkyl , Aryl, or heterocyclic) amino group, ureido group, alkylthio , An arylthio group, (including and salts thereof) a sulfo group and the like.

  In general formula (T4), n represents the integer of 0-4. In the present invention, n preferably represents 0 to 2, more preferably 0 or 1.

In the general formula (T4), A ² represents an oxygen atom, a sulfur atom or NR ¹¹ , but in the present invention, it preferably represents an oxygen atom or a sulfur atom.

In the present invention, among the compounds represented by general formula (SE3), preferred compounds are those in which E ¹ is general formula (T1), E ² is general formula (T1), E ¹ is general formula (T1), and E ² is formula (T2), ^{E 2} is the formula by ^{E 1} general formula ^{(T1) (T3), E} 2 is the formula by ^{E 1} general formula ^{(T1) (T4), E} 1 is the general formula (T2) E ² is general formula (T3), E ¹ is general formula (T2), E ² is general formula (T4), E ¹ is general formula (T3), E ² is general formula (T3), and E ¹ is general In the formula (T3), E ² is the general formula (T4), E ¹ is the general formula (T4), and E ² is the general formula (T4). More preferably, E ¹ is the general formula (T1) and E ² There general formula (T1), ^{E 2} is the formula by ^{E 1} general formula ^{(T1) (T2), E} 2 is the formula by ^{E 1} general formula (T1) (T3), ^{E 1} is the general formula (T1 ) E ² is general formula (T4), E ¹ is general formula (T2), E ² is general formula (T3), E ¹ is general formula (T3), E ² is general formula (T4), and E ¹ is general formula ( ^{E 2} in T4) is a case of the general formula (T4), more preferably ^{E 2} is the general formula ^{E 1} is the general formula (T1) (T2), ^{E 1} is ^{E 2} in the general formula (T1) is generally in formula (T3), ^{E 2} is the formula by ^{E 1} general formula ^{(T1) (T4), E} 2 is the formula by ^{E 1} general formula (T2) (T3), ^{E 1} is the general formula (T3) E ² is the case of general formula (T4), most preferably E ¹ is general formula (T1), E ² is general formula (T2), E ¹ is general formula (T1) and E ² is general formula (T3 ), E ¹ is the general formula (T2), and E ² is the general formula (T3).

  Specific examples of the selenium compound represented by the general formula (SE3) are shown below, but the compound of the present invention is not limited thereto. In addition, the three-dimensional structure of a compound in which a plurality of stereoisomers can exist is not limited.

  The compound represented by the general formula (SE3) is already known in the following literature, edited by S. Patai, Z. Rappoport, The Chemistry of Organic Selenium and Tellurium Compounds, No. 1 (1986), 2 (1987), D. Liotta, Organo-selenium Chemistry, (1987) and the like.

  In the present invention, as other selenium compounds, JP-B Nos. 43-13489, 44-15748, JP-A-4-25832, JP-A-4-109240, JP-A-4-271341, JP-A-5-40324, 5-11385, 6-51415, 6-175258, 6-180478, 6-208186, 6-208184, 6-317867, 7-92599, 7- No. 98483, No. 7-140579, No. 7-301879, No. 7-301880, No. 8-114882, No. 9-138475, No. 9-197603, No. 10-10666, etc. Selenium compounds, specifically colloidal metal selenium, selenoketones (eg, selenobenzophenone), isoselenocyanates, Or the like can be used Renokarubon acids. Furthermore, non-labile selenium compounds described in JP-B Nos. 46-4553 and 52-34492, such as selenious acid, selenocyanic acids (for example, potassium selenocyanate), selenazoles, selenides, and the like may be used. it can. Of these, selenocyanic acids are particularly preferred.

  As mentioned above, although the structure which can be used as a selenium compound has been shown, this invention is not limited to these. The selenium compound used in the present invention preferably has a binding energy value of 3d orbital electrons of selenium atoms of 54.0 eV or more and 65.0 eV or less as measured with an X-ray photoelectron spectrometer in terms of high contrast and low fog.

The amount of selenium sensitizer used in the present invention varies depending on the selenium compound used, silver halide grains, chemical ripening conditions, etc., but is generally 1 × 10 ⁻⁸ to 1 × 10 ⁻⁴ mol per mol of silver halide. Preferably, about 1 × 10 ⁻⁷ to 1 × 10 ⁻⁵ mol is used. In addition, the chemical sensitization conditions in the present invention are not particularly limited, but pCl is preferably 0 to 7, more preferably 0 to 5, and still more preferably 1 to 3. As temperature, 40-80 degreeC is preferable and 50-70 degreeC is more preferable.

  The selenium compound used in the present invention can be added at any stage from immediately after grain formation to immediately before the end of chemical sensitization. The preferred addition time is between the chemical sensitization step after desalting.

In the present invention, sulfur sensitization, tellurium sensitization, other gold sensitization and noble metal sensitization can be used in combination. As the gold sensitizer, colloidal gold sulfide or a gold sensitizer having a complex stability constant log β ₂ of gold of 21 or more and 35 or less can be preferably used in combination. In addition to these, commonly used gold compounds (for example, chloroaurate, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiocyanate, pyridyltrichlorogold, etc.) Can be used together.

  Reduction sensitizers can also be used in combination. Specific examples include stannous chloride, aminoiminomethanesulfinic acid, hydrazine derivatives, borane compounds, silane compounds, and polyamine compounds.

In the present invention, chemical sensitization with a selenium compound is preferably performed in the presence of a silver halide solvent. Specifically, thiocyanate (for example, potassium thiocyanate, etc.), a thioether compound (for example, U.S. Pat. Nos. 3,021,215 and 3,271,157, JP-B-58-30571, JP-A-60-136736) Compounds, particularly 3,6-dithia-1,8 octanediol, etc.), tetrasubstituted thiourea compounds (for example, compounds described in Japanese Patent Publication No. 59-11892, US Pat. No. 4,221,863, etc.), particularly tetramethylthiourea Further, thione compounds described in JP-B-60-11341, mercapto compounds described in JP-B-63-29727, mesoionic compounds described in JP-A-60-163042, and US Pat. No. 4,78,2013. Selenoether compounds, telluroether compounds described in Japanese Patent Application No. 63-173474, sulfites And the like. Among these, thiocyanate, thioether compound, tetrasubstituted thiourea compound and thione compound can be preferably used. The amount used may be about 1 × 10 ⁻⁵ to 1 × 10 ⁻² mole per mole of silver halide.

Particular silver halide emulsion used in the present invention, it contains a compound represented by the following general formula (D1).
General formula (D1)
[M ^D1 X ^D1 _n1 L ^D1 _(6-n1) ] ^m1
In the general formula (D1), M ^D1 represents Cr, Mo, Re, Fe, Ru, Os, Co, Rh, Pd, or Pt, and X ^D1 represents a halogen ion. L ^D1 represents an arbitrary ligand different from X ^D1 . n ₁ represents 3, 4, 5, or 6, m ₁ represents the charge of the metal complex and represents 4-, 3-, 2-, 1-, 0, or 1+. Further, a plurality of X ^D1 may be the same or different from each other, and when a plurality of L ^D1 are present, these may be the same or different from each other. However, the metal complex represented by general formula (D1) does not have a cyano (CN < ^- >) ligand, or when it has, it is only one.

Among the metal complexes represented by the general formula (D1), metal complexes represented by the following general formula (D1A) are preferable.
General formula (D1A)
[M ^D1A X ^D1A _n3 L ^D1A _(6-n3) ] ^m3
In the general formula (D1A), M ^D1A represents Re, Ru, Os, Rh, and X ^D1A represents a halogen ion. L ^D1A represents NO or NS when M ^D1A is Re, Ru or Os, and represents H ₂ O, OH or O when M ^D1A is Rh. n ₃ represents ₃ , 4, 5 or 6, and m ₃ represents the charge of the metal complex and represents 4-, 3-, 2-, 1-, 0 or 1+. X ^D1A has the same meaning as X ^{D1 in} formula (D1), and the preferred range is also the same.
Here, three to six X ^D1A may be the same or different from each other. When L ^D1A there are a plurality, a plurality of L ^D1A may be the same or different from each other.

These metal complexes include, for example, inorganic compounds and complex dictionaries (Katsuaki Nakahara / Author, Kodansha Scientific / editor, Kodansha Co., Ltd./published on June 10, 1997, first edition), Fourth Edition Experimental Chemistry Course. (Maruzen Co., Ltd.) Volume 17, Gmelin handbook of inorganic and organometallic chemistry, Comprehensive Coordination Chemistry Volume 4, Middle Transition Elements Pergamon Publishing (Comprehensive Coordination Chemistry, Volume 4, Middle Transition Elements, Pergamon Press), Chelate Chemistry (1) to (6) Edited by Keihei Ueno Nanedo, etc. In addition to these, U.S. Pat. No. 5,360,712, JP-A No. 2001-302558, JP-A No. 2002-155055, JP-A No. 2002-274855, JP-A No. 2002-357879, JP-A No. 2003-95661, etc. It can be synthesized with reference to the publication.
Preferable specific examples of the metal complex represented by the general formula (D1) are listed below, but the present invention is not limited thereto.
[ReCl ₆ ] ²⁻
[ReCl ₅ (NO)] ²⁻
[RuCl ₆ ] ²⁻
[RuCl ₆ ] ³⁻
[RuCl ₅ (NO)] ²⁻
[RuCl ₅ (NS)] ²⁻
[RuBr ₅ (NS)] ²⁻
[OsCl ₆ ] ³⁻
[OsCl ₆ ] ²⁻
[OsCl ₅ (NO)] ²⁻
[OsBr ₅ (NS)] ²⁻
[RhCl ₆ ] ³⁻
[RhCl ₅ (H ₂ O)] ²⁻
[RhCl ₄ (H ₂ O) ₂ ] ⁻
[RhBr ₆ ] ³⁻
[RhBr ₅ (H ₂ O)] ²⁻
[RhBr ₄ (H ₂ O) ₂ ] ⁻
[PdCl ₆ ] ²⁻
[PtCl ₆ ] ²⁻
Among these, [RuCl ₅ (NO)] ²⁻ , [OsCl ₅ (NO)] ²⁻ , [RhBr ₆ ] ³⁻ and [RhCl ₆ ] ³⁻ are preferable, and [RuCl ₅ (NO)] ²⁻ is preferable. Particularly preferred.

The specific silver halide emulsion used in the present invention preferably contains a compound represented by the following general formula (D2).
General formula (D2)
[IrX ^D2 _n2 L ^D2 _(6-n2) ] ^m2
In formula ^{(D2), X D2} is a halogen ion or a pseudohalogen ion (although cyanate ion OCN ^- excluding) representative of. L ^D2 represents an arbitrary ligand different from X ^D2 . n ₂ represents 3, 4, or 5, and m ₂ represents the charge of the metal complex and represents 4-, 3-, 2-, 1-, 0, or 1+. In addition, a plurality of X ^D2 may be the same as or different from each other, and when a plurality of L ^D2 are present, these may be the same as or different from each other.

Here, 3 to 5 X ^D2 may be the same as or different from each other, and when a plurality of L ^D2 exist, the plurality of L ^I may be the same as or different from each other. In the above, the pseudohalogen (halogenoid) ion is an ion having properties similar to a halogen ion. For example, cyanide ion (CN ⁻ ), thiocyanate ion (SCN ⁻ ), selenocyanate ion (SeCN ^−). ), Tellurocyanate ion (TeCN ⁻ ), azidodithiocarbonate ion (SCSN ₃ ⁻ ), thunderate ion (ONC ⁻ ), azide ion (N ₃ ⁻ ) and the like. However, cyanate ion (OCN ⁻ ) is excluded.
X ^D2 is preferably fluoride ion, chloride ion, bromide ion, iodide ion, cyanide ion, isocyanate ion, thiocyanate ion, nitrate ion, nitrite ion, or azide ion, among which chloride Particularly preferred are ions and bromide ions. L ^D2 is not particularly limited and may be an inorganic compound or an organic compound, and may be charged or uncharged, but may be an uncharged inorganic compound or organic compound. preferable.

Among the metal complexes of the general formula (D2), a metal complex represented by the following general formula (D2A) is preferable.
General formula (D2A)
[IrX ^D2A _n4 L ^D2A _(6-n4) ] ^m4
In the general formula (D2A), X ^D2A represents a pseudohalogen ion other than a halogen ion or a cyanate ion, and L ^D2A represents an arbitrary inorganic ligand different from X ^D2A . n ₄ represents 3, 4 or 5, and m ₄ represents the charge of the metal complex and represents 4-, 3-, 2-, 1-, 0, or 1+. X ^D2A has the same meaning as X ^{D2 in} formula (I), and the preferred range is also the same. L ^D2A is preferably water (aqua; H ₂ O), OCN, ammonia (NH ₃ ), phosphine (PH ₃ ), or carbonyl (CO), and particularly preferably water (H ₂ O).
Here, three to five X ^D2A may be the same or different from each other. When L ^D2A there are a plurality, a plurality of L ^D2A may be the same or different from each other.

Among the metal complexes represented by the general formula (D2), a metal complex represented by the following general formula (D2B) is more preferable.
General formula (D2B)
[IrX ^D2B _n5 L ^D2B _(6-n5) ] ^m5
In the general formula (D2B), X ^D2B represents a pseudohalogen ion other than a halogen ion or a cyanate ion, and L ^D2B has a base structure of a chain or cyclic hydrocarbon, or a part of the base structure. Represents a ligand in which a carbon or hydrogen atom is replaced by another atom or atomic group. n ₅ represents 3, 4 or 5, and m ₅ represents the charge of the metal complex and represents 4-, 3-, 2-, 1-, 0 or 1+. X ^D2B has the same meaning as X ^{D2 in} formula (D2), and the preferred range is also the same. L ^D2B represents a ligand in which a chain or cyclic hydrocarbon is a base structure, or a carbon or hydrogen atom in a part of the base structure is replaced with another atom or atomic group. Ions are not included. 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, it is further a compound containing at least one nitrogen atom and at least one sulfur atom in a five-membered ring skeleton. preferable.
Here, three to five X ^D2B may be the same or different from each other. When L ^D2B there are a plurality, a plurality of L ^D2B may be the same or different from each other.

Among the metal complexes represented by the general formula (D2B), a metal complex represented by the following general formula (D2C) is more preferable.
General formula (D2C)
[IrX ^D2C _n6 L ^D2C _(6-n6) ] ^m6
In the general formula (D2C), X ^D2C represents a pseudohalogen ion 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 one sulfur atom in the ring skeleton. Represents a ligand containing In addition, you may have arbitrary substituents on the carbon atom in this ring skeleton. n ₆ represents 3, 4 or 5, and m ₆ represents the charge of the metal complex and represents 4-, 3-, 2-, 1-, 0 or 1+.
X ^D2C has the same meaning as X ^{D2 in} formula (I), and the preferred range is also the same. The substituent on the carbon atom in the ring skeleton in L ^D2C is preferably a substituent having a smaller volume than the n-propyl group. As substituents, methyl group, ethyl group, methoxy group, ethoxy group, cyano group, isocyano group, cyanato 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, hydroxyamino group, carboxyl group, carbamoyl group, fluoro group, chloro group, bromo group and iodo group are preferred.
Here, three to five X ^D2C may be the same or different from each other. When L ^D2C there are a plurality, a plurality of L ^D2C may be the same or different from each other.

Among the metal complexes represented by the general formula (D2C), metal complexes represented by the following general formula (D2D) are more preferable.
General formula (D2D)
[IrX ^D2D _n7 L ^D2D _(6-n7) ] ^m7
In the general formula (D2D), X ^D2D represents a pseudohalogen ion other than a halogen ion or a cyanate ion, L ^D2D is a 5-membered ring ligand, and at least two nitrogen atoms and at least one sulfur atom in the ring skeleton. Represents a ligand containing In addition, you may have arbitrary substituents on the carbon atom in this ring skeleton. n ₇ represents 3, 4 or 5, and m ₇ represents the charge of the metal complex and represents 4-, 3-, 2-, 1-, 0 or 1+.
X ^D2D has the same meaning as X ^{D2 in} formula (I), and the preferred range is also the same. L ^D2D is preferably a compound having a thiadiazole as a skeleton, and a substituent other than hydrogen is preferably bonded to a carbon atom in the compound. Preferred substituents are halogen (fluorine, chlorine, bromine, iodine), methoxy group, ethoxy group, carboxyl group, methoxycarboxyl group, acyl group, acetyl group, chloroformyl group, mercapto group, methylthio group, thioformyl group, thiocarboxyl Group, dithiocarboxy group, sulfino group, sulfo group, sulfamoyl group, methylamino group, cyano group, isocyano group, cyanato group, isocyanato group, thiocyanato group, hydroxyamino group, hydroxyimino group, carbamoyl group, nitroso group, nitro group Hydrazino group, hydrazono group or azide group, more preferably halogen (fluorine, chlorine, bromine, iodine), chloroformyl group, sulfino group, sulfo group, sulfamoyl group, isocyano group, cyanato group, isocyanato group, thiocyanato group Base , A hydroxyimino group, a nitroso group, a nitro group, or an azide group. Of these, chlorine, bromine, chloroformyl group, isocyano group, cyanato group, isocyanato group, and thiocyanato group are particularly preferable. n ₇ is preferably 4 or 5, and m ₇ is preferably -2 or -1.
Here, three to five X ^D2D may be the same or different from each other. When L ^D2D there are a plurality, a plurality of L ^D2D may be the same or different from each other.

Although the preferable specific example of a metal complex represented by general formula (D2) below is given, this invention is not limited to these.
[IrCl ₅ (H ₂ O)] ²⁻
[IrCl ₄ (H ₂ O) ₂ ] ⁻
[IrCl ₅ (H ₂ O)] ⁻
[IrCl ₄ (H ₂ O) ₂ ] ⁰
[IrCl ₅ (OH)] ³⁻
[IrCl ₄ (OH) ₂ ] ³⁻
[IrCl ₅ (OH)] ²⁻
[IrCl ₄ (OH) ₂ ] ²⁻
[IrCl ₅ (O)] ⁴⁻
[IrCl ₅ (O)] ³⁻
[IrCl ₄ (O) ₂ ] ⁴⁻
[IrBr ₅ (H ₂ O)] ²⁻
[IrBr ₄ (H ₂ O) ₂ ] ⁻
[IrBr ₅ (H ₂ O)] ⁻
[IrBr ₄ (H ₂ O) ₂ ] ⁰
[IrBr ₅ (OH)] ³⁻
[IrBr ₄ (OH) ₂ ] ³⁻
[IrBr ₅ (OH)] ²⁻
[IrBr ₄ (OH) ₂ ] ²⁻
[IrBr ₅ (O)] ⁴⁻
[IrBr ₅ (O)] ³⁻
[IrBr ₄ (O) ₂ ] ⁴⁻
[IrCl ₅ (OCN)] ³⁻
[IrBr ₅ (OCN)] ³⁻
[IrCl ₅ (thiazole)] ²⁻
[IrCl ₄ (thiazole) ₂ ] ⁻
[IrCl ₃ (thiazole) ₃ ] ⁰
[IrBr ₅ (thiazole)] ²⁻
[IrBr ₄ (thiazole) ₂ ] ⁻
[IrBr ₃ (thiazole) ₃ ] ⁰
[IrCl ₅ (5-methylthiazole)] ²⁻
[IrCl ₄ (5-methylthiazole) ₂ ] ⁻
[IrBr ₅ (5-methylthiazole)] ²⁻
[IrBr ₄ (5-methylthiazole) ₂ ] ⁻
Among these, [IrCl ₅ (H ₂ O)] ²⁻ , [IrCl ₅ (thiazole)] ²⁻ , and [IrCl ₅ (5-methylthiazole)] ²⁻ are preferable.

The metal complex represented by the general formula (D1) or the general formula (D2) mentioned above is an anion or is electrically neutral. An anion that, when forming a salt with a cation, is preferably a counter cation that is easily dissolved in water. Specifically, alkali metal ions such as sodium ion, potassium ion, rubidium ion, cesium ion and lithium ion, ammonium ion and alkylammonium ion are preferable. In addition to water, these metal complexes should be dissolved in a mixed solvent with an appropriate organic solvent (for example, alcohols, ethers, glycols, ketones, esters, amides, etc.) that can be mixed with water. Can do. The metal complex represented by the general formula (D1) is preferably added in an amount of 1 × 10 ⁻¹¹ mol to 1 × 10 ⁻⁶ mol per mol of silver during grain formation, and 1 × 10 ⁻¹⁰ mol to 1 × 10 6 Most preferably, ^-7 mol is added. The metal complex represented by the general formula (D2) is preferably added in an amount of 1 × 10 ⁻¹⁰ mol to 1 × 10 ⁻³ mol per mol of silver during grain formation, and 1 × 10 ⁻⁸ mol to 1 × 10 It is most preferable to add ^-5 mol.

  In the present invention, the above metal complex is added directly to the reaction solution at the time of silver halide grain formation, or added to an aqueous halide solution for forming silver halide grains, or in other solutions to form grains. It is preferably incorporated into the silver halide grains by adding to the reaction solution. It is also preferable to physically ripen the fine particles in which the metal complex has been previously incorporated in the grains and to incorporate them in the silver halide grains. Further, these methods can be combined and contained in the silver halide grains.

When these metal complexes are incorporated into silver halide grains, they can be uniformly present inside the grains, but disclosed in JP-A-4-208936, JP-A-2-125245, and JP-A-3-188437. As described above, it is also preferable to be present only in the particle surface layer, and it is also preferable to add a layer that does not contain a complex on the particle surface while the complex exists only in the particle interior. Further, as disclosed in US Pat. Nos. 5,252,451 and 5,256,530, physical ripening is performed with fine particles in which the complex is incorporated in the particles to modify the particle surface phase. It is also preferable. Furthermore, these methods can be used in combination, and a plurality of types of complexes may be incorporated in one silver halide grain.
In the present invention, it is preferable to use two or more, preferably three or more iridium complexes.

  The specific silver halide emulsion used in the present invention can further contain an iridium complex in which all six ligands are composed of Cl, Br, or I in addition to the iridium complex represented by the general formula (D2). In this case, Cl, Br, or I may be mixed in the hexacoordinate 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 high gradation at high illumination exposure.

Specific examples of iridium complexes in which all six ligands are Cl, Br, or I are given below, but are not limited thereto.
[IrCl ₆ ] ²⁻
[IrCl ₆ ] ³⁻
[IrBr ₆ ] ²⁻
[IrBr ₆ ] ³⁻
[IrI ₆ ] ³⁻

  In the present invention, in addition to the metal complexes described above, other metal ions can be doped inside and / or on the surface of silver halide grains. As a metal ion to be used, a transition metal ion is preferable, and iron, ruthenium, osmium, lead, cadmium, or zinc is particularly preferable. Further, these metal ions are more preferably used as a hexacoordinate octahedral complex with a ligand. When an inorganic compound is used as a ligand, cyanide ion, halide ion, thiocyan, hydroxide ion, peroxide ion, azide ion, nitrite ion, water, ammonia, nitrosyl ion, or thiol It is preferable to use a nitrosyl ion, and it is also preferable to use it in coordination with any of the above metal ions of iron, ruthenium, osmium, lead, cadmium, or zinc, and a plurality of kinds of ligands are contained in one complex molecule. It is also preferable to use it. An organic compound can also be used as the ligand, and preferred organic compounds include a chain compound having 5 or less carbon atoms in the main chain and / or a 5-membered or 6-membered heterocyclic compound. . More preferable organic compounds are compounds having a nitrogen atom, a phosphorus atom, an oxygen atom or a sulfur atom in the molecule as a coordination atom to the metal, particularly preferably furan, thiophene, oxazole, isoxazole, thiazole, isothiazole. , Imidazole, pyrazole, triazole, furazane, pyran, pyridine, pyridazine, pyrimidine, and pyrazine, and compounds in which these compounds are used as a basic skeleton and substituents are introduced into them are also preferable.

A combination of metal ions and ligands is preferably a combination of iron ions, ruthenium ions and cyanide ions. In the present invention, it is preferable to use the above-described metal complex and these compounds in combination. In these compounds, the cyanide ion preferably accounts for a majority of the coordination number to iron or ruthenium as the central metal, and the remaining coordination sites are thiocyanate, ammonia, water, nitrosyl ion, dimethyl sulfoxide, pyridine, It is preferably occupied by pyrazine or 4,4′-bipyridine. Most preferably, all six coordination sites of the central metal are occupied by cyanide ions to form a hexacyanoiron complex or a hexacyanoruthenium complex. These complexes containing cyanide ions as ligands are preferably added in an amount of 1 × 10 ⁻⁸ to 1 × 10 ⁻² mol per mol of silver during grain formation, and 1 × 10 ^{−6 to} 5 × 10 Most preferably, ^-4 mol is added.

In the present invention, the silver halide grains contained in the silver halide emulsion used in the light-sensitive material are not particularly limited, but the grain shape is substantially cubic or tetradecahedral grains having {100} faces ( These may have rounded grain vertices and may have higher-order planes), octahedral crystal grains, and a flat surface with an aspect ratio of 3 or more, the main surface comprising {100} planes or {111} planes It is preferable to consist of particles. The aspect ratio is a value obtained by dividing the diameter of a circle corresponding to the projected area by the thickness of the particle.
In the present invention, cubic and tetrahedral crystal grains having substantially {100} faces are preferred.

In the present invention, the particle size is represented by the length of one side (also referred to as a side length) of a cube having a volume equal to the volume of each particle, or the diameter of a sphere having a volume equal to the volume of each particle. The emulsion used in the color photographic light-sensitive material of the present invention is preferably a so-called monodispersed emulsion composed of grains having a monodispersed grain size distribution. The variation coefficient of the grain size in all grains contained in each silver halide emulsion is preferably 20% or less, more preferably 15% or less, and further preferably 10% or less. The variation coefficient 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. In this case, for the purpose of obtaining a wide latitude, it is also preferable to use the above monodispersed emulsion blended in the same layer or to apply multiple layers as the same color sensitive layer.
In the present invention, the equivalent sphere diameter of the grains contained in the silver halide emulsion containing the selenium compound is preferably 0.65 μm or less, more preferably 0.6 μm or less, and 0.5 μm or less. More preferably, it is particularly preferably 0.4 μm or less. The lower limit of the equivalent sphere diameter of the silver halide grains is preferably 0.05 μm, more preferably 0.1 μm. Particles with a sphere equivalent diameter of 0.6 μm correspond to cubic particles with a side length of about 0.48 μm, particles with a sphere equivalent diameter of 0.5 μm correspond to cubic particles with a side length of about 0.4 μm, and a sphere equivalent diameter of 0. A 4 μm particle corresponds to a cubic particle having a side length of about 0.32 μm.

  In the present invention, the silver halide emulsion used in the light-sensitive material is preferably subjected to gold sensitization known in the art. This is because gold sensitization can increase the sensitivity of the emulsion, and can reduce variations in photographic performance when scanning exposure is performed with laser light or the like. For gold sensitization, various inorganic gold compounds, gold (I) complexes having inorganic ligands, and gold (I) compounds having organic ligands can be used. Examples of the inorganic gold compound include chloroauric acid or a salt thereof, and a gold (I) complex having an inorganic ligand, for example, a gold dithiocyanate such as gold (I) potassium dithiocyanate or gold (I) 3 dithiosulfate. Compounds such as gold dithiosulfate compounds such as sodium can be used.

Examples of the gold (I) compound having an organic ligand (organic compound) include bisgold (I) mesoionic heterocycles described in JP-A-4-267249, such as bis (1,4,5-trimethyl-1, 2,4-triazolium-3-thiolate) orate (I) tetrafluoroborate, organomercaptogold (I) complexes described in JP-A-11-218870, such as potassium bis (1- [3- (2-sulfonate benzamide) ) Phenyl] -5-mercaptotetrazole potassium salt) Aurate (I) pentahydrate, gold (I) compound coordinated with nitrogen compound anion described in JP-A-4-268550, such as bis (1-methylhydan) Toinert) gold (I) sodium salt tetrahydrate can be used. The gold (I) compound having these organic ligands is prepared by previously synthesizing and isolating the organic ligand and an Au compound (for example, chloroauric acid or a salt thereof). Can be added to the emulsion without generation and isolation. Furthermore, an organic ligand and an Au compound (for example, chloroauric acid or a salt thereof) may be added separately to the emulsion to generate a gold (I) compound having an organic ligand in the emulsion.
Further, gold (I) thiolate compounds described in US Pat. No. 3,503,749, gold compounds described in JP-A-8-69074, JP-A-8-69075, and JP-A-9-269554, The compounds described in Japanese Patent Nos. 5620841, 5912112, 5620841, 5939245, and 5912111 can also be used.
The amount of these compounds added may vary widely depending on the case, but is 5 × 10 ^{−7 to} 5 × 10 ⁻³ mol, preferably 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol per mol of silver halide. is there.

Colloidal gold sulfide can also be used. The manufacturing method thereof is Research Disclosure (37154), Solid State Ionics 79, 60-66, 1995, Compt. Rend.Hebt.Seances Acad.Sci.Sect.B Vol.263, p.1328, published in 1966. The Research Disclosure describes a method using a thiocyanate ion in the production of colloidal gold sulfide, but a thioether compound such as methionine or thiodiethanol can be used instead.
Various sizes of colloidal gold sulfide can be used, those having an average particle size of 50 nm or less are preferred, average particle size of 10 nm or less is more preferred, and average particle size of 3 nm or less is even more preferred. This particle size can be measured from a TEM photograph. The composition of the colloidal gold sulfide may also Au ₂ S _1, may be of Au ₂ S ₁ ~Au ₂ S ₂ in such sulfur excess composition, sulfur excess composition is preferred. Au ₂ S _1.1 ~Au ₂ S _1.8 is more preferred.
The composition analysis of the colloidal gold sulfide can be obtained, for example, by taking out gold sulfide particles and determining the gold content and sulfur content by using an analysis method such as ICP or iodometry, respectively. The presence of gold ions and sulfur ions dissolved in the liquid phase (including hydrogen sulfide and its salts) in the gold sulfide colloid affects the composition analysis of the gold sulfide colloid particles. The analysis is performed after separation. The addition amount of the gold sulfide colloid may vary widely depending on the case, but 5 × ¹⁰ -7 ~5 × ^{10 -3} mol as per mole of silver halide gold atoms, preferably 5 × ¹⁰ -6 ~5 × ^{10 - 4} moles.

Chalcogen sensitization together with gold sensitization is also possible to perform the same molecule, AuCh ^- can be used capable of releasing molecule. Here, Au represents Au (I), and Ch represents a sulfur atom, a selenium atom, or a tellurium atom. AuCh ^- The releasable molecules, for example, gold compounds represented by AuCh-L. Here, L represents an atomic group constituting a molecule by bonding with AuCh. Further, one or more ligands may be coordinated with Au together with Ch-L. In addition, the gold compound represented by AuCh-L, when reacted in a solvent in the presence of silver ions, easily produces AgAuS when Ch is S, AgAuSe when Ch is Se, and AgAuTe when Ch is Te It is what has. Examples of such a compound include those in which L is an acyl group, and other examples include compounds represented by the following formula (AuCh1), formula (AuCh2), and formula (AuCh3).

Formula (AuCh1) R ₁ -X-M-ChAu
Here, Au represents Au (I), Ch represents a sulfur atom, selenium atom, tellurium atom, M represents a substituted or unsubstituted methylene group, X represents an oxygen atom, sulfur atom, selenium atom, NR ₂ R ₁ represents an atomic group (for example, an organic group such as an alkyl group, an aryl group, or a heterocyclic group) that forms a molecule by binding to X, and R ₂ represents a hydrogen atom and a substituent (for example, Represents an organic group such as an alkyl group, an aryl group, and a heterocyclic group. R ₁ and M may be bonded to each other to form a ring.
In the compounds of the formula (AuCh1), Ch is preferably a sulfur atom, and selenium atom, X represents an oxygen atom, a sulfur atom are preferred, R ₁ is an alkyl group, an aryl group is preferable. Examples of more specific compounds include Au (I) salts of thiosugars (gold thioglucose such as α-gold thioglucose, gold peracetylthioglucose, gold thiomannose, gold thiogalactose, and gold thioarabinose), seleno Au (I) salts of sugars (gold peracetylselenoglucose, gold peracetylselenomannose, etc.), Au (I) salts of tellurosugar, and the like. Here, thio sugar, seleno sugar, and telluro sugar represent compounds in which the anomeric hydroxyl group of the sugar is replaced with an SH group, a SeH group, and a TeH group, respectively.

Formula (AuCh2) W ₁ W ₂ C = CR ₃ ChAu
Here, Au represents Au (I), Ch represents a sulfur atom, a selenium atom, or a tellurium atom, and R ₃ and W ₂ are substituents (for example, a hydrogen atom, a halogen atom, an alkyl group, an aryl group) And W ₁ represents an electron-withdrawing group having a positive Hammett's substituent constant σ _p value. R ₃ and W ₁ , R ₃ and W ₂ , W ₁ and W ₂ may be bonded to each other to form a ring.
In the compound represented by the formula (AuCh2), those in which Ch is a sulfur atom and a selenium atom are preferred, R ₃ is preferably a hydrogen atom or an alkyl group, and W ₁ and W ₂ are Hammett's substituent constants σ _p An electron withdrawing group having a value of 0.2 or more is preferred. More specific examples of the compound include (NC) ₂ C═CHSAu, (CH ₃ OCO) ₂ C═CHSAu, CH ₃ CO (CH ₃ OCO) C═CHSAu, and the like.

Formula (AuCh3) W ₃ -E-ChAu
Here, 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 Hammett's substituent constant σ _p value is positive. Represents an electron-withdrawing group having a value of.
In the compounds of the formula (AuCh3), Ch sulfur atom, and preferably has a selenium atom, E is an ethylene group having an electron attractive group is a substituent constant sigma _p value is a positive value of Hammett W ₃ is preferably an electron-withdrawing group having a Hammett's substituent constant σ _p value of 0.2 or more.
The addition amount of these compounds may vary widely depending on the case, but is 5 × 10 ^{−7 to} 5 × 10 ⁻³ mol, preferably 3 × 10 ^{−6 to} 3 × 10 ⁻⁴ mol per mol of silver halide. is there.

  Various compounds or their precursors are added to the silver halide emulsion for use in the present invention in order to prevent fogging during the production process, storage or photographic processing of the light-sensitive material, or to stabilize photographic performance. be able to. Specific examples of these compounds are preferably those described on pages 39 to 72 of JP-A-62-215272. Further, 5-arylamino-1,2,3,4-thiatriazole compounds described in EP 0447647 (the aryl residue has at least one electron-withdrawing group) are also preferably used.

  In the present invention, in order to enhance the storage stability of the silver halide emulsion, both ends are adjacent to the hydroxamic acid derivative described in JP-A-11-109576 and the carbonyl group described in JP-A-11-327094. Cyclic ketones having a double bond substituted with an amino group or a hydroxyl group (particularly those represented by the general formula (S1), paragraph numbers 0036 to 0071 can be incorporated in the present specification), The sulfo-substituted catechol and hydroquinones described in JP-A-11-143011 (for example, 4,5-dihydroxy-1,3-benzenedisulfonic acid, 2,5-dihydroxy-1,4-benzenedisulfonic acid, 3,4- Dihydroxybenzenesulfonic acid, 2,3-dihydroxybenzenesulfonic acid, 2,5-dihydroxybenzenesulfonic acid 3,4,5-trihydroxybenzenesulfonic acid and salts thereof), hydroxylamines represented by the general formula (A) in US Pat. No. 5,556,741 (US Pat. No. 5,556,56) No. 741 column 4 line 56 to 11 column 22 line description is preferably applied to the present invention and is incorporated as part of this specification), JP-A-11-102045 The water-soluble reducing agents represented by the general formulas (I) to (III) are also preferably used in the present invention.

  The silver halide emulsion used in the present invention may contain a spectral sensitizing dye for the purpose of imparting so-called spectral sensitivity exhibiting photosensitivity in a desired light wavelength range. Examples of spectral sensitizing dyes used for spectral sensitization in the blue, green, and red regions include F.I. M.M. Examples include those described in Harmer's Heterocyclic compounds-Cyanine dyes and related compounds (John Wiley & Sons [New York, London, 1964)]. As specific examples of compounds and spectral sensitization, those described in JP-A-62-215272, page 22, right upper column to page 38 are preferably used. Further, as a red-sensitive spectral sensitizing dye of silver halide emulsion grains having a particularly high silver chloride content, the spectral sensitizing dye described in JP-A-3-123340 is stable, adsorbed, and exposed. This is very preferable from the viewpoint of temperature dependency.

The amount of these spectral sensitizing dyes to be added varies widely depending on the case, and is preferably in the range of 0.5 × 10 ⁻⁶ mol to 1.0 × 10 ⁻² mol per mol of silver halide. More preferably in the range of 1.0 × 10 ^-6 mol to 5.0 × ^{0 -3} mol.

  The silver halide color photographic light-sensitive material of the present invention (hereinafter sometimes simply referred to as “light-sensitive material”) has at least one of red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layers on a support. And at least one of the silver halide emulsion layers contains the specific silver halide emulsion referred to in the present invention and satisfies the above-mentioned formula (1).

  The light-sensitive material 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 silver halide emulsion layer containing a cyan dye-forming coupler on a support. It is preferable to have at least one layer of each. In the present invention, the silver halide emulsion layer containing the yellow dye-forming coupler contains a yellow coloring layer, the silver halide emulsion layer containing the magenta dye-forming coupler contains a magenta coloring layer, and the cyan dye-forming coupler. The silver halide emulsion layer functions as a cyan color-developing layer. The silver halide emulsion contained in each of the yellow color developing layer, the magenta color developing layer, and the cyan color developing layer preferably has photosensitivity to light in different wavelength regions. As a preferred example, a halogen containing an emulsion having sensitivity in the blue region in the yellow coloring layer, an emulsion having sensitivity in the green region in the magenta coloring layer, and an emulsion having sensitivity in the red region in the cyan coloring layer. Examples thereof include, but are not limited to, silver halide color photographic light-sensitive materials.

  In the present invention, it is preferable that the silver halide emulsion layer contains at least two types of silver halide emulsions having different silver chloride contents having a sensitivity of 90 mol% or more. Two or more types of silver halide emulsions having different sensitivities may be used, but two or three types are preferable in the design of the photosensitive material. The plurality of silver halide emulsions may be different or the same in grain size, halogen composition and structure, sensitizing dye, chemical sensitizer, antifogging agent and the like.

  It is preferable that at least two types of silver halide emulsions having different silver chloride contents of 90 mol% or more with different sensitivities are mixed in the same silver halide emulsion layer. However, emulsions having different sensitivities are in separate emulsion layers. It may be painted separately. However, these layers are required to have almost the same color sensitivity and color hue. Here, in the case of a color photographic light-sensitive material, substantially equal color sensitivities are, for example, blue color sensitivities, green color sensitivities, or red color sensitivities. Good. In the case of a color photographic light-sensitive material, for example, yellow color development, magenta color development, or cyan color development, and the color development hues may be different within the range.

  The light-sensitive material of the present invention may have a hydrophilic colloid layer, an antihalation layer, an intermediate layer, and a colored layer, which will be described later, if desired, in addition to the yellow coloring layer, magenta coloring layer, and cyan coloring layer.

Conventionally known photographic materials and additives can be used in the light-sensitive material of the present invention.
For example, as the photographic support, a transmissive support or a reflective support can be used. As the transmissive support, transparent films such as cellulose nitrate film and polyethylene terephthalate, and polyester of 2,6-naphthalenedicarboxylic acid (NDCA) and ethylene glycol (EG), NDCA, terephthalic acid and EG are used. A polyester provided with an information recording layer such as a magnetic layer is preferably used. As the reflective support, 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 layer of such a water-resistant resin layer (laminate layer) is particularly preferable. In the present invention, a reflective support is preferred.

  In the present invention, more preferred reflective supports include those having a polyolefin layer having fine pores on the paper substrate on the side on which the silver halide emulsion layer is provided. The polyolefin layer may consist of multiple layers, in which case the polyolefin layer adjacent to the gelatin layer on the silver halide emulsion layer side preferably has no micropores (eg, polypropylene, polyethylene) and is on a paper substrate. More preferred is a polyolefin (for example, polypropylene or polyethylene) having micropores on the near side. The density of the multi-layer or single-layer polyolefin layer located between the paper substrate and the photographic constituent layer is preferably 0.40 to 1.0 g / ml, more preferably 0.50 to 0.70 g / ml. The thickness of the multilayer or single layer of polyolefin positioned between the paper substrate and the photographic composition layer is preferably 10 to 100 μm, and more preferably 15 to 70 μm. Further, the ratio of the thickness of the polyolefin layer to the paper substrate is preferably 0.05 to 0.2, more preferably 0.1 to 0.15.

  In addition, it is also preferable to provide a polyolefin layer on the opposite side (back surface) to the photographic constituent layer of the paper substrate from the viewpoint of increasing the rigidity of the reflective support. In this case, the back surface polyolefin layer has a matte polyethylene surface. Alternatively, polypropylene is preferable, and polypropylene is more preferable. The polyolefin layer on the back surface is preferably 5 to 50 μm, more preferably 10 to 30 μm, and further preferably the density is 0.7 to 1.1 g / ml. In the reflective support in the present invention, preferred embodiments relating to the polyolefin layer provided on the paper substrate are disclosed in JP-A-10-333277, JP-A-10-333278, JP-A-11-52513, and JP-A-11-65024. Examples are described in EP0880065 and EP0880066.

Furthermore, it is preferable to contain a fluorescent brightening agent in the water-resistant resin layer. In addition, a hydrophilic colloid layer containing the fluorescent brightening agent in a dispersed manner may be separately formed. As the optical brightener, benzoxazole-based, coumarin-based, and pyrazoline-based compounds can be preferably used, and benzoxazolylnaphthalene-based and benzoxazolyl stilbene-based fluorescent whitening agents are more preferable. Although the usage-amount is not specifically limited, Preferably it is 1-100 mg / m < ² >. The mixing ratio in the case of mixing with a water-resistant resin is preferably 0.0005 to 3 mass%, more preferably 0.001 to 0.5 mass%, based on the resin.

  The reflective support may be a transmissive support or a reflective colloid coated with a hydrophilic colloid layer containing a white pigment. Further, the reflective support may be a support having a specular or second-type diffuse reflective metal surface.

  Further, as a support used in the light-sensitive material of the present invention, a white polyester support or a support in which a layer containing a white pigment is provided on a support having a silver halide emulsion layer is used for a display. May be. In order to further improve the sharpness, an antihalation layer is preferably coated on the silver halide emulsion layer coating side or the back surface of the support. In particular, 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 either reflected light or transmitted light.

  In the light-sensitive material of the present invention, a dye which can be decolored by processing as described in pages 27 to 76 of European Patent EP0,337,490A2 is applied to a hydrophilic colloid layer for the purpose of improving the sharpness of an image. Among them, oxonol dyes are added so that the optical reflection density at 680 nm of the light-sensitive material is 0.70 or more, or divalent to tetravalent alcohols (for example, trimethylolethane) are added to the water-resistant resin layer of the support. ) Etc. It is preferable to contain 12% by mass or more (more preferably 14% by mass or more) of titanium oxide surface-treated.

  In the light-sensitive material of the present invention, the processing described in pages 27 to 76 of EP 0337490 A2 is carried out on the hydrophilic colloid layer for the purpose of preventing irradiation and halation or improving the safety light safety. It is preferable to add a decolorizable dye (in particular, an oxonol dye or a cyanine dye). Furthermore, the dyes described in European Patent EP0819977 are also preferably added to the present invention. Some of these water-soluble dyes degrade color separation and safelight safety when the amount used is increased. As a dye that can be used without deteriorating color separation, water-soluble dyes described in JP-A Nos. 5-127324, 5-127325, and 5-216185 are preferable.

  In the present invention, a colored layer that can be decolored by treatment in place of the water-soluble dye or in combination with the water-soluble dye is used. The colored layer that can be decolored by the treatment used may be in direct contact with the emulsion layer, or may be disposed so as to be in contact with an intermediate layer containing a treatment color mixing inhibitor such as gelatin or hydroquinone. This colored layer is preferably placed under the emulsion layer (support side) 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 select and install only some of them. It is also possible to install a colored layer that has been colored corresponding to a plurality of primary color gamuts. The optical reflection density of the colored layer is the wavelength having the highest optical density in the wavelength range used for exposure (visible light range of 400 nm to 700 nm for normal printer exposure, wavelength of the scanning exposure light source used for scanning exposure). The optical density value at is preferably 0.2 or more and 3.0 or less. More preferably, it is 0.5 or more and 2.5 or less, and particularly preferably 0.8 or more and 2.0 or less.

  In order to form the colored layer, a conventionally known method can be applied. For example, the dyes described in JP-A-2-282244, page 3 from the upper right column to page 8, and the dyes described in JP-A-3-7931, page 3 from upper right column to page 11, lower left column are solid. A method of incorporating a hydrophilic colloid layer in the form of a fine particle dispersion, a method of mordanting an anionic dye into a cationic polymer, a method of adsorbing a dye to fine particles such as silver halide and fixing it in the layer, JP-A-1-239544 For example, a method using colloidal silver as described in Japanese Patent Publication. As a method of dispersing a fine powder of a pigment in a solid state, for example, a method of containing a fine powder dye which is substantially water-insoluble at least at pH 6 or less but substantially water-soluble at least at pH 8 or more is disclosed in Japanese Patent Application Laid-Open No. Hei. No. 2-308244, pages 4 to 13. Further, for example, a method for mordanting an anionic dye into a cationic polymer is described on pages 18 to 26 of JP-A-2-84737. US Pat. Nos. 2,688,601 and 3,459,563 show preparation methods for colloidal silver as a light absorber. Among these methods, a method of containing a fine powder dye and a method of using colloidal silver are preferable.

  The silver halide photographic light-sensitive 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, etc., among which it is preferably used as a color photographic paper. The color photographic paper has at least one yellow color-forming silver halide emulsion layer, magenta color-forming silver halide emulsion layer, and cyan color-forming silver halide emulsion layer. Generally, these silver halides are used. The emulsion layers are a yellow color-developing silver halide emulsion layer, a magenta color-developing silver halide emulsion layer, and a cyan color-developing silver halide emulsion layer in the order from the support, but are not limited thereto.

  The silver halide emulsion layer containing a yellow coupler may be disposed at any position on the support. However, when the yellow coupler-containing layer contains silver halide tabular grains, a magenta coupler-containing silver halide is contained. It is preferably coated at a position farther from the support than at least one emulsion layer or cyan coupler-containing silver halide emulsion layer. Further, from the viewpoints of accelerating color development, accelerating desilvering, and reducing residual color by sensitizing dye, the yellow coupler-containing silver halide emulsion layer is coated at a position farthest from the support than other silver halide emulsion layers. It is preferable to be provided. Further, from the viewpoint of reducing Blix fading, the cyan coupler-containing silver halide emulsion layer is preferably the center layer of other silver halide emulsion layers, and from the viewpoint of reducing photobleaching, cyan coupler-containing silver halide emulsion layers. Is preferably the lowermost layer. Each of the color developing layers of yellow, magenta and cyan may be composed of two layers or three layers. For example, couplers containing no silver halide emulsion as described in JP-A-4-75055, JP-A-9-1114035, JP-A-10-246940, US Pat. No. 5,576,159, etc. It is also preferable to provide a layer adjacent to the silver halide emulsion layer to form a color developing layer.

  As silver halide emulsions and other materials (additives, etc.) and photographic composition layers (layer arrangement, etc.) applied in the present invention, and processing methods and processing additives applied to process this photosensitive material, Disclosed in JP-A-62-215272, JP-A-2-33144, European Patent EP0,355,660A2, and particularly described in European Patent EP0,355,660A2. Are preferably used. Furthermore, JP-A-5-34889, JP-A-4-359249, JP-A-4-313733, JP-A-4-270344, JP-A-5-66527, JP-A-4-34548, JP-A-4-145433. No. 2-854, No. 1-158431, No. 2-90145, No. 3-194539, No. 2-93641, EP-A-0520457A2, and the like. A silver halide color photographic light-sensitive material and a processing method thereof are also preferable.

  In particular, in the present invention, the reflection type support and silver halide emulsion described above, further different metal ion species doped in the silver halide grains, storage stabilizer or antifoggant for silver halide emulsion, chemical enhancement, Sensitization method (sensitizer), spectral sensitization method (spectral sensitizer), cyan, magenta, yellow coupler and its emulsifying dispersion method, color image preservability improving agent (stain inhibitor and anti-fading agent), dye (coloring) As for the layer), the gelatin type, the layer structure of the photosensitive material, the coating pH of the photosensitive material, and the like, those described in each part of the patent literature shown in Table 1 below are particularly preferably applicable.

Other examples of cyan, magenta and yellow couplers used in the present invention include those described 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, upper left column, last line, page 30, upper right column, line 6 to page 35, lower right column, line 11 and page 0, line 15 to 27 of EP0355,660A2. Couplers described in the 5th line, 5th page, 30th line to 28th page, 45th page, 29th line to 31st line, 47th page, 23rd line to 63rd page, 50th line are also useful.
In the present invention, compounds represented by the general formulas (II) and (III) of WO 98/33760 and the general formula (D) of JP-A-10-221825 may be added.

  As a cyan dye-forming coupler (sometimes simply referred to as “cyan coupler”) that can be used in the present invention, a pyrrolotriazole coupler is preferably used, and is represented by the general formula (I) or (II) of JP-A-5-313324. ), Couplers represented by general formula (I) of JP-A-6-347960, and exemplified couplers described in these patent documents are particularly preferred. Phenol-based and naphthol-based cyan couplers are also preferable. For example, cyan couplers represented by the general formula (ADF) described in JP-A-10-333297 are preferable. Other cyan couplers include pyrroloazole type cyan couplers described in European Patents EP 0488248 and EP 0491197A1, 2,5-diacylaminophenol couplers described in US Pat. No. 5,888,716, US Pyrazoloazole-type cyan couplers having an electron-withdrawing group and a hydrogen-bonding group at the 6-position described in Japanese Patent Nos. 4,873,183 and 4,916,051 are disclosed. Pyrazoloazole type cyan couplers having a carbamoyl group at the 6-position described in JP-A Nos. 171185, 8-31360, and 8-339060 are also preferable.

  In addition to the diphenylimidazole cyan coupler described in JP-A-2-33144, a 3-hydroxypyridine cyan coupler described in European Patent EP 0333185A2 (particularly, coupler (42) listed as a specific example) A 4-equivalent coupler having a chlorine leaving group to give 2 equivalents, couplers (6) and (9) are particularly preferred) and cyclic active methylene-based cyan couplers described in JP-A 64-32260 (among others) (Examples of couplers 3, 8, and 34 listed as specific examples are particularly preferred), pyrrolopyrazole type cyan couplers described in EP 0456226A1, and pyrroloimidazole type cyan couplers described in EP 0484909 are used. You can also.

  Of these cyan couplers, pyrroloazole cyan couplers represented by the general formula (I) described in JP-A No. 11-282138 are particularly preferred, and the descriptions in paragraphs 0012 to 0059 of the patent document are exemplified. The cyan couplers (1) to (47) are applied to the present invention as they are, and are preferably incorporated as part of the present specification.

  Examples of the magenta dye-forming coupler used in the present invention (sometimes simply referred to as “magenta coupler”) include 5-pyrazolone-based magenta couplers and pyrazoloazole-based magenta couplers described in the publicly known literatures in the above table. Among them, a secondary or tertiary alkyl group as described in JP-A-61-65245 is the 2, 3, or 6 position of the pyrazolotriazole ring among them in terms of hue, image stability, color developability, etc. A pyrazolotriazole coupler directly connected to a pyrazoloazole coupler containing a sulfonamide group in the molecule as described in JP-A-61-65246, as described in JP-A-61-147254 Pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group, European Patent No. 226,849A, Use of pyrazoloazole couplers having a 6-position alkoxy or aryloxy group as described in the 294,785A Pat are preferred. In particular, the magenta coupler is preferably a pyrazoloazole coupler represented by the general formula (M-I) described in JP-A-8-122984. Paragraph Nos. 0009 to 0026 of the patent document are directly applied to the present invention. , Incorporated herein as part of this specification. In addition to this, pyrazoloazole couplers having sterically hindered groups at both the 3-position and the 6-position described in EP 854384 and EP 844640 are also preferably used.

  Further, as yellow dye-forming couplers (sometimes simply referred to as “yellow couplers”), in addition to the compounds described in the above table, a 3- to 5-membered cyclic group is added to the acyl group described in European Patent EP 0447969A1. An acylacetamide type yellow coupler having a structure, a malondianilide type yellow coupler having a cyclic structure described in European Patent EP 0482552A1, European Patent Publications Nos. Pyrrole-2 or 3-yl or indole-2 or 3-ylcarbonylacetic acid anilide type couplers described in U.S. Pat. Nos. 5,953,873, 953874, 1,953875A1, etc. Described in the specification of 5,118,599 Acylacetamide yellow couplers or JP acetanilide type yellow couplers heterocyclic acyl group is substituted as described in 2003-173007 JP preferably used having a dioxane structure. Among them, an acylacetamide type yellow coupler in which the acyl group is a 1-alkylcyclopropane-1-carbonyl group, a malondianilide type yellow coupler in which one of the anilides constitutes an indoline ring, or an acetanilide in which a heterocyclic ring is substituted on the acyl group The use of type yellow couplers is preferred. These couplers can be used alone or in combination. Among them, an acylacetamide type yellow coupler in which the acyl group is a 1-alkylcyclopropane-1-carbonyl group, a malondianilide type yellow coupler in which one of the anilides constitutes an indoline ring, or an acetanilide in which a heterocyclic ring is substituted on the acyl group The use of type yellow couplers is preferred. These couplers can be used alone or in combination.

  The coupler used in the present invention is impregnated into a loadable latex polymer (eg, US Pat. No. 4,203,716) in the presence (or absence) of the high boiling organic solvent described in the above table. Alternatively, it is preferably dissolved together with a water-insoluble and organic solvent-soluble polymer and emulsified and dispersed in a hydrophilic colloid aqueous solution. Water-insoluble and organic solvent-soluble polymers that 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 30. The described homopolymers or copolymers are mentioned. More preferably, use of a methacrylate or acrylamide polymer, particularly an acrylamide polymer is preferred in view of color image stability.

In the present invention, known color mixing inhibitors can be used, and among them, those described in the following patent documents are preferable.
For example, high molecular weight redox compounds described in JP-A-5-333501, phenidone and hydrazine compounds described in WO98 / 33760, US Pat. No. 4,923,787, etc. White couplers described in Japanese Patent No. 249637, Japanese Patent Application Laid-Open No. 10-282615, German Patent No. 19629142A1, and the like can be used. In particular, in the case of increasing the pH of the developer to speed up development, German Patent No. 19618786A1, European Patent No. 839623A1, European Patent No. 842975A1, German Patent No. 180686846A1 And redox compounds described in French Patent No. 2760460A1 and the like are also preferably used.

  In the present invention, it is preferable to use a compound having a triazine bone core having a high molar extinction coefficient as the ultraviolet absorber, and for example, compounds described in the following patent documents can be used. These are preferably added to the photosensitive layer and / or non-photosensitive. For example, JP-A-46-3335, JP-A-55-15276, JP-A-5-197074, JP-A-5-232630, JP-A-5-307232, JP-A-6-218131, and 8- No. 53427, No. 8-234364, No. 8-239368, No. 9-31067, No. 10-115898, No. 10-147777, No. 10-182621, German Patent No. The compounds described in the specification of 19739797A, European Patent No. 711804A and JP-A-8-501291 can be used.

As the binder or protective colloid that can be used in the light-sensitive material of the present invention, gelatin is advantageously used, but other hydrophilic colloids can be used alone or in combination with gelatin. As a preferable gelatin, the heavy metal contained as impurities such as iron, copper, zinc and manganese is preferably 5 ppm or less, more preferably 3 ppm or less. The amount of calcium contained in the light-sensitive material is preferably 20 mg / m ² or less, more preferably 10 mg / m ² or less, and most preferably 5 mg / m ² or less.

  In the present invention, an antibacterial / antifungal agent as described in JP-A-63-271247 is added in order to prevent various wrinkles and bacteria that propagate in the hydrophilic colloid layer and degrade the image. Is preferred. Further, the film pH of the photosensitive material is preferably 4.0 to 7.0, more preferably 4.0 to 6.5.

Total Coating amount of gelatin photographic constituent layer in the present invention is more preferably preferably not more than 3 g / m ² or more 6 g / m ^2, is 3 g / m ² or more 5 g / m ² or less. Even in the case of ultra-rapid processing, the film thickness of the entire photographic composition layer is preferably 3 μm to 7.5 μm, and more preferably 3 μm to 6. It is preferably 5 μm. The dry film thickness can be measured by measuring the change in film thickness before and after peeling the dry film, or by observing the cross section with an optical microscope or an electron microscope. In the present invention, the swelling film thickness is preferably 8 μm to 19 μm, and more preferably 9 μm to 18 μm, in order to achieve both development progress and increase in the drying speed. The swollen film thickness can be measured by the dot method in a state where the dried photosensitive material is immersed in an aqueous solution at 35 ° C. and swelled to reach a sufficient equilibrium. The total coating設銀weight in the present invention is more preferably is preferably ^{0.2g / m 2 ~0.5g / m 2} , a ^{0.2g / m 2 ~0.45g / m 2} , 0 Most preferably, it is from ² g / m ^{2 to} 0.40 g / m ² .

In the present invention, a surfactant can be added to the photosensitive material from the viewpoints of improving the coating stability of the photosensitive material, preventing the generation of static electricity, and adjusting the charge amount. Examples of the surfactant include an anionic surfactant, a cationic surfactant, a betaine surfactant, and a nonionic surfactant, and examples thereof include those described in JP-A-5-333492. The surfactant used in the present invention is preferably a fluorine atom-containing surfactant. In particular, 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, but are preferably used in combination with other conventionally known surfactants. The amount of these surfactants added to the photosensitive material is not particularly limited, but is generally 1 × 10 ^{−5 to} 1 g / m ² , preferably 1 × 10 ⁻⁴ to 1 × 10 ^{−. 1} g / m ² , more preferably 1 × 10 ⁻³ to 1 × 10 ⁻² g / m ² .

The photosensitive material of the present invention can form an image by an exposure process in which light is irradiated according to image information and a development process in which the photosensitive material irradiated with light is developed.
The photosensitive material of the present invention is suitable for a scanning exposure system using a cathode ray (CRT) in addition to being used in a printing system using a normal negative printer. The cathode ray tube exposure apparatus is simpler and more compact and less expensive than an apparatus using a laser. Also, the adjustment of the optical axis and color is easy. As the cathode ray tube used for image exposure, various light emitters that emit light in the spectral region are used as necessary. For example, any one of red light emitters, green light emitters, and blue light emitters, or a mixture of two or more thereof may be used. The spectral region is not limited to the above red, green, and blue, and a phosphor that emits light in the yellow, orange, purple, or infrared region is also used. In particular, a cathode ray tube that emits white light by mixing these light emitters is often used.

  When the photosensitive material has a plurality of photosensitive layers having different spectral sensitivity distributions, and the cathode tube also has a phosphor exhibiting light emission in a plurality of spectral regions, a plurality of colors are exposed at the same time, that is, a plurality of colors are applied to the cathode ray tube. It is also possible to emit light from the tube surface by inputting a color image signal. A method of sequentially inputting image signals for each color to cause each color to emit light sequentially and exposing through a film that cuts the colors other than that color (surface sequential exposure) may be adopted. However, since a high-resolution cathode ray tube can be used, it is preferable for improving image quality.

  The photosensitive material of the present invention is a monochromatic high light source such as a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser, or a second harmonic light source (SHG) using a combination of a solid state laser using a semiconductor laser and a nonlinear optical crystal. A digital scanning exposure method using density light is preferably used. In order to make the system compact and inexpensive, it is preferable to use a second harmonic generation light source (SHG) that combines a semiconductor laser, a semiconductor laser, or a solid-state laser and a nonlinear optical crystal. In particular, in order to design a compact, inexpensive, long-life and high-stability device, it is preferable to use a semiconductor laser, and at least one of the exposure light sources is preferably a semiconductor laser.

When such a scanning exposure light source is used, 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. In a solid laser using a semiconductor laser as an excitation light source or an SHG light source obtained by combining a semiconductor laser and a nonlinear optical crystal, the oscillation wavelength of the laser can be halved, so that blue light and green light can be obtained. Therefore, the spectral sensitivity maximum of the photosensitive material can be given to the usual three wavelength regions of blue, green, and red. When the exposure time in such scanning exposure is defined as the time for exposing the pixel size when the pixel density is 400 dpi, the preferable exposure time is 1 × 10 ⁻⁴ seconds or less, more preferably 1 × 10 ⁻⁶ seconds. It is as follows.

When the present invention is applied to a silver halide color photographic light-sensitive material, imagewise exposure is preferably performed with coherent light of a blue laser having an emission wavelength of 420 nm to 460 nm. Among blue lasers, it is particularly preferable to use a blue semiconductor laser.
Specifically, as a laser light source, a blue semiconductor laser having a wavelength of 430 to 450 nm (announced by Nichia Chemical Co., Ltd. at the 48th Applied Physics Related Conference in March 2001) and a semiconductor laser (oscillation wavelength of about 940 nm) are used. waveguide-like inverted domain structure about 470nm blue laser taken out by wavelength conversion by the SHG crystal of LiNbO ₃ having the semiconductor laser SHG crystal of LiNbO ₃ having a reversal domain structure of (oscillation wavelength of about 1060 nm) a waveguide-like About 530 nm green laser, wavelength 685 nm red semiconductor laser (Hitachi type No. HL6738MG, trade name), wavelength 650 nm red semiconductor laser (Hitachi type No. HL6501MG, trade name), etc. Preferably used.

  The silver halide photographic light-sensitive material of the present invention can be preferably used in combination with the exposure and development systems described in the following known materials. Examples of the developing system include an automatic printing and developing system described in JP-A-10-333253, a photosensitive material conveying apparatus described in JP-A-2000-10206, and an image reading apparatus described in JP-A-11-215312. , An exposure system comprising a color image recording system described in JP-A-11-88619 and JP-A-10-202950, and a digital photo print including a remote diagnosis system described in JP-A-10-210206 And a photo print system including an image recording apparatus described in JP 2000-310822 A.

  Preferred scanning exposure systems applicable to the present invention are described in detail in the patent documents listed in the above table.

When the photosensitive material of the present invention is subjected to printer exposure, it is preferable to use a band stop filter described in US Pat. No. 4,880,726. This removes light color mixing and remarkably improves color reproducibility.
In the present invention, as described in European Patents EP0789270A1 and EP0789480A1, the yellow microdot pattern may be pre-exposed in advance and copy restrictions may be applied before image information is added. .

  In the processing of the photosensitive material of the present invention, JP-A-2-207250, page 26, lower right column, line 1 to page 34, upper right column, line 9 and JP-A-4-97355, page 5, upper left column. The processing materials and processing methods described in the 17th line to the 18th page, lower right column, 20th line are preferably applicable. As the preservative used in the developer, compounds described in the patent documents listed in the above table are preferably used.

The present invention is applied as a light-sensitive material having rapid processing suitability. The color development time is 28 seconds or less, preferably 25 seconds or less and 6 seconds or more, more preferably 20 seconds or less and 6 seconds or more. Similarly, the bleach-fixing time is preferably 30 seconds or shorter, more preferably 25 seconds or shorter and 6 seconds or longer, more preferably 20 seconds or shorter and 6 seconds or longer. The washing or stabilizing time is preferably 60 seconds or less, more preferably 40 seconds or less and 6 seconds or more.
The color development time is the time from when the photosensitive material enters the color developer until it enters the bleach-fixing solution in the next processing step. For example, when processed by an automatic developing machine, the time during which the photosensitive material is immersed in the color developer (so-called submerged time) and the photosensitive material leaves the color developer and is bleach-fixed in the next processing step. The total of both the time during which air is conveyed toward the bath (so-called air time) is called color development time. Similarly, the bleach-fixing time refers to the time from when the photosensitive material enters the bleach-fixing solution until the next washing or stabilizing bath. The water washing or stabilization time refers to the time (so-called liquid time) that the photosensitive material is in the liquid for the drying process after entering the water washing or stabilizing liquid.

As a method for developing the photosensitive material of the present invention after exposure, a developing method containing a conventional alkaline agent and a developing agent (especially p-phenylenediamine-based color developing agent), a developing agent is incorporated in the photosensitive material. In addition to a wet method such as a method of developing with an activator solution such as an alkaline solution that does not contain a developing agent, a heat developing method that does not use a processing solution can be used. In particular, the activator method is a preferable method from the viewpoint of environmental protection because it does not contain a developing agent in the processing solution, so that the processing solution can be easily managed and handled, and the load during processing of the waste liquid is small.
In the present invention, a method of developing with a developer containing an alkali agent and a developing agent (particularly a p-phenylenediamine color developing agent) is preferred.
In the activator method, as a developing agent or a precursor thereof incorporated in the light-sensitive material, for example, JP-A-8-234388, JP-A-9-152686, JP-A-9-152893, and JP-A-9-212814. The hydrazine type compounds described in JP-A-9-160193 are preferred.

  Further, a developing method in which the amount of silver applied to the photosensitive material is reduced and image amplification processing (compensation processing) using hydrogen peroxide is preferably used. In particular, it is preferable to use this method for the activator method. Specifically, an image forming method using an activator solution containing hydrogen peroxide described in JP-A-8-297354 and 9-152695 is preferably used. In the activator method, after processing with an activator solution, desilvering is usually performed. However, in the image amplification processing method using a low silver amount of light-sensitive material, desilvering is omitted and washing or stabilization is simplified. Can be done. Further, in a method of reading image information from a photosensitive material with a scanner or the like, it is possible to adopt a processing form that does not require a desilvering process even when a high silver amount photosensitive material such as a photographic photosensitive material is used.

  For the activator solution, desilvering solution (bleaching / fixing solution), water washing and stabilizing solution used in the present invention, known processing materials and processing methods can be used. Preferably, those described in Research Disclosure Item 36544 (September 1994), pages 536 to 541 and JP-A-8-234388 can be used.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Example 1
(Preparation of emulsion B-1)
High silver chloride cubic grains were prepared by a method in which a silver nitrate aqueous solution and a sodium chloride aqueous solution were simultaneously added to and mixed with deionized water containing stirred deionized gelatin. In the course of this preparation, the nucleation portion was added from 0% to 3% addition of silver nitrate. From the time when the addition of silver nitrate was 3% to the time when it was 80%, the addition rate of the aqueous silver nitrate solution and the aqueous sodium chloride solution was accelerated as a linear function with respect to time. Potassium bromide (4.0 mole% per mole of finished silver halide) was added from the time when the addition of silver nitrate was 80% to 100%. When the addition of silver nitrate was completed 90%, potassium iodide (0.3 mol% per mol of the finished silver halide) was added with vigorous stirring. Toward the time the addition of 97% from the time of 92% of the silver nitrate _was added _{K 4 [Ru (CN) 6} ]. The obtained emulsion grains were silver iodobromochloride grains. According to observation and measurement using a transmission electron micrograph (direct method), the emulsion grains were monodisperse cubic grains having a side length of 0.50 μm and a coefficient of variation of 9.0%. there were. The emulsion was subjected to precipitation desalting treatment, and then deionized gelatin, compounds (Ab-1), (Ab-2), (Ab-3), and calcium nitrate were added and redispersed.

(Preparation of emulsion B-2)
In the preparation of Emulsion B-1, K ₂ [IrCl ₅ (H ₂ O)] (1.0 × 10 ⁻⁷ mol per mol of finished silver halide) was observed from the time when the addition of silver nitrate was 92% to 97%. ) And K [IrCl ₄ (H ₂ O) ₂ ] (1.0 × 10 ⁻⁸ mole per mole of finished silver halide) are added in the same manner as emulsion B-1 except that emulsion B-2 is prepared. Prepared.

(Preparation of emulsion B-3)
In the preparation of Emulsion B-2, K ₂ [IrCl ₅ (5-methylthiazole)] (3.4 × 10 ⁻⁸ mol per mol of finished silver halide) was added from the point of 82% to 88% of the addition of silver nitrate. Emulsion B-3 was prepared in the same manner as Emulsion B-2 except that

(Preparation of emulsion B-4)
In the preparation of emulsion B-3, the ratio of K ₂ [IrCl ₅ (H ₂ O)] and K [IrCl ₄ (H ₂ O) ₂ ] and K ₂ [IrCl ₅ (5-methylthiazole)] was maintained, Emulsion B-4 was prepared in the same manner as Emulsion B-3 except that each addition amount was increased 3 times.

(Preparation of emulsion B-5)
In the preparation of emulsion B-3, the ratio of K ₂ [IrCl ₅ (H ₂ O)] and K [IrCl ₄ (H ₂ O) ₂ ] and K ₂ [IrCl ₅ (5-methylthiazole)] was maintained, Emulsion B-5 was prepared in the same manner as Emulsion B-3 except that each addition amount was increased 10-fold.

(Preparation of emulsion B-6)
In the preparation of emulsion B-3, the ratio of K ₂ [IrCl ₅ (H ₂ O)] and K [IrCl ₄ (H ₂ O) ₂ ] and K ₂ [IrCl ₅ (5-methylthiazole)] was maintained, Emulsion B-6 was prepared in the same manner as Emulsion B-3 except that each addition amount was increased 30-fold.

(Preparation of emulsion B-7)
In the preparation of emulsion B-3, the ratio of K ₂ [IrCl ₅ (H ₂ O)] and K [IrCl ₄ (H ₂ O) ₂ ] and K ₂ [IrCl ₅ (5-methylthiazole)] was maintained, Emulsion B-7 was prepared in the same manner as Emulsion B-3 except that each addition amount was increased 100-fold.

(Preparation of Emulsion B-8 to Emulsion B-14)
In the preparation of Emulsion B-1 to Emulsion B-7, K ₂ [RuCl ₅ (NO)] (3.4 × 10 4 per mol of the finished silver halide) was added from the time point when the addition of silver nitrate was 0% to the time point of 3%. Emulsion B-8 to Emulsion B-14 were prepared in the same manner as Emulsion B-1 to Emulsion B-7 except that ^-9 mol) was added.

(Preparation of emulsion B-1a)
The redispersed emulsion B-1 was dissolved at 40 ° C., and sodium benzenethiosulfonate, 1- (5-methylureidophenyl) -5-mercaptotetrazole (1/10 of the addition amount at the end of chemical sensitization), sulfur Triethylthiourea as a sensitizer and (bis (1,4,5-trimethyl-1,2,4-triazolium-3-thiolate) orate (I) tetrafluoroborate) as a gold sensitizer are added, The chemical sensitization was optimized so that the gradation at the exposure of × 10 ⁻⁶ seconds was the hardest, and ripened at 60 ° C. Thereafter, the temperature was lowered to 40 ° C., and 1-phenyl-5-mercaptotetrazole, 1- (3-acetamidophenyl) -5-mercaptotetrazole, 1- (5-methylureidophenyl) -5-mercaptotetrazole, compound-2, Compound 3 having repeating unit 2 or 3 represented by compound-3 as a main component (terminal X ₁ and X ₂ are hydroxyl groups), compound-4 and potassium bromide (0.30 mol% per mol of finished silver halide) ) Was added. Further, spectral sensitization was performed by adding sensitizing dyes S-1, S-2, S-3, and S-9 before addition of the sensitizer. The emulsion thus obtained was designated as Emulsion B-1a.

(Preparation of Emulsion B-2a to Emulsion B-7a)
Emulsion B-2a to Emulsion B-7a were prepared in the same manner as Emulsion B-1a, except that Emulsion B-2 to Emulsion B-7 were used instead of Emulsion B-1. .

(Preparation of emulsion B-1b)
Re-dispersed emulsion B-1 was dissolved at 40 ° C., and sodium benzenethiosulfonate, 1- (5-methylureidophenyl) -5-mercaptotetrazole (1/10 of the addition amount at the end of chemical sensitization), selenium The exemplified compound (SE3-29) as a sensitizer and (bis (1,4,5-trimethyl-1,2,4-triazolium-3-thiolate) orate (I) tetrafluoroborate as a gold sensitizer ) Was added, and the chemical sensitization was optimized so that the gradation at the exposure of 1 × 10 ⁻⁶ seconds was the hardest, and the mixture was aged at 60 ° C. Thereafter, the temperature was lowered to 40 ° C., and 1-phenyl-5-mercaptotetrazole, 1- (3-acetamidophenyl) -5-mercaptotetrazole, 1- (5-methylureidophenyl) -5-mercaptotetrazole, compound-2, Compound 3 having repeating unit 2 or 3 represented by compound-3 as a main component (terminal X ₁ and X ₂ are hydroxyl groups), compound-4 and potassium bromide (0.30 mol% per mol of finished silver halide) ) Was added. Further, spectral sensitization was performed by adding sensitizing dyes S-1, S-2, and S-3 before addition of the sensitizer. The emulsion thus obtained was designated as Emulsion B-1b.

(Preparation of Emulsion B-2b to Emulsion B-7b)
Emulsion B-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. .

(Preparation of Emulsion B-8b to Emulsion B-14b)
Emulsion B-8b to Emulsion B-14b were prepared in the same manner as Emulsion B-1b except that Emulsion B-8 to Emulsion B-14 were used instead of Emulsion B-1. .

(Preparation of emulsion G-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 1 mol of the finished silver halide. Otherwise, Emulsion G-1 was prepared in the same manner as Emulsion B-1. The obtained emulsion grains were silver iodobromochloride grains. According to observation and measurement using a transmission electron micrograph (direct method), the emulsion grains were monodisperse cubic grains having a side length of 0.40 μm and a coefficient of variation of 9.5%. there were. The emulsion was subjected to precipitation desalting treatment, and then deionized gelatin, compounds (Ab-1), (Ab-2), (Ab-3), and calcium nitrate were added and redispersed.

(Preparation of emulsion G-2)
In the preparation of Emulsion G-1, K ₂ [IrCl ₅ (H ₂ O)] (2.0 × 10 ⁻⁸ mol per mol of finished silver halide) from the time when silver nitrate was added to 92% to 97% ) And K [IrCl ₄ (H ₂ O) ₂ ] (2.0 × 10 ⁻⁷ mol per mol of the finished silver halide) are added in the same manner as Emulsion G-1, except for adding Emulsion G-2. Prepared.

(Preparation of emulsion G-3)
In the preparation of Emulsion G-2, K ₂ [IrCl ₅ (5-methylthiazole)] (6.6 × 10 ⁻⁸ mol per mol of finished silver halide) from the time when the addition of silver nitrate was 82% to 88% Emulsion G-3 was prepared in the same manner as Emulsion G-2, except that

(Preparation of Emulsion G-4 to Emulsion G-7)
In the preparation of emulsion G-3, the ratio of K ₂ [IrCl ₅ (H ₂ O)] and K [IrCl ₄ (H ₂ O) ₂ ] and K ₂ [IrCl ₅ (5-methylthiazole)] was maintained, Emulsion G-4 to Emulsion G-7 were prepared in the same manner as Emulsion G-3 except that the respective addition amounts were increased to 3, 10, 30, and 100 times.

(Preparation of Emulsion G-8 to Emulsion G-14)
In the preparation of Emulsion G-1 to Emulsion G-7, K ₂ [RuCl ₅ (NO)] (6.6 × 10 6 per mole of finished silver halide) was observed from the time when the addition of silver nitrate was 0% to 3%. Emulsion G-8 to Emulsion G-14 were prepared in the same manner as Emulsion G-1 to Emulsion G-7 except that ^-9 mol) was added.

(Preparation of emulsion G-1a)
The redispersed emulsion G-1 was dissolved at 40 ° C., and sodium benzenethiosulfonate, p-glutaramide phenyl disulfide, sodium thiosulfate as a sulfur sensitizer, and (bis (1,4,5) as a gold sensitizer. -Trimethyl-1,2,4-triazolium-3-thiolate) aurate (I) tetrafluoroborate) is added, and chemical sensitization is optimized so that the gradation is the hardest when exposed to 1 × 10 ⁻⁶ seconds Aged at 65 ° C. 1- (3-acetamidophenyl) -5-mercaptotetrazole, 1- (5-methylureidophenyl) -5-mercaptotetrazole, compound-2, compound-4 and potassium bromide (1 mol of the finished silver halide) Per 0.35 mol%) was added. Further, spectral sensitization was performed by adding sensitizing dyes S-4, S-5, S-6 and S-7 before addition of the sensitizer. The emulsion thus obtained was designated as Emulsion G-1a.

(Preparation of Emulsion G-2a to Emulsion G-7a)
Emulsion G-2a to Emulsion G-7a were prepared in the same manner as Emulsion G-1a except that Emulsion G-2 to Emulsion G-7 were used instead of Emulsion G-1. .

(Preparation of emulsion G-1b)
The redispersed emulsion G-1 was dissolved at 40 ° C., and sodium benzenethiosulfonate, p-glutaramide phenyl disulfide, the above exemplified compound (SE3-29) as a selenium sensitizer, and (bis (1,4,5-trimethyl-1,2,4-triazolium-3-thiolate) orate (I) tetrafluoroborate) is added, so that the gradation at 1 × 10 ⁻⁶ second exposure becomes the hardest tone. Aged at 65 ° C. with optimum chemical sensitization. 1- (3-acetamidophenyl) -5-mercaptotetrazole, 1- (5-methylureidophenyl) -5-mercaptotetrazole, compound-2, compound-4 and potassium bromide (1 mol of the finished silver halide) Per 0.35 mol%) was added. Further, spectral sensitization was performed by adding sensitizing dyes S-4, S-5, S-6 and S-7 before addition of the sensitizer. The emulsion thus obtained was designated as Emulsion G-1b.

(Preparation of Emulsion G-2b to Emulsion G-7b)
Emulsion G-2b to Emulsion G-7b were prepared in the same manner as Emulsion G-1b, except that Emulsion G-2 to Emulsion G-7 were used instead of Emulsion G-1. .

(Preparation of Emulsion G-8b to Emulsion G-14b)
Emulsion G-1b to Emulsion G-14b were prepared in the same manner as Emulsion G-1b, except that Emulsion G-8 to Emulsion G-14 were used instead of Emulsion G-1. .

(Preparation of emulsion R-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 amount of K ₄ [Ru (CN) ₆ ] added was increased three times. Otherwise, the emulsion R-1 was prepared in the same manner as the emulsion B-1. The obtained emulsion grains were silver iodobromochloride grains. According to observation and measurement using a transmission electron micrograph (direct method), the emulsion grains were monodisperse cubic grains having a side length of 0.40 μm and a coefficient of variation of 9.5%. there were. The emulsion was subjected to precipitation desalting treatment, and then deionized gelatin, compounds Ab-1, Ab-2, Ab-3, and calcium nitrate were added and redispersed.

(Preparation of emulsion R-2)
In the preparation of Emulsion R-1, K ₂ [IrCl ₅ (H ₂ O)] (6.0 × 10 ⁻⁸ mole per mole of finished silver halide) from 92% to 97% addition of silver nitrate ) And K [IrCl ₄ (H ₂ O) ₂ ] (6.0 × 10 ⁻⁷ mole per mole of finished silver halide) are added in the same manner as emulsion R-1 except that emulsion R-2 is prepared. Prepared.

(Preparation of emulsion R-3)
In the preparation of Emulsion R-2, K ₂ [IrCl ₅ (5-methylthiazole)] (1.0 × 10 ⁻⁷ mol per mol of finished silver halide) from the point when the addition of silver nitrate was between 82% and 88% Emulsion R-3 was prepared in the same manner as Emulsion R-2, except that

(Preparation of Emulsion R-4 to Emulsion R-7)
In the preparation of emulsion R-3, the ratio of K ₂ [IrCl ₅ (H ₂ O)] and K [IrCl ₄ (H ₂ O) ₂ ] and K ₂ [IrCl ₅ (5-methylthiazole)] was maintained, Emulsion R-4 to Emulsion R-7 were prepared in the same manner as Emulsion R-3 except that the respective addition amounts were increased to 3, 10, 30, and 100 times.

(Preparation of Emulsion R-8 to Emulsion R-14)
In the preparation of Emulsion R-1 to Emulsion R-7, K ₂ [RuCl ₅ (NO)] (3.3 × 10 6 per mole of finished silver halide) was added from 0% to 3% of the addition 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 ^-9 mol) was added.

(Preparation of emulsion R-1a)
Re-dispersed emulsion R-1 is dissolved at 40 ° C., and compound-1 is added as sodium benzenethiosulfonate, sulfur, and gold sensitizer, and the gradation at 1 × 10 ⁻⁶ second exposure is the hardest. Thus, aging was carried out at 55 ° C. with optimum chemical sensitization. 1- (3-acetamidophenyl) -5-mercaptotetrazole, 1- (5-methylureidophenyl) -5-mercaptotetrazole, compound-2, compound-4 and potassium bromide (1 mol of the finished silver halide) Per 0.35 mol%) was added. Further, spectral sensitization was performed by adding sensitizing dye S-8 and compound-5 before adding the sensitizer. The emulsion thus obtained was designated as Emulsion R-1a.

(Preparation of emulsion R-2a to emulsion R-7a)
Emulsion R-2a to Emulsion R-7a were prepared in the same manner as Emulsion R-1a except that Emulsion R-2 to Emulsion R-7 were used instead of Emulsion R-1. .

(Preparation of emulsion R-1b)
The re-dispersed emulsion R-1 was dissolved at 40 ° C., sodium benzenethiosulfate, the above exemplified compound (SE3-9) as a selenium sensitizer, and (bis (1,4,5-trimethyl-) as a gold sensitizer. 1,2,4-triazolium-3-thiolate) olate (I) tetrafluoroborate), and the chemical sensitization was optimized so that the gradation at 1 × 10 ⁻⁶ second exposure would be the hardest tone. Aged at ℃. 1- (3-acetamidophenyl) -5-mercaptotetrazole, 1- (5-methylureidophenyl) -5-mercaptotetrazole, compound-2, compound-4 and potassium bromide (1 mol of the finished silver halide) Per 0.35 mol%) was added. Further, spectral sensitization was performed by adding sensitizing dye S-8 and compound-5 before adding the sensitizer. The emulsion thus obtained was designated as Emulsion R-1b.

(Preparation of emulsion R-2b to emulsion R-7b)
Emulsion R-2b to Emulsion R-7b were prepared in the same manner as Emulsion R-1b except that Emulsion R-2 to Emulsion R-7 were used instead of Emulsion R-1. .

(Preparation of Emulsion R-8b to Emulsion R-14b)
Emulsion R-8b to Emulsion R-14b were prepared in the same manner as Emulsion R-1b except that Emulsion R-8 to Emulsion R-14 were used instead of Emulsion R-1 in the preparation of Emulsion R-1b. .

(First layer coating solution preparation)
24 g yellow coupler (Ex-Y), 6 g color image stabilizer (Cpd-8), 1 g color image stabilizer (Cpd-16), 1 g color image stabilizer (Cpd-17), color image stabilizer (Cpd-18) 11 g, 1 g of color image stabilizer (Cpd-19), 11 g of color image stabilizer (Cpd-21), 0.1 g of additive (ExC-3), and 1 g of color image stabilizer (UV-A) as a solvent (Solv) -4) Dissolve in 17 g, 3 g of solvent (Solv-6), 17 g of solvent (Solv-9) and 45 ml of ethyl acetate. Emulsified and dispersed with an emulsifier (dissolver), and water was added to prepare 700 g of an emulsified dispersion A.
The emulsified dispersion A and the emulsion B-1a were mixed in a dissolved state, and a first layer coating solution was prepared so as to have the composition described later. The emulsion coating amount indicates the silver coating amount.

The coating solutions for the second to seventh layers were prepared in the same manner as the first layer coating solution. (H-1), (H-2), and (H-3) were used as gelatin hardeners for each layer. In addition, (Ab-1), (Ab-2), (Ab-3), and (Ab-4) were added to each layer in a total amount of 10.0 mg / m ² , 43.0 mg / m ² , 3.5 mg / was added such that the m ² and 7.0 mg / m ^2.

1- (3-Methylureidophenyl) -5-mercaptotetrazole was added to the second layer, the third layer, and the fifth layer, respectively, 1.20 mg / m ² , 0.36 mg / m ² , 0.44 mg / m ² was added. In the first and fourth layers, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added at 1.5 × 10 ⁻⁴ mol, 1.8 mol per mol of silver halide, respectively. × 10 ^-4 mol was added. 0.05 g / m ² of a copolymer latex of methacrylic acid and butyl acrylate (mass ratio 1: 1, average molecular weight 200,000 to 400,000) was added to the red sensitive emulsion layer. The second layer, was added the third layer and the fifth layer to the disodium catechol-3,5-disulfonate as respectively a ^{25mg / m 2, 11mg / m} 2, 14mg / m 2. Sodium polystyrene sulfonate was added to each layer as necessary to adjust the viscosity of the coating solution. In order to prevent irradiation, the following water-soluble dyes (Dye-1) to (Dye-4) were added (the amount in parentheses represents the coating amount).

(Layer structure)
The structure of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.
Note that in Sample 101, total gelatin coating amount is 4.44 g / ^{m 2,} the total coating設銀weight 0.33 g / ^{m 2,} thickness is 6.2 .mu.m, swollen film thickness was 16.7.

Support Polyethylene resin-laminated paper [White pigment (TiO ₂ ; content: 16% by mass, ZnO; content: 4% by mass), polyethylene brightening agent (4,4′-bis (5- Methylbenzoxazolyl) stilbene (content 0.03% by mass)) and bluish dye (ultraviolet, content 0.33% by mass). The amount of polyethylene resin is 29.2 g / m ² ]

First layer (blue photosensitive emulsion layer)
Emulsion (B-1a) 0.14
Gelatin 1.00
Yellow coupler (Ex-Y) 0.250
Color image stabilizer (Cpd-8) 0.063
Color image stabilizer (Cpd-16) 0.010
Color image stabilizer (Cpd-17) 0.010
Color image stabilizer (Cpd-18) 0.115
Color image stabilizer (Cpd-19) 0.010
Color image stabilizer (Cpd-21) 0.115
Additive (ExC-3) 0.001
Color image stabilizer (UV-A) 0.010
Solvent (Solv-4) 0.177
Solvent (Solv-6) 0.031
Solvent (Solv-9) 0.177

Second layer (intermediate coloring layer)
Gelatin 0.34
Yellow coupler (Ex-Y) 0.085
Color image stabilizer (Cpd-8) 0.021
Color image stabilizer (Cpd-16) 0.004
Color image stabilizer (Cpd-17) 0.004
Color image stabilizer (Cpd-18) 0.039
Color image stabilizer (Cpd-19) 0.004
Color image stabilizer (Cpd-21) 0.039
Additive (ExC-3) 0.0004
Color image stabilizer (UV-A) 0.004
Solvent (Solv-4) 0.060
Solvent (Solv-6) 0.011
Solvent (Solv-9) 0.060

Third layer (color mixing prevention layer)
Gelatin 0.32
Color mixing inhibitor (Cpd-4) 0.020
Color mixing inhibitor (Cpd-12) 0.004
Color image stabilizer (Cpd-3) 0.004
Color image stabilizer (Cpd-5) 0.004
Color image stabilizer (Cpd-6) 0.020
Color image stabilizer (UV-A) 0.020
Color image stabilizer (Cpd-7) 0.002
Solvent (Solv-1) 0.024
Solvent (Solv-2) 0.024
Solvent (Solv-5) 0.028
Solvent (Solv-8) 0.028

Fourth layer (red photosensitive emulsion layer)
Emulsion (R-1a) 0.10
Gelatin 0.80
Cyan coupler (ExC-1) 0.175
Cyan coupler (ExC-2) 0.005
Cyan coupler (ExC-3) 0.015
Color image stabilizer (Cpd-1) 0.011
Color image stabilizer (Cpd-7) 0.011
Color image stabilizer (Cpd-9) 0.033
Color image stabilizer (Cpd-10) 0.001
Color image stabilizer (Cpd-14) 0.001
Color image stabilizer (Cpd-15) 0.165
Color image stabilizer (Cpd-16) 0.035
Color image stabilizer (Cpd-17) 0.022
Color image stabilizer (UV-5) 0.077
Solvent (Solv-5) 0.077

5th layer (color mixing prevention layer)
Gelatin 0.38
Color mixing inhibitor (Cpd-4) 0.024
Color mixing inhibitor (Cpd-12) 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 (Solv-1) 0.029
Solvent (Solv-2) 0.029
Solvent (Solv-5) 0.033
Solvent (Solv-8) 0.033

Sixth layer (green photosensitive emulsion layer)
Emulsion (G-1a) 0.09
Gelatin 1.10
Magenta coupler (Ex-M) 0.14
Color image stabilizer (Cpd-2) 0.01
Color image stabilizer (Cpd-8) 0.01
Color image stabilizer (Cpd-9) 0.005
Color image stabilizer (Cpd-10) 0.005
Color image stabilizer (Cpd-11) 0.0001
Color image stabilizer (Cpd-18) 0.01
Ultraviolet absorber (UV-B) 0.26
Solvent (Solv-3) 0.04
Solvent (Solv-4) 0.08
Solvent (Solv-6) 0.05
Solvent (Solv-9) 0.12
Solvent (Solv-7) 0.11
Compound (S1-4) 0.0015

Seventh layer (protective layer)
Gelatin 0.50
Additive (Cpd-20) 0.015
Liquid paraffin 0.01
Surfactant (Cpd-13) 0.01

  The sample prepared as described above was designated as Sample 101. In Sample 101, a photosensitive material was prepared in which the above emulsion was replaced with the same silver amount instead of the photosensitive emulsions of the first layer, the fourth layer and the sixth layer. Table 2 shows the sample numbers and sample contents.

  Each sample after application was 25 ° C. and 55% R.D. H. In this atmosphere, the film was allowed to elapse for 10 days, and the dural reaction was sufficiently advanced.

(Evaluation 1: Measurement and evaluation of characteristic curve in high illumination exposure)
Each sample was subjected to wedge exposure of 1 × 10 ⁻⁶ seconds using a high illuminance photometer (HIE type, trade name, manufactured by Yamashita Denso Co., Ltd.).
At the time of exposure, so-called blue separation exposure, green separation exposure, or red separation exposure was performed through SP-1, SP-2, or SP-3 filters (all trade names) manufactured by Fuji Photo Film Co., Ltd. After being left for 30 minutes after exposure, color development processing was performed according to the following processing A. Each yellow, magenta, or cyan image reflection density was measured with an optical densitometer, and a characteristic curve of each color image having a vertical axis: reflection density (D) and a horizontal axis: logarithmic exposure (log E) was prepared. In these samples, the yellow image corresponds to the characteristic curve of the blue photosensitive emulsion layer, the magenta image corresponds to the green photosensitive emulsion layer, and the cyan image corresponds to the characteristic curve of the red photosensitive emulsion layer.
In the obtained characteristic curve, the minimum density (Dmin) corresponding to the unexposed portion was defined as fog. In addition, the reciprocal of the exposure amount in the A point giving a reflection density of 0.5 was defined as the sensitivity S _H. A larger value indicates higher sensitivity and is preferable. Furthermore, the point that gives a reflection density of 1.5 is defined as B, and the slope of the straight line connecting points A and B is defined as gradation γ _H. The larger this value is, the higher the gradation is.

(Evaluation 2: Measurement and evaluation of characteristic curve in low illumination exposure)
Each sample was given a 100 second wedge exposure using a sensitometer (FWH type, trade name, manufactured by Fuji Photo Film Co., Ltd.). At the time of exposure, so-called blue separation exposure, green separation exposure, or red separation exposure was performed through SP-1, SP-2, or SP-3 filters (all trade names) manufactured by Fuji Photo Film Co., Ltd. After standing for 30 minutes after exposure, subjected to color development processing according to the processing A below, it was determined sensitivity S _L and gradation gamma _L to create a curve in the same manner as in Evaluation 1. Since the fog does not depend on the exposure conditions, it is the same as the value in the evaluation 1.

(Evaluation 3: Evaluation of storage stability)
Each sample was subjected to 40 ° C 55% R.D. H. After being stored for 30 days in the above atmosphere, exposure, color development processing, and density measurement were performed in the same manner as in the above (Evaluation 1) to prepare a characteristic curve. For each sample, respectively Δ fog fog and sensitivity change amount, as [Delta] S _H, was calculated on the basis of the results of evaluation 1. Δ fog is an amount of change in fog density, which means that ± 0 does not change at all. [Delta] S _H is expressed by a relative value taken as 100 the sensitivity of the evaluation 1, small enough sensitivity change close to 100, preferred.

<Process A>
A 127 mm wide roll sample of “EVER-BEAUTY PAPER TYPE II for LASER (trade name, manufactured by Fuji Photo Film Co., Ltd.)” is added to Digital Minilab Frontier 350 (trade name, manufactured by Fuji Photo Film Co., Ltd.). A standard photographic image was given using a printer. Thereafter, continuous processing (running) was performed in the following processing steps until the volume of the color developer replenisher became twice the volume of the color developer tank. The treatment using this running treatment liquid was designated as treatment A.

As a laser light source for exposure, a blue laser having a wavelength of about 470 nm and a semiconductor laser (oscillation wavelength) obtained by converting the wavelength of a semiconductor laser (oscillation wavelength of about 940 nm) with a LiNbO ₃ SHG crystal having a waveguide inversion domain structure. A green laser having a wavelength of about 530 nm and a red semiconductor laser having a wavelength of about 680 nm were extracted by converting the wavelength of about 1060 nm using a SHG crystal of LiNbO ₃ having a waveguide inversion domain structure. The laser beams of the three colors are moved in the direction perpendicular to the scanning direction by a polygon mirror so that the sample can be sequentially scanned and exposed. The light quantity fluctuation due to the temperature of the semiconductor laser is suppressed by keeping the temperature constant using a Peltier element. The effective beam diameter was 80 μm, the scanning pitch was 42.3 μm (600 dpi), and the average exposure time per pixel was 1.7 × 10 ⁻⁷ seconds. The temperature of the semiconductor laser was made constant by using a Peltier element in order to suppress the change in light quantity due to temperature.

Processing process Temperature Time Replenishment color development 38.5 ° C 45 seconds 45 mL
Bleach fixing 38.0 ° C 45 seconds A 17.5mL
B agent 17.5mL
Rinse 1 38.0 ° C. 20 seconds −
Rinse 2 38.0 ° C 20 seconds-
Rinse 3 38.0 ° C. 20 seconds −
Rinse 4 38.0 ° C 20 seconds 121mL
Dry 80 ° C
(note)
* Replenishment amount per 1 m ^{2 of} photosensitive material ** A rinsing screening system RC50D manufactured by Fuji Photo Film Co., Ltd. is attached to the rinsing 3, and the rinsing liquid is taken out from the rinsing 3 and sent to the reverse osmosis module (RC50D) by a pump. The permeated water sent in the tank is supplied to the rinse 4 and the concentrated solution is returned to the rinse 3. The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 mL / min, and the temperature was circulated for 10 hours per day. The rinsing was a 4-tank counterflow system from 1 to 4.

The composition of each treatment liquid is as follows.
[Color developer] [Tank solution] [Replenisher]
800 ml of water 800 ml
Optical brightener (FL-1) 2.2g 5.1g
Optical brightener (FL-2) 0.35 g 1.75 g
Triisopropanolamine 8.8g 8.8g
Polyethylene glycol average molecular weight 300 10.0 g 10.0 g
Ethylenediaminetetraacetic acid 4.0 g 4.0 g
Sodium sulfite 0.10g 0.20g
Potassium chloride 10.0 g −
4,5-dihydroxybenzene-1,3-
Sodium disulfonate 0.50g 0.50g
Disodium-N, N-bis (sulfonate ethyl) hydroxylamine 8.5 g 14.0 g
4-Amino-3-methyl-N-ethyl-N-
(Β-Methanesulfonamidoethyl) aniline, 3/2 sulfate, monohydrate 4.8 g 14.0 g
Potassium carbonate 26.3g 26.3g
Add water for a total volume of 1000 mL 1000 mL
pH (adjusted with sulfuric acid and KOH at 25 ° C.) 10.15 12.40

[Bleaching Fixer] [Tank Solution] [Replenisher A] [Replenisher B]
Water 800mL 500mL 300mL
Ammonium thiosulfate (750 g / L) 107 mL-386 mL
Ammonium bisulfite (65%) 30.0g-190g
Ethylenediaminetetraacetic acid iron (III)
Ammonium 47.0 g 133 g −
Ethylenediaminetetraacetic acid 1.4g 5g 6g
Nitric acid (67%) 16.5 g 66.0 g −
Imidazole 14.6 g 50.0 g −
m-carboxybenzenesulfinic acid 8.3 g 33.0 g −
Add water to total volume 1000mL 1000mL 1000mL
pH (adjusted with nitric acid and aqueous ammonia at 25 ° C.) 6.5 6.0 6.0

[Rinse solution] [Tank solution] [Replenisher solution]
Chlorinated isocyanurate sodium 0.02g 0.02g
Deionized water (conductivity 5μS / cm or less) 1000mL 1000mL
pH (25 ° C.) 6.5 6.5

The results for the yellow image obtained above are shown in Table 3. The fog, sensitivity S _L , and sensitivity _SH are shown as relative values with the value of the sample 101 being 100, and the higher the value, the higher the sensitivity.

As shown in Table 3, the sample of the present invention was higher in sensitivity than the comparative sample, but had low fog and excellent storage stability. The sample of the present invention has high sensitivity and high contrast, particularly in high illumination exposure, and is excellent in suitability for digital exposure. In addition, when a selenium compound is used, fog is increased and storability is deteriorated as sensitivity is increased. However, in the present invention, it is possible to achieve high sensitivity while keeping fog low. Furthermore, low fog can be maintained even after storage over time, and the film has suitable performance as a color print material.
What is revolutionary in the present invention is that a correlation between these excellent performances and γ _H / γ _L has been found. That is, by using a selenium compound, there is a preferable range in the relationship of γ _H / γ _{L in} order to obtain high sensitivity, high contrast, low fog, and excellent storage stability with respect to digital exposure. I found out that

  A characteristic curve was created for a magenta image and a cyan image in the same manner as described above, and sensitivity, fog, gradation, and storability were evaluated. As in the case of a yellow image, a magenta image and a cyan image were obtained. Also, the result of the sample of the present invention was superior to the comparative sample.

  Further, each sample was subjected to image-wise exposure using digital data using an exposure unit of Digital Minilab Frontier 350 (trade name, manufactured by Fuji Photo Film Co., Ltd.), and then processing A was performed. As a result, it was found that the sample of the present invention had high sensitivity, high contrast, and excellent white background.

Example 2
(Preparation of emulsion B-15)
In the preparation of Emulsion B-8, the addition rate of the nucleation part was changed. The amount of K ₂ [RuCl ₅ (NO)] added was doubled. Otherwise, the emulsion B-15 was prepared in the same manner as the emulsion B-8. The obtained emulsion grains were silver iodobromochloride grains. According to observation and measurement using a transmission electron micrograph (direct method), the emulsion grains were monodisperse cubic grains having a side length of 0.40 μm and a coefficient of variation of 9.5%. there were. The emulsion was subjected to precipitation desalting treatment, and then deionized gelatin, compounds (Ab-1), (Ab-2), (Ab-3), and calcium nitrate were added and redispersed.

(Preparation of emulsion B-16)
In the preparation of Emulsion B-15, K ₂ [IrCl ₅ (H ₂ O)] (2.0 × 10 ⁻⁷ mol per mol of finished silver halide) was added from the point of 92% to 97% of the addition of silver nitrate. ) And K [IrCl ₄ (H ₂ O) ₂ ] (2.0 × 10 ⁻⁸ mole per mole of finished silver halide) are added in the same manner as emulsion B-15 except that emulsion B-16 is prepared. Prepared.

(Preparation of emulsion B-17)
In the preparation of Emulsion B-16, K ₂ [IrCl ₅ (5-methylthiazole)] (6.7 × 10 ⁻⁸ mole per mole of finished silver halide) from the point when the addition of silver nitrate was 82% to the point of 88% Emulsion B-17 was prepared in the same manner as Emulsion B-16, except that (A) was added.

(Preparation of emulsion B-18)
In the preparation of emulsion B-17, the ratio of K ₂ [IrCl ₅ (H ₂ O)] and K [IrCl ₄ (H ₂ O) ₂ ] and K ₂ [IrCl ₅ (5-methylthiazole)] was maintained, Emulsion B-18 was prepared in the same manner as Emulsion B-17 except that each addition amount was increased 3 times.

(Preparation of emulsion B-19)
In the preparation of emulsion B-17, the ratio of K ₂ [IrCl ₅ (H ₂ O)] and K [IrCl ₄ (H ₂ O) ₂ ] and K ₂ [IrCl ₅ (5-methylthiazole)] was maintained, Emulsion B-19 was prepared in the same manner as Emulsion B-17 except that each addition amount was increased 10-fold.

(Preparation of emulsion B-20)
In the preparation of emulsion B-17, the ratio of K ₂ [IrCl ₅ (H ₂ O)] and K [IrCl ₄ (H ₂ O) ₂ ] and K ₂ [IrCl ₅ (5-methylthiazole)] was maintained, Emulsion B-20 was prepared in the same manner as Emulsion B-17 except that each addition amount was increased 30-fold.

(Preparation of emulsion B-21)
In the preparation of emulsion B-17, the ratio of K ₂ [IrCl ₅ (H ₂ O)] and K [IrCl ₄ (H ₂ O) ₂ ] and K ₂ [IrCl ₅ (5-methylthiazole)] was maintained, Emulsion B-21 was prepared in the same manner as Emulsion B-17 except that each addition amount was increased 100-fold.

(Preparation of emulsion B-15b)
Re-dispersed emulsion B-15 was dissolved at 40 ° C., and sodium benzenethiosulfonate, 1- (5-methylureidophenyl) -5-mercaptotetrazole (1/10 of the addition amount at the end of chemical sensitization), selenium The exemplified compound (SE3-29) as a sensitizer and (bis (1,4,5-trimethyl-1,2,4-triazolium-3-thiolate) orate (I) tetrafluoroborate as a gold sensitizer ) Was added, and the chemical sensitization was optimized so that the gradation at the exposure of 1 × 10 ⁻⁶ seconds was the hardest, and the mixture was aged at 60 ° C. Thereafter, the temperature was lowered to 40 ° C., and 1-phenyl-5-mercaptotetrazole, 1- (3-acetamidophenyl) -5-mercaptotetrazole, 1- (5-methylureidophenyl) -5-mercaptotetrazole, compound-2, A compound having repeating unit 2 or 3 represented by compound-3 as a main component (terminal X ₁ and X ₂ are hydroxyl groups), compound-4 and potassium bromide (0.38 mol% per mol of finished silver halide) ) Was added. Further, spectral sensitization was performed by adding sensitizing dyes S-1, S-2, and S-3 before addition of the sensitizer. The emulsion thus obtained was designated as Emulsion B-15b.

(Preparation of Emulsion B-16b to Emulsion B-21b)
Emulsion B-16b to Emulsion B-21b were prepared in the same manner as Emulsion B-15b, except that Emulsion B-16 to Emulsion B-21 were used instead of Emulsion B-15. .

(Preparation of emulsion G-15)
In the preparation of Emulsion G-8, the addition rate of the nucleation part was changed. The amount of K ₂ [RuCl ₅ (NO)] added was increased 2.4 times. Otherwise, the emulsion G-15 was prepared in the same manner as the emulsion G-8. The obtained emulsion grains were silver iodobromochloride grains. According to observation and measurement using a transmission electron micrograph (direct method), the emulsion grains were monodisperse cubic grains having a side length of 0.30 μm and a coefficient of variation of 9.9%. there were. The emulsion was subjected to precipitation desalting treatment, and then deionized gelatin, compounds (Ab-1), (Ab-2), (Ab-3), and calcium nitrate were added and redispersed.

(Preparation of emulsion G-16)
In the preparation of Emulsion G-15, K ₂ [IrCl ₅ (H ₂ O)] (4.8 × 10 ⁻⁸ mole per mole of finished silver halide) from the point of 92% to 97% of addition of silver nitrate ) And K [IrCl ₄ (H ₂ O) ₂ ] (4.8 × 10 ⁻⁷ mol per mol of the finished silver halide) are added in the same manner as Emulsion G-15 except that Emulsion G-16 Prepared.

(Preparation of emulsion G-17)
In the preparation of Emulsion G-16, K ₂ [IrCl ₅ (5-methylthiazole)] (1.6 × 10 ⁻⁷ mole per mole of finished silver halide) from the point when the addition of silver nitrate was 82% to the point of 88% Emulsion G-17 was prepared in the same manner as Emulsion G-16, except that (A) was added.

(Preparation of Emulsion G-18 to Emulsion G-21)
In the preparation of emulsion G-17, the ratio of K ₂ [IrCl ₅ (H ₂ O)] and K [IrCl ₄ (H ₂ O) ₂ ] and K ₂ [IrCl ₅ (5-methylthiazole)] was maintained, Emulsion G-18 to Emulsion G-21 were prepared in the same manner as Emulsion G-17, except that the respective addition amounts were increased to 3, 10, 30, and 100 times.

(Preparation of emulsion G-15b)
The redispersed emulsion G-15 was dissolved at 40 ° C., and sodium benzenethiosulfonate, p-glutaramide phenyl disulfide, the above exemplified compound (SE3-29) as a selenium sensitizer, and (bis (1,4,5-trimethyl-1,2,4-triazolium-3-thiolate) orate (I) tetrafluoroborate) is added, so that the gradation at 1 × 10 ⁻⁶ second exposure becomes the hardest tone. Aged at 65 ° C. with optimum chemical sensitization. 1- (3-acetamidophenyl) -5-mercaptotetrazole, 1- (5-methylureidophenyl) -5-mercaptotetrazole, compound-2, compound-4 and potassium bromide (1 mol of finished silver halide) Per 0.47 mol%). Further, spectral sensitization was performed by adding sensitizing dyes S-4, S-5, S-6 and S-7 before addition of the sensitizer. The thus obtained emulsion was designated as Emulsion G-15b.

(Preparation of Emulsion G-16b to Emulsion G-21b)
Emulsion G-15b to Emulsion G-21b were prepared in the same manner as Emulsion G-15b, except that Emulsion G-16 to Emulsion G-21 were used instead of Emulsion G-15. .

(Preparation of emulsion R-15)
In the preparation of emulsion R-8, the addition rate of the nucleation part was changed. The amount of K ₂ [RuCl ₅ (NO)] added was increased 2.4 times. Otherwise, the emulsion R-15 was prepared in the same manner as the emulsion R-8. The obtained emulsion grains were silver iodobromochloride grains. According to observation and measurement using a transmission electron micrograph (direct method), the emulsion grains were monodisperse cubic grains having a side length of 0.30 μm and a coefficient of variation of 9.9%. there were. The emulsion was subjected to precipitation desalting treatment, and then deionized gelatin, compounds (Ab-1), (Ab-2), (Ab-3), and calcium nitrate were added and redispersed.

(Preparation of emulsion R-16)
In the preparation of Emulsion R-15, K ₂ [IrCl ₅ (H ₂ O)] (1.4 × 10 ⁻⁷ mol per mol of the finished silver halide) was added from the point of 92% to 97% of the addition of silver nitrate. ) And K [IrCl ₄ (H ₂ O) ₂ ] (1.4 × 10 ⁻⁸ mole per mole of finished silver halide) are added in the same manner as emulsion R-15 except that emulsion R-16 is prepared. Prepared.

(Preparation of emulsion R-17)
In the preparation of Emulsion R-16, K ₂ [IrCl ₅ (5-methylthiazole)] (2.4 × 10 ⁻⁷ mol per mol of finished silver halide) from the point when the addition of silver nitrate was 82% to 88% Emulsion R-17 was prepared in the same manner as Emulsion R-16, except that (A) was added.

(Preparation of emulsion R-18 to emulsion R-21)
In the preparation of emulsion R-17, the ratio of K ₂ [IrCl ₅ (H ₂ O)] and K [IrCl ₄ (H ₂ O) ₂ ] and K ₂ [IrCl ₅ (5-methylthiazole)] was maintained. Emulsion R-18 to Emulsion R-21 were prepared in the same manner as Emulsion R-17, except that the respective addition amounts were increased to 3, 10, 30, and 100 times.

(Preparation of emulsion R-15b)
The re-dispersed emulsion R-15 was dissolved at 40 ° C., sodium benzenethiosulfate, the above exemplified compound (SE3-9) as a selenium sensitizer, and (bis (1,4,5-trimethyl-) as a gold sensitizer. 1,2,4-triazolium-3-thiolate) olate (I) tetrafluoroborate), and the chemical sensitization is optimized so that the tone is the hardest when exposed to 1 × 10 ⁻⁶ seconds. Aged at ℃. 1- (3-acetamidophenyl) -5-mercaptotetrazole, 1- (5-methylureidophenyl) -5-mercaptotetrazole, compound-2, compound-4 and potassium bromide (1 mol of finished silver halide) Per 0.47 mol%). Furthermore, spectral sensitization was performed by adding sensitizing dye S-8 and compound-5 before the addition of the sensitizer. The emulsion thus obtained was designated as Emulsion R-15b.

(Preparation of emulsion R-16b to emulsion R-21b)
Emulsion R-16b to Emulsion R-21b were prepared in the same manner as Emulsion R-15b except that Emulsion R-15 to Emulsion R-21 were used instead of Emulsion R-15. .

  In the sample 101 of Example 1, a light-sensitive material was prepared in which the above emulsion was replaced with the same amount of silver instead of the first, fourth and sixth layers. Table 4 shows the sample numbers and sample contents.

  Each sample after application was 25 ° C. and 55% R.D. H. In this atmosphere, the film was allowed to elapse for 10 days, and the dural reaction was sufficiently advanced. These samples 201 to 207 were tested in the same manner as in Example 1, and the results obtained for the yellow image are shown in Table 5 in comparison with the results of samples 101 to 107.

  As shown in Table 5, the sample of the present invention has the same low-illuminance exposure sensitivity as compared to the comparative sample, but is highly sensitive under high-illuminance exposure, has low fog, and is excellent in storage stability. . Similar effects were obtained for magenta images and cyan images. According to the present invention, a color photographic light-sensitive material for high-illuminance exposure that is excellent on a white background can be provided.

  Further, each sample was subjected to image-wise exposure using digital data using a printer of Digital Minilab Frontier 350 (trade name, manufactured by Fuji Photo Film Co., Ltd.), and then processing A was performed. As a result, it was confirmed that the sample of the present invention had high sensitivity, high contrast, and excellent white background.

Example 3
In Example 2, evaluation was performed in the same manner as in Example 2 except that the following process B was used instead of process A. The results obtained for the yellow image are shown in Table 6.

  A standard photographic image was given to a 127 mm-wide roll sample of “EVER-BEAUTY PAPER TYPE II for LASER (trade name, manufactured by Fuji Photo Film Co., Ltd.) by laser exposure described later. Then, using the processor of Digital Minilab Frontier 340 (trade name, manufactured by Fuji Photo Film Co., Ltd.), the processing is continued until the volume of the color developer replenisher is double the color developer tank capacity in the following processing steps (running) ). The treatment using this running treatment liquid was designated as treatment B. In addition, the processor changed the conveyance speed by modifying the processing rack in order to make the following processing time.

<Process B>
Processing process Temperature Time Replenishment amount Color development 45.0 ℃ 12 seconds 35mL
Bleach fixing 40.0 ° C 12 seconds A agent 15mL
B agent 15mL
Rinse 1 45.0 ° C. 4 seconds −
Rinse 2 45.0 ° C. 2 seconds −
Rinse 3 45.0 ° C. 2 seconds −
Rinse 4 45.0 ° C 3 seconds 175 mL
Drying 80 ° C 15 seconds (Note)
* Per photosensitive material 1 m ² replenishment rate

As a laser light source for exposure, a blue semiconductor laser with a wavelength of about 440 nm (announced by Nichia Chemical Co., Ltd. at the 48th Japan Society for Applied Physics) was introduced, and a semiconductor laser (with an oscillation wavelength of about 1060 nm) was introduced. A green laser having a wavelength of about 530 nm and a red semiconductor laser having a wavelength of about 650 nm (Hitachi type No. HL6501MG, trade name) extracted by wavelength conversion using a SHG crystal of LiNbO ₃ having a waveguide inversion domain structure were used. The laser beams of the three colors are moved in the direction perpendicular to the scanning direction by a polygon mirror so that the sample can be sequentially scanned and exposed. The light quantity fluctuation due to the temperature of the semiconductor laser is suppressed by keeping the temperature constant using a Peltier element. The effective beam diameter was 80 μm, the scanning pitch was 42.3 μm (600 dpi), and the average exposure time per pixel was 1.7 × 10 ⁻⁷ seconds. The temperature of the semiconductor laser was made constant by using a Peltier element in order to suppress the change in light quantity due to temperature.

The composition of each treatment liquid is as follows.
[Color developer] [Tank solution] [Replenisher]
800 ml of water 800 ml
Optical brightening agent (FL-3) 4.0 g 10.0 g
Residual color reducing agent (SR-1) 3.0 g 3.0 g
m-Carboxybenzenesulfinic acid 2.0 g 4.0 g
Sodium p-toluenesulfonate 10.0 g 10.0 g
Ethylenediaminetetraacetic acid 4.0 g 4.0 g
Sodium sulfite 0.10g 0.10g
Potassium chloride 10.0 g −
4,5-dihydroxybenzene-1,3-
Sodium disulfonate 0.50g 0.50g
Disodium-N, N-bis (sulfonate ethyl) hydroxylamine 8.5 g 14.0 g
4-Amino-3-methyl-N-ethyl-N-
(Β-Methanesulfonamidoethyl) aniline
3/2 Sulfate / Monohydride 7.0g 19.0g
Potassium carbonate 26.3g 26.3g
Add water for a total volume of 1000 mL 1000 mL
pH (adjusted with sulfuric acid and KOH at 25 ° C.) 10.25 12.8

[Bleaching Fixer] [Tank Solution] [Replenisher A] [Replenisher B]
Water 700mL 300mL 300mL
Ammonium thiosulfate (750 g / L) 107 mL-400 mL
Ammonium sulfite 30.0 g − −
Ethylenediaminetetraacetic acid iron (III)
Ammonium 47.0g 200g-
Ethylenediaminetetraacetic acid 1.4 g 0.5 g 10.0 g
Nitric acid (67%) 7.0 g 30.0 g −
m-carboxybenzenesulfinic acid 3.0 g 13.0 g −
Ammonium bisulfite solution (65%)--200 g
Succinic acid 7.0 g 30.0 g −
Add water to total volume 1000mL 1000mL 1000mL
pH (adjusted with 25 ° C, nitric acid and aqueous ammonia) 6.0 2.0 5.6

[Rinse solution] [Tank solution] [Replenisher solution]
Chlorinated isocyanurate sodium 0.02g 0.02g
Deionized water (conductivity 5μS / cm or less) 1000mL 1000mL
pH (25 ° C.) 6.5 6.5

  As shown in Table 6, the sample of the present invention has the same low illuminance exposure sensitivity as compared to the comparative sample, is highly sensitive under high illuminance exposure, has low fog, and is excellent in storage stability. . Compared with the results of Example 2, the sample using the selenium compound tends to increase fog by rapid treatment, but it is clear that the present invention suppresses this adverse effect and gives favorable results. The same effect could be obtained for magenta images and cyan images. According to the present invention, a color photographic light-sensitive material suitable for rapid processing excellent in white background can be provided.

Further, each sample was subjected to image-wise exposure using digital data using the laser exposure unit used when the running processing solution was prepared, and then the processing B was performed. As a result, it was found that the sample of the present invention had high sensitivity, high contrast, and excellent white background.

Claims (5)

A silver halide color photographic light-sensitive material having at least one red-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer and blue-sensitive silver halide emulsion layer on a support, the silver halide emulsion layer At least one layer of 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 and at least a metal complex represented by the following general formula (D1): A silver halide color photographic light-sensitive material containing one kind , wherein a characteristic curve of a silver halide emulsion layer containing the silver halide emulsion satisfies the following formula (1).
Formula (1) 2.0 ≧ γ _H / γ _L ≧ 0.5
Here, γ represents the gradation of the characteristic curve, γ _H represents the gradation in 1 × 10 ⁻⁶ second exposure, and γ _L represents the gradation in 100 second exposure.
General formula (D1)
[M ^D1 X ^D1 _n1 L ^D1 _(6-n1) ] ^m1
In the general formula (D1), M ^D1 represents Cr, Mo, Re, Fe, Ru, Os, Co, Rh, Pd, or Pt, and X ^D1 represents a halogen ion. L ^D1 represents an arbitrary ligand different from X ^D1 . n1 represents 3, 4, 5, or 6, m1 represents the charge of the metal complex, and represents 4-, 3-, 2-, 1-, 0, or 1+. Further, a plurality of X ^D1 may be the same or different from each other , and when a plurality of L ^D1 are present, these may be the same or different from each other. However, the metal complex represented by the general formula (D1) does not have or has only one cyano (CN ⁻ ) ligand. Said silver halide emulsion containing selenium compound, further silver halide color photographic described metal complex represented by the following general formula (D2) to 請 Motomeko 1 you characterized in that it contains at least one material.
General formula (D2)
[IrX ^D2 _n2 L ^D2 _(6-n2) ] ^m2
In formula ^{(D2), X D2} is a halogen ion or a pseudohalogen ion (although cyanate ion OCN ^- excluding) representative of. L ^D2 represents an arbitrary ligand different from X ^D2 . n2 represents 3, 4, or 5, m2 represents the charge of the metal complex, and represents 4-, 3-, 2-, 1-, 0, or 1+. In addition, a plurality of X ^D2 may be the same as or different from each other, and when a plurality of L ^D2 are present, these may be the same as or different from each other. 3. The silver halide color photographic light-sensitive material according to claim 1, wherein an average equivalent sphere diameter of silver halide grains of the silver halide emulsion containing a selenium compound is 0.65 [mu] m or less. The silver halide color photographic light-sensitive material according to any one of claims 1 to 3 , wherein the total coated silver amount is 0.2 g / m ² or more and 0.5 g / m ² or less. The silver halide color photographic light-sensitive material according to any one of claims 1 to 4 , wherein the total coated gelatin amount is 3 g / m ² or more and 6 g / m ² or less.