JPH07209783A - Silver halide emulsion and silver halide photographic sensitive material using same - Google Patents

Abstract

PURPOSE:To obtain the silver halide emulsion superior in storage stability and rapid processability and high in sensitivity by spectrally sensitizing high silver chloride content flat grains with a specified dye. CONSTITUTION:The silver halide emulsion contains the flat silver grains having two parallel principal faces (100), an aspect ratio of >=2, and a silver chloride content of >=50mol% in 50% of the projection areas of the total silver halide grains, and the emulsion is spectrally sensitized with the cyanine dye of formula I and/or that of formula II in both of which Z1 is O, S, or the like; Z2 is S or Se; each of W1, W3, W4, and W6 is H; W2 is Br, aryl, or the like; W5 is Br, alkyl, or the like: each of R1 and R2 is alkyl or alkenyl: each of Y1 and Y2 is S or Se; each of V1 and V3 is H; V2 is CE, aryl, or the like; V5 is a group necessary to form a benzene ring together with V4 or V6; and each of R3 and R4 is same as R1 and R2.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide emulsion excellent in photographic sensitivity and a photographic light-sensitive material using the emulsion.

[0002]

2. Description of the Related Art At present, there is an increasing demand for rapid processing of silver halide photographic light-sensitive materials. Although silver bromide is generally used as a photographic light-sensitive material, silver chloride is advantageous for rapid processing. Further, use of tabular grains is advantageous from the viewpoint of photographic sensitivity, sharpness, etc., but since the main plane is the {111} plane, there is a problem in that intrinsic desensitization by the dye is large. Therefore, {100} on the main plane
The use of flat plates with faces is conceivable. The silver chloride particles as the silver halide particles have a problem that the dye is weakly adsorbed, the color sensitization is weak, and the storage stability is deteriorated. From the above, it has been desired to develop silver halide grains and sensitizing dyes which have both rapid processing and improved color sensitization and storage stability.

A. MIGNOT, E.I. FRANCOIS
AND M. CATINAT, "CRISTAUX
DE RBOMURE D'ARGENT PLAT
S, LIMITES PAR DES FACES (1
00) ET NON MACLES ”, Journal
of Crystal Growth 123 (19
74) According to the report of 207-213, tabular silver bromide crystals formed of {100} planes having a square or rectangular main plane are observed.

According to the disclosure of US Pat. No. 4,063,951 the tabular grains formed by {100} crystal faces are formed from monodisperse seed grains and, when aged in the presence of ammonia, the tabular grains average. Aspect ratio is 1.5
Formed to have a range of ˜7. U.S. Pat. No. 4,386,156 discloses a tabular silver bromide emulsion formed so as to have an average aspect ratio of 8 or more by aging seed grains in the absence of a non-halide silver ion complexing agent. Is shown. A method for producing tabular grains having a high silver chloride content is disclosed in European Patent 534,395A1.

Although there are reports of emulsions occupied by tabular silver halide grains having {100} crystal planes as the main planes, when these are used as silver halide photographic light-sensitive materials, they are particularly sensitized by color. From the viewpoint, further improvement is required.

[0006]

DISCLOSURE OF THE INVENTION The present invention is {100}
A high-sensitivity silver halide emulsion excellent in storability and rapid processing was prepared by subjecting a high-silver chloride tabular grain emulsion whose main surface is a plane to spectral sensitization using a dye having a specific structure, and using the emulsion. It is to provide a photographic light-sensitive material.

[0007]

[Means for Solving the Problems] The above-mentioned problems are as follows (1)
It was solved by means of (4).

(1) A tabular silver halide grain having two parallel main planes of {100} planes, an aspect ratio of 2 or more, and an average silver chloride content of the grain of 50 mol% or more is halogen. At least one cyanine dye having a structure represented by the general formula (I) in a silver halide emulsion characterized by occupying 50% or more of the total projected area of silver halide grains or /
And a silver halide emulsion characterized by being spectrally sensitized with at least one cyanine dye having a structure represented by the general formula (II). General formula (I)

[0009]

[Chemical 3]

In the formula, Z ₁ represents an oxygen atom, a sulfur atom or a selenium atom, and Z ₂ represents a sulfur atom or a selenium atom. W ₁ , W ₃ , W ₄ and W ₆ represent a hydrogen atom. W ₂
Represents a bromine atom or an optionally substituted aryl group having 9 or less carbon atoms, and when Z ₁ represents an oxygen atom, it may combine with W ₁ or W ₃ to form a benzene ring. . W ₅ is a bromine atom or an aryl group having a total carbon number of 9 or less, an alkyl group having a carbon number of 3 to 6 (for example, a propyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, etc.), a carbon number of 3 to 6 Alkoxy group (eg, propoxy group, butoxy group, pentyloxy group, hexyloxy group, etc.), phenoxy group having a total carbon number of 9 or less (eg, tolyloxy group, anisyloxy group,
Chlorophenoxy group, etc.), an optionally substituted phenylthio group having a total carbon number of 8 or less (eg, tolylthio group, anisylthio group, chlorophenylthio group, etc.), and Z
_{When 1} represents an oxygen atom, it may combine with W ₄ or W ₆ to form a benzene ring. The substituent of the aryl group represented by W ₂ and W ₅ is an optionally branched alkyl group having 5 or less carbon atoms (eg, methyl group, ethyl group, butyl group, isobutyl group, pentyl group, etc.). ), An alkoxy group having a total carbon number of 4 or less (for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a methoxymethoxy group, a methoxyethoxy group, etc.), a chlorine atom, a bromine atom, and a carbon number of 4 or less. It is an acylamino group (eg, an acetylamino group, a propionylamino group, etc.). Further, a plurality of these different or the same kind of substituents may be substituted.

R ₁ and R ₂ may be the same or different and each represents an optionally substituted alkyl group or alkenyl group having 10 or less carbon atoms, and at least one of R _{1 and} R ₂ is a sulfo group. A group having a group. More preferable substituents of the alkyl group and the alkenyl group include, for example, a sulfo group, a carboxy group, a halogen atom, a hydroxy group, an alkoxy group having 6 or less carbon atoms, and an optionally substituted aryl group having 8 or less carbon atoms (for example, , Phenyl group,
Tolyl group, sulfophenyl group, carboxyphenyl group, etc.), heterocyclic group (eg, furyl group, cenyl group, etc.),
An optionally substituted aryloxy group having 8 or less carbon atoms (eg, chlorophenoxy group, phenoxy group, sulfophenoxy group, hydroxyphenoxy group), an acyl group having 8 or less carbon atoms (eg, acetyl group, propionyl group, etc.) , An alkyl or phenylsulfonyl group having 8 or less carbon atoms (eg, benzenesulfonyl group, methanesulfonyl group, etc.), an alkoxycarbonyl group having 6 or less carbon atoms (eg, ethoxycarbonyl group, butoxycarbonyl group, etc.), cyano group, carbon number An alkylthio group having 6 or less (eg, methylthio group, ethylthio group, etc.), an arylthio group having 8 or less carbon atoms which may be substituted (eg, phenylthio group, tolylthio group, etc.), and having 8 or less carbon atoms A good carbamoyl group (eg, carbamoyl group, N-ethylcarbamoyl group Group, etc.), an acylamino group having 8 or less carbon atoms (eg, acetylamino group, etc.), an alkylsulfonylamino group having 8 or less carbon atoms (eg, methanesulfonylamino group, etc.), a ureido group, an alkylureido having 6 or less carbon atoms. Group (eg, methylureido group, ethylureido group, etc.), acylaminocarbonyl group having 6 or less carbon atoms (eg, acetylaminocarbonyl group, propionylaminocarbonyl group, etc.), alkylsulfonylaminocarbonyl group (eg, methanesulfonylaminocarbonyl) Group, ethanesulfonylaminocarbonyl group, etc.)
Is mentioned. It may have one or more substituents.

X ₁ represents a counter ion necessary for neutralizing the electric charge. n ₁ represents 0 or 1, and is 0 in the case of an inner salt.

General formula (II)

[0014]

[Chemical 4]

In the formula, Y ₁ and Y ₂ may be the same or different and each represents a sulfur atom or a selenium atom. V ₁ and V ₃ represent a hydrogen atom. V ₂ is a chlorine atom, a bromine atom or an aryl group having a total carbon number of 9 or less (for example, a tolyl group,
Anisyl group, chlorophenyl group, bromophenyl group, phenyl group, pyridyl group, cenyl group, etc.), C3-6
An alkyl group (for example, propyl group, butyl group, isobutyl group, pentyl group, hexyl group, etc.), an alkoxy group having 3 to 6 carbon atoms (for example, propoxy group, butoxy group, pentyloxy group, hexyloxy group, etc.), An optionally substituted phenoxy group having a total carbon number of 9 or less (eg, tolyloxy group, anisyloxy group, chlorophenoxy group, etc.), an optionally substituted phenylthio group having a total carbon number of 8 or less (eg, tolylthio group, anisylthio group, etc. Group, a chlorophenylthio group, etc.) and may be linked to V ₁ or V ₃ to form a benzene ring. V ₅ represents connecting with V ₄ or V ₆ to form a benzene ring.

R ₃ and R _{4, which} may be the same or different, have the same meaning as R ₁ or R _{2 in} formula (I), and at least one of R ₃ and R ₄ has a sulfo group. Is. X ₂ represents a counter ion necessary for neutralizing the charge. n ₂ represents 0 or 1, and is 0 in the case of an inner salt.
Is. (2) A silver halide photographic light-sensitive material characterized in that at least one silver halide emulsion layer provided on a support contains the silver halide emulsion of (1) above. (3) The silver halide photographic light-sensitive material according to (2) above, wherein the tabular silver halide grains are sensitized with gold and sulfur. (4) In the presence of a dye in which the tabular silver halide grains have at least one cyanine dye having a structure represented by the general formula (I) and / or a cyanine dye having a structure represented by the general formula (II). The silver halide photographic light-sensitive material according to (2) above, which is sensitized with gold and sulfur.

The tabular grain emulsion having a high silver chloride content of the present invention can be produced as follows. 1) Nucleation process The tabular nuclei, which are the nuclei of tabular grains, have a high production ratio under the condition that the introduction of lattice defects easily occurs. As a method for obtaining plate nuclei with high reproducibility and a high production ratio, a method utilizing halogen conversion of product nuclei is effective. In this method, first, silver halide nucleation is carried out, and subsequently, halogen ions for forming a more sparingly soluble silver halide are introduced to carry out halogen conversion. More specifically, the halogen composition structure of the nuclei formed during nucleation is, for example, (AgX ₁ | AgX ₂ ) or (AgX ₁ | AgX ₂ ).
gX ₁ | AgX ₄ | AgX ₃ ). The structure is obtained, for example, by simultaneously mixing and adding a silver salt aqueous solution (hereinafter referred to as “Ag ⁺ liquid”) and a halide salt aqueous solution (hereinafter referred to as “X ⁻ liquid”), and adding X ⁻ liquid at the gap surface. Can be formed by discontinuously changing the halogen composition of. Or a dispersion medium solution X ^- solution was added, followed by the addition of Ag ⁺ solution to form AgX _1, then another X ^- adding liquid, followed by addition of Ag ⁺ solution, (AgX ₁ The | AgX ₂ ) structure can be prepared, or a combination thereof can be prepared.

AgX ₁ and AgX ₂ and AgX ₁ and Ag
X ₄ , AgX ₄ and AgX ₃ are Cl ⁻ content or Br ⁻
The contents differ by 25 to 100 mol%, preferably 50 to 100 mol%, more preferably 75 to 100 mol%.
Further / or the I ^- contents differ by 5-100 mol%, preferably 10-100 mol%, more preferably 30-100 mol%. In addition, an embodiment in which the difference in Cl ⁻ content or the difference in Br ⁻ content is in accordance with the above definition and the difference in I ⁻ content is 0 to 5 mol% can be mentioned. The size of the nucleus is 0.15
It is preferably not more than μm, more preferably 0.01 to 0.1 μm. AgX ₁ : Ag in the case of (AgX ₁ | AgX ₂ ).
X ₂ molar ratio, and (AgX ₁ | AgX ₄ | Ag
The molar ratio of AgX ₁ : AgX ₂ : AgX ₃ in X ₃ ) can be variously changed, and the molar ratio that provides the most preferable embodiment of the present invention can be selected and used.

The atmosphere of the dispersion medium solution at the time of nucleation is {10
It is necessary to create a 0} plane forming atmosphere. In the case of nucleation performed under Cl ^- excess concentration, most of the usual conditions (pCl
0.8-3.0, pH 2-9) is a {100} plane forming atmosphere. The defect formation frequency is pH 1 to 7
Becomes higher and the pCl value becomes higher, the frequency of defect formation becomes higher. Here, pCl = −log [mol of Cl ⁻ / L].

The concentration of the dispersion medium in the dispersion medium solution at the time of nucleation is 0.
1 to 10% by weight is preferable, and 0.3 to 5% by weight is more preferable. 1-10 are preferable and, as for pH, 2-8 are more preferable. The temperature is preferably 10 to 80 ° C, more preferably 30 to 60 ° C. The excess Br ⁻ concentration is preferably 10 ⁻² mol / L or less, more preferably 10 ^−2.5 mol / L or less. The excess Cl ⁻ concentration is preferably pCl = 0.8 to 3.0.
2-2.8 is more preferable.

Can be included salt solution in the dispersion medium ^- The silver salt solution and / or X during nucleation is added to allow for uniform nucleation. Dispersion medium concentration is 0.1% by weight
The above is preferable, 0.1 to 2% by weight is more preferable,
0.2 to 1% by weight is more preferable. Molecular weight 3000-6
10,000, preferably 8,000 to 40,000 low molecular weight gelatin is more preferable. Furthermore Ag ⁺ solution and X ^- liquid addition porosities 3
10 ^15, preferably through 30 to 10 ¹⁵ porous addition system, it is more preferably added directly to the liquid. The details are described in JP-A-3-21339 and 4-193336.
The description in Japanese Patent Application No. 4-240283 can be referred to. Gelatin having a lower methionine content has a higher frequency of defect formation. Methionine content is 1 to
From 60 μmol / g of gelatin, the most preferable gelatin can be selected and used according to each case.

Excess X ^- salt concentration during nucleation, or excess A
By lowering the g ⁺ salt concentration, the mixing ratio of twin grains can be reduced.

In a dispersion medium solution containing at least a dispersion medium and water, an aqueous silver salt solution and a halide salt (hereinafter,
X ^- salt) solution is added by a double-mix method to form nuclei. The Cl ⁻ concentration in the dispersion medium solution during nucleation is preferably 10 ^−1.5 mol / liter or less, and the Ag ⁺ concentration is preferably 10 ⁻² mol / liter or less. The pH is preferably 2 or more,
5-10 are more preferable. The gelatin concentration is preferably 0.1 to 3% by weight, more preferably 0.2 to 2% by weight.

The temperature during nucleation is not limited, but usually 1
0 degreeC or more is preferable and 20-70 degreeC is preferable. After the nucleation, physical ripening is performed to eliminate non-tabular grains and grow the tabular grains. The addition rate of the aqueous silver salt solution is 1 for container solution.
0.5-20 g / min is preferable per liter, 1-1
5 g / min is more preferred. The pH of the container solution is not particularly limited, but is usually pH 1 to 11, preferably pH 3 to 10.
Is used. The most preferable pH value can be selected and used according to the combination of excess silver salt concentration, temperature, and the like.

2) Aging Process It is not possible to separately prepare tabular grain nuclei during nucleation. Therefore, in the next ripening process, Ostwald ripening causes the tabular grains to grow and the other grains to disappear. The aging temperature is 40 ° C or higher, preferably 45 to 90 ° C, more preferably 50 to 80 ° C.

Aging is preferably performed in a {100} plane forming atmosphere. Aging conditions are preferably selected from the nucleation condition range. The ripening rate generally becomes faster in the region of pH 1 to 6 as the pH becomes higher, and in the region of pCl1 to 3 as the Cl ^- concentration increases.

In the present invention, it is preferable that a silver halide solvent is not substantially allowed to coexist during ripening. Here, substantially means that the silver halide solvent concentration d ₀ is preferably d ₀ ≦ 0.5 mol / liter, more preferably d _0.
<0.1 mol / liter, more preferably d ₀ <0.0
Refers to 2 mol / liter.

The pH during aging is 1 to 12, preferably 2 to
8, more preferably 2-6.

As the dispersion medium for nucleation, ripening and growth, a conventionally known dispersion medium for silver halide emulsions can be used, but the methionine content is particularly preferably 0-5.
0 μmol / g, more preferably 0 to 30 μmol / g gelatin can be preferably used. When the gelatin is used during ripening and growth, thinner tabular grains having a uniform diameter size distribution are formed, which is preferable. Also, Japanese Examined Patent Publication No. 52-16365, Journal of the Photographic Society of Japan, 29 volumes (1), 17, 22 (1966), 30 volumes (1),
10, 19 (1967), 30 volumes (2), 17 (1)
967), 33 (3), 24 (1967). Further, the crystal habit controlling agent described in European Patent 0534395A1 can be used in combination. The dispersion medium concentration is 0.1 to
10 wt% is preferable, and the control agent is preferably 10 ^-1 to
10 ⁻⁶ mol / L, more preferably 10 ⁻² to 10 ⁻⁵ mol / L
Can be used for L. These can be added at any time from before nucleation to the end of growth. It can be added in the form of additional addition to the existing dispersion medium, or can be added after removing the existing dispersion medium by centrifugation or the like. 3) Growth process After increasing the tabular grain ratio by aging, a solute is added next to further grow the tabular grains. As a solute addition method, 1) a solution addition method (a method of adding a silver salt aqueous solution and a halide salt aqueous solution), 2) a method of previously forming fine silver halide grains and adding the fine grains, 3) a combination of both A method can be mentioned. In order to preferentially grow the tabular grains in the edge direction, it is necessary to grow the tabular grains at a low supersaturation concentration within a range that does not undergo Ostwald ripening. That is, it is necessary to control the concentration at a low supersaturation level with high accuracy. The method 2) is more preferable because it enables this.

In the fine grain emulsion addition method, the diameter is 0.15 μm or less, preferably 0.1 μm or less, more preferably 0.1 μm or less.
A silver halide fine grain emulsion having a grain size of 06 μm or less is added, and the tabular grains are grown by Ostwald ripening. The fine grain emulsion can be added continuously or intermittently. The fine grain emulsion can be continuously prepared by supplying an aqueous solution of silver salt and an aqueous solution of halide salt in a mixer provided in the vicinity of the reaction vessel, and can be continuously added to the reaction vessel immediately or in advance in another vessel. It is also possible to add it continuously or intermittently after it is prepared in a batch manner. It is preferable that the fine particles are substantially free of twin grains. The term “substantially free” means that the twin crystal grain number ratio is 5% or less, preferably 1% or less, and more preferably 0.1% or less.

The halogen composition of the fine grains may be silver chloride, silver bromide, silver iodide, or a mixed crystal of two or more kinds thereof.

The solution conditions during grain growth are the same as the above-mentioned aging conditions. This is because both are steps in which tabular grains are grown by Ostwald ripening and other fine particles are eliminated, and they are mechanically the same. For details of the method for adding a fine grain emulsion, see Japanese Patent Application No. 2-142635,
The description in JP-A-4-77261 and JP-A-1-183417 can be referred to. In order to form fine particles having substantially no twin planes, the excess halogen ion concentration or the excess silver ion concentration is preferably 10 ^-2 mol / liter or less, and the silver salt aqueous solution and the halide salt aqueous solution are simultaneously mixed and added. It may be added by a method.

The fine particle forming temperature is preferably 50 ° C. or lower,
5-40 degreeC is more preferable, and 10-30 degreeC is still more preferable. The dispersion medium preferably has a molecular weight of 2000 to 6 × 10.
⁴ , more preferably 5000-4 × 10 ⁴ low molecular weight gelatin, preferably 30% by weight or more, more preferably 6
Gelatin occupying 0% by weight or more, and more preferably 80% by weight or more is preferable. The dispersion medium concentration is preferably 0.2% by weight or more, more preferably 0.5 to 5% by weight.

In the nucleation process, substantially NH₃Coexist with
Preferably not. Here, “substantially” means according to the above rules.
U NH during growth₃It is preferred not to coexist.
Here, “substantially” means NH₃Concentration Z₁Is Z₁≤ 0.5 mol
/ Liter, more preferably Z ₁<0.1 mol / lit
And more preferably Z₁<0.02 mol / liter
Means that. NH for nucleation and growth process₃Other than
It is preferable that substantially no AgX solvent is also allowed to coexist.
Here, “substantially” means Z₁It is the same as the concentration regulation. N
H₃Other than AgX solvent, thioethers, thio
Urea, thiocyanate, organic amine compounds, tetra
Antifoggants such as Zaindene compounds
Thioethers, thioureas, thiosines
Anionate.

Dislocation lines can be introduced into the grains during the grain formation by the halogen composition gap method, the halogen conversion method, the epitaxial growth method and a combination thereof. The pressure fog characteristics and reciprocity law characteristics and the color sensitization characteristics are further improved, which is preferable. Regarding this, JP-A-63-2
20238, 64-26839, JP-A-2-1276
35, ibid 3-189642, ibid 3-175440, ibid 2
-123346, European Patent 0460656A1 Journal
of Imaging Science, 32 volumes, 160-177 (19
88) can be referred to.

The obtained particles may be used as host particles to form epitaxial particles for use. Further, particles having dislocation lines inside may be formed using the particles as a core.
In addition, using the grains as a substrate, a silver halide layer having a halogen composition different from that of the substrate is laminated,
It is also possible to make particles of various known particle structures. Regarding these, it is possible to refer to the description of the literature described later.

Further, a shallow inner latent emulsion may be formed and used by using the tabular grains as a core. It is also possible to form core / shell type particles. Regarding this, JP-A-59-
133542, 63-151618, U.S. Pat. Nos. 3,206,313, 3,317,322, 3,761,276, 4,269,927, 3,367,778. Can be referred to.

As described above, the most important parameter for finally obtaining a silver halide grain having a high aspect ratio is pAg at the time of ripening and growth, and the aspect ratio of the tabular grain in the present invention is 2 or more. It is 15 or less. The aspect ratio is preferably 3 or more and 13 or less, and more preferably 4 or more and 10 or less. The aspect ratio is preferably in the above range mainly due to the balance between sensitivity and pressure.

As used herein, "aspect ratio" refers to the ratio of the thickness between major planes to the average edge length that forms the major plane of the grain, and "major plane" substantially forms the cuboid emulsion grains. Of the crystal surfaces, the area is defined as a set of parallel planes having the largest area, and the fact that the main plane is the {100} plane can be examined by an electron beam diffraction method or an X-ray diffraction method. A substantially rectangular parallelepiped emulsion grain has a main plane of {10
Although it is formed from the 0} plane, it means that it may have 1 to 8 {111} crystal planes. That is, 1 to 8 out of the eight corners of the rectangular parallelepiped may have a cornered shape. The "average edge length" is defined as the length of one side of a square having an area equal to the projected area of each grain seen in the micrograph of the emulsion grain sample.

The tabular grains in the present invention account for 50% or more, preferably 60% or more, and more preferably 70% or more of the total projected area of the silver halide grains. In both cases, the upper limit is 100%.

The present invention is based on the invention of adsorbing a dye having a specific structure on the surface of a tabular grain having a {100} plane as a main plane formed through a nucleation process, a ripening process and a growth process. The average silver chloride content in the tabular grains present in the emulsion is 50 mol% or more and less than 100 mol%, and 70 mol% or more and 99.9% or more.
It is preferably 9 mol% or less, and 80 mol% or more 9
It is more preferably 9.95 mol% or less.

Specific examples of the groups represented by R ₁ , R ₂ , R ₃ and R _{4 in the} cyanine dye represented by the general formula (I) or the general formula (II) used in the present invention are as follows. Are, for example, methyl group, ethyl group, propyl group, allyl group, pentyl group, hexyl group, methoxyethyl group, ethoxyethyl group, phenethyl group, tolylethyl group, sulfophenethyl group, 2,2,2-trifluoroethyl group,
2,2,3,3-tetrafluoropropyl group, carbamoylethyl group, hydroxyethyl group, 2- (2-hydroxyethoxy) ethyl group, carboxymethyl group, carboxyethyl group, ethoxycarbonylmethyl group, sulfoethyl group, 2- Chloro-3-sulfopropyl group, 3-sulfopropyl group, 2-hydroxy-3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, 2-
(2,3-Dihydroxypropyloxy) ethyl group or 2- [2- (3-sulfopropyloxy) ethoxy]
Examples thereof include an ethyl group, a methanesulfonylaminocarbonylmethyl group, a methanesulfonylaminocarbonylethyl group, an ethanesulfonylaminocarbonylethyl group and an acetylaminocarbonyl group.

The general formula (I) or the general formula (I
Among the cyanine dyes represented by I), the following cyanine dyes are more preferably used in the present invention.

That is, in the cyanine dye represented by the general formula (I), more preferable dye is that when Z ₁ represents an oxygen atom, W ₂ represents an unsubstituted phenyl group or a substituted phenyl group. Or W ₅ or W ₃ to form a benzene ring, and W ₅ represents a bromine atom, an unsubstituted phenyl group or a substituted phenyl group, or is connected to W ₄ or W _6. To form a benzene ring. Further, when Z ₁ represents a sulfur atom or a selenium atom, W ₂ represents a bromine atom, an unsubstituted phenyl group or a substituted phenyl group, and W ₅ represents a bromine atom or a substituted phenyl group. Furthermore, in the cyanine dye represented by the general formula (I), a particularly preferred cyanine dye is such that when Z ₁ represents an oxygen atom, W ₂ represents a chlorine atom, a bromine atom, a methoxy group or an ethoxy group. Represents a phenyl group substituted with a methyl group or an ethyl group, and W ₅ represents a phenyl group or a bromine atom substituted with a chlorine atom, a bromine atom, a methoxy group, an ethoxy group, a methyl group, an ethyl group, or W _This is the case where ₄ or W ₆ is linked to form a benzene ring. A particularly preferred cyanine dye when Z ₁ represents a sulfur atom or a selenium atom is a case where W ₂ and W ₅ represent a bromine atom or the above-mentioned substituted phenyl group.

In the cyanine dye represented by the general formula (II), more preferable dye is a phenyl group in which Z ₁ is substituted with chlorine atom, bromine atom, methoxy group, ethoxy group, methyl group or ethyl group. Or represents a bromine atom, or forms a benzene ring by coupling with V ₁ or V ₃ , Z
_It is particularly preferable that ₁ is a phenyl group substituted with the above-mentioned substituent or a bromine atom.

The cyanine dyes represented by formula (I) and / or formula (II) used in the present invention can be incorporated in the silver halide emulsion of the present invention by dispersing them directly in the emulsion. Or water, methanol, ethanol, propanol, acetone, methyl cellosolve, 2,
2,3,3-tetrafluoropropanol, 2,2,2
-Dissolved in a solvent such as trifluoroethanol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, 1-methoxy-2-propanol, acetonitrile, tetrahydrofuran, N, N-dimethylformamide, alone or in a mixed solvent. May be added to the emulsion. Further, as described in US Pat. No. 3,469,987, etc., a dye is dissolved in a volatile organic solvent, the solution is dispersed in water or a hydrophilic colloid, and this dispersion is added to an emulsion. And a method in which a water-insoluble dye is dispersed in a water-soluble solvent without being dissolved and the dispersion is added to an emulsion, US Pat. No. 3,822, for example. , 135, U.S. Pat. No. 4,006,0
25, etc., a method of adding an aqueous solution or colloidal dispersion in the presence of a surfactant into an emulsion, JP-A-53-102,733, JP-A-58-105, No. 141, a method in which a dye is directly dispersed in a hydrophilic colloid and the dispersion is added to an emulsion, and a compound for red-shifting is used, as described in JP-A-51-74624. Dissolve the dye,
It is also possible to use a method of adding the solution into the emulsion.
Also, ultrasonic waves can be used for dissolution. A more preferred method of incorporating the cyanine dye represented by the general formula (I) or / and the general formula (II) used in the present invention into the silver halide emulsion of the present invention is to add them to water or a hydrophilic colloid. A dissolved aqueous solution or a solubility at 25 ° C of 1.
The cyanine dye of 5 × 10 ^-2 mol / liter or less is a method in which the dye is directly finely dispersed in water or a hydrophilic colloid to 1 μm or less, and the dispersion is added to an emulsion. A method of dissolving or finely dispersing in a water-soluble organic solvent solution and adding it to the emulsion is also preferably used, but the amount of the organic solvent to be added is preferably 5% by volume or less of the amount of the silver halide emulsion to be prepared. Good
Furthermore, the general formula (I) or the general formula (I
When the solubility of the cyanine dye represented by I) in water at 25 ° C. is 5 × 10 ⁻⁴ mol / liter or more, the cyanine dye is directly added to a silver halide emulsion in a finely ground solid state. The method of doing is also more preferable.

The sensitizing dye used in the present invention may be added to the silver halide emulsion of the present invention in any step of emulsion preparation which has been recognized to be useful so far. For example, US Pat. No. 2,735,766, US Pat. No. 3,628,960, US Pat. No. 4,183,756.
No. 4,225,666, JP-A-58-18.
No. 4,142, JP-A-60-196749, and the like, as disclosed in the specification, silver halide grain forming step and / or timing before desalting, during desalting step and / or desalting step. From the time after salting to before the start of chemical aging, JP-A-58-1
As disclosed in the specification of No. 13,920, etc., it may be added at any time or step immediately before or during the chemical ripening, at any time before the emulsion is coated until after the chemical ripening and before the coating. Although it may be used, any time before the completion of chemical sensitization is more preferable. Also, US Pat. No. 4,225,666
As disclosed in the specification of JP-A-58-7,629 and the like, the same compound alone or in combination with a compound having a different structure can be used, for example, in the same step or in the particle forming step. It may be added separately in different steps such as during the chemical ripening step or after the chemical ripening, or before the chemical aging or during the step and after the chemical aging. The kind of combination may be changed and added. In addition, a predetermined amount may be added in a short time, or continuously for a long time, for example, from the nucleation in the particle forming process to the completion of particle formation or most of the chemical ripening process in any step. You may add. In such a case, the addition speed may be a constant flow rate, or the flow rate may be accelerated or decelerated. The temperature at which the sensitizing dye is added to the silver halide emulsion is not particularly limited, but is usually 35 ° C to 70 ° C, and the addition temperature and the ripening temperature may be changed. A method of increasing the temperature and aging after adding at 45 ° C. or lower is more preferable.

General formula (I) or general formula used in the present invention
The total addition amount of the cyanine dye represented by (II) varies depending on the shape and size of the silver halide grains, but is 5.5 × 10 ^{−6 to} 1.2 × 10 ⁻² per mol of silver halide. It can be used in moles. For example, when the silver halide grain size is 0.2 to 2.0 μm, the surface area of the silver halide grain is 1 m ^{2 and the} concentration is 4.0 × 10 ^{−7 to} 6.5 × 10.
^-6 mol addition amount is preferable, 1.0 x 10 ^{-6 to} 4.2 x
The addition amount of 10 ⁻⁶ mol is more preferable.

The silver chloride grains according to the present invention have little absorption in the blue region. In particular, in the production of color photographic light-sensitive materials and color photographic paper, the blue light-sensitive emulsion layer is 400 nm thick.
It is necessary to be sensitive to light of about 500 nm, and in order to sufficiently achieve such an object, at least one of the dyes represented by the general formula (I) and at least one of the dyes represented by the general formula (II). It is more preferable to use one kind in combination, and in the case of using plural kinds of cyanine dyes in combination including such a case, the total addition amount of those cyanine dyes should be the above-mentioned addition amount. Is more preferable.

These sensitizing dyes may be used alone as described above, or may be used in combination.
Combinations of sensitizing dyes are often used especially for the purpose of supersensitization.

Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion.

Specific examples of the dye used in the present invention are shown below. The present invention is not limited to these.

[0053]

[Chemical 5]

[0054]

[Chemical 6]

[0055]

[Chemical 7]

[0056]

[Chemical 8]

[0057]

[Chemical 9]

[0058]

[Chemical 10]

[0059]

[Chemical 11]

[0060]

[Chemical 12]

[0061]

[Chemical 13]

[0062]

[Chemical 14]

[0063]

[Chemical 15]

The above-mentioned various additives are used in the emulsion of the present invention, but various additives other than the above can be used according to the purpose.

More specifically, these additives are described in Research Disclosure Item 17643 (December 1978) and Item 18716 (December 1979).
Mon) and Item 308119 (December 1989)
Month), and the relevant parts are summarized in Table 1 below.

The light-sensitive material of the present invention may have at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer provided on a support. There is no particular limitation on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. And the photosensitive layer is blue light, green light,
And a unit light-sensitive layer having color sensitivity to red light. In a multilayer silver halide color photographic light-sensitive material, the unit light-sensitive layers are generally arranged in order from the support side to the red-color-sensitive layer and green. The color sensitive layer and the blue color sensitive layer are installed in this order. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers.

Non-photosensitive layers such as various intermediate layers may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer.

For the intermediate layer, Japanese Patent Laid-Open No. 61-43748 is used.
No. 59-113438, No. 59-113440
Nos. 61-20037 and 61-20038, the couplers, the DIR compounds, etc. may be contained, and a color mixing inhibitor may be contained as usual.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are a high sensitivity emulsion layer and a low sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer constitution of emulsion layers can be preferably used. In general, it is preferable that the layers are arranged so that the photosensitivity is gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also,
JP-A-57-112751, JP-A-62-200350
No. 62-206541, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side farther from the support, and a high-sensitivity emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support,
Low sensitivity blue photosensitive layer (BL) / high sensitivity blue photosensitive layer (BH)
/ High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (G
L) / high-sensitivity red photosensitive layer (RH) / low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH /
RL order or BH / BL / GH / GL / RL / RH
It can be installed in the order of.

Further, as described in JP-B-55-34932, the layers may be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Also, JP-A-56-25738 and 62-6393.
As described in No. 6, it is also possible to arrange in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.

As described in JP-B-49-15495, the upper layer is the silver halide emulsion layer having the highest sensitivity, the middle layer is the silver halide emulsion layer having a lower sensitivity, and the lower layer is the middle layer. Another example is an arrangement in which a silver halide emulsion layer having a lower photosensitivity is arranged and three layers having different sensitivities are sequentially lowered toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side remote from the support in the same color-sensitive layer. Layers / high-speed emulsion layers / low-speed emulsion layers may be arranged in this order.

In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. Also, 4
In the case of more than one layer, the arrangement may be changed as described above.

As described above, various layer structures and arrangements can be selected according to the purpose of each photosensitive material.

In the photographic light-sensitive material of the present invention, at least one silver halide emulsion layer provided on the support has 30% or more, preferably 50% or more, more preferably the silver halide emulsion of the present invention. It is a silver halide photographic light-sensitive material containing 70% or more.

The silver halide grains other than the silver halide of the present invention in the photographic emulsion include those having regular crystals such as cubes, octahedra and tetradecahedrons, and irregular grains such as spheres and plates. Those having different crystal forms, those having crystal defects such as twin planes, or a composite form thereof may be used.

The grain size of the silver halide other than the silver halide of the present invention may be fine grains of about 0.2 micron or less, or large grains having a projected area diameter of up to about 10 microns, and may be a monodisperse emulsion or a monodisperse emulsion. It may be a dispersion emulsion.

The silver halide emulsion used in the present invention is usually one which has been physically ripened, chemically ripened and spectrally sensitized.

The method of adding a chalcogen compound as described in US Pat. No. 3,772,031 during emulsion preparation may be useful. In addition to S, Se and Te, cyanate, thiocyanate, selenocyanic acid, carbonate, phosphate and acetate may be present.

The silver halide grains used in the present invention are at least one of sulfur sensitization, selenium sensitization, gold sensitization, palladium sensitization or other noble metal sensitization and reduction sensitization, and a process for producing a silver halide emulsion. Can be applied in any step.
It is preferable to combine two or more sensitizing methods. Various types of emulsions can be prepared depending on which step is chemically sensitized. There are a type in which chemically sensitized nuclei are embedded inside a grain, a type in which a chemical sensitized nucleus is embedded at a shallow position from the grain surface, and a type in which a chemically sensitized nucleus is formed on the surface. In the emulsion of the present invention, the location of the chemically sensitized nucleus can be selected according to the purpose, but it is generally preferable that at least one type of chemically sensitized nucleus is formed near the surface.

One of the chemical sensitizations which can be preferably carried out in the present invention is chalcogen sensitization and noble metal sensitization, either alone or in combination, by TH James, The Photographic Process, 4th. Edition, published by Macmillan, 1
977, (TH James, The Theor
y of the Photographic Pro
cess, 4th ed, Macmillan, 197
7) Active gelatin as described on pages 67-76, and Research Disclosure 120, April 1974, 12008; Research Disclosure, 34, June 1975, 1
3452, U.S. Pat. Nos. 2,642,361 and 3,2.
97,446, 3,772,031, 3,85
7,711, 3,901,714, 4,26
6,018, and 3,904,415, and British Patent 1,315,755, p.
It can be sulfur, selenium, tellurium, gold, platinum, palladium, iridium or combinations of these sensitizers at Ag 5-10, pH 5-8 and temperature 30-80 ° C. In the noble metal sensitization, noble metal salts such as gold, platinum, palladium and iridium can be used, and among them, gold sensitization, palladium sensitization and a combination of both are preferable. In the case of gold sensitization, known compounds such as chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide and gold selenide can be used. The palladium compound means a divalent or tetravalent palladium salt. Preferred palladium compounds are represented by R ₂ PdX ₆ or R ₂ PdX ₄ . Where R is a hydrogen atom,
Represents an alkali metal atom or an ammonium group. X represents a halogen atom and represents a chlorine, bromine or iodine atom.

Specifically, K ₂ PdCl ₄ , (NH ₄ )
₂ PdCl ₆ , Na ₂ PdCl ₄ , (NH ₄ ) ₂ PdC
l ₄ , Li ₂ PdCl ₄ , Na ₂ PdCl ₆ or K ₂
PdBr ₄ is preferred. The gold compound and the palladium compound are preferably used in combination with thiocyanate or selenocyanate.

As sulfur sensitizers, hypo, thiourea compounds, rhodanine compounds and US Pat. No. 3,857,
711, 4,266,018 and 4,05
It is more preferable to use the sulfur-containing compounds described in 4,457. It is also possible to carry out chemical sensitization in the presence of a so-called chemical sensitization aid. Useful chemical sensitization aids include
Compounds such as azaindene, azapyridazine and azapyrimidine which are known to suppress fog and increase sensitivity in the process of chemical sensitization are used. Examples of chemical sensitization aid modifiers are described in US Pat. No. 2,131,038,
No. 3,411,914, No. 3,554,757, JP-A-58-126526 and the above-mentioned Daffin's "Photographic Emulsion Chemistry", pages 138-143.

The emulsion of the present invention is preferably combined with gold sensitization and sulfur sensitization. The preferred amount of gold sensitizer and sulfur sensitizer is 1 × 1 per mol of silver halide.
0 ⁻⁴ to 1 × 10 ⁻⁷ mol, more preferably 1 ×
It is 10 ^{−5 to} 5 × 10 ⁻⁷ mol.

Selenium sensitization is a preferable sensitizing method for the emulsion of the present invention. In the selenium sensitization, a known unstable selenium compound is used, and specifically, colloidal metal selenium, selenoureas (for example, N, N-dimethylselenourea, N, N-diethylselenourea, etc.), selenoketone And selenium compounds such as selenoamides can be used. In some cases, selenium sensitization is preferably used in combination with sulfur sensitization, precious metal sensitization, or both.

During grain formation of the silver halide emulsion of the present invention,
It is preferable to carry out reduction sensitization after grain formation and before or during chemical sensitization or after chemical sensitization.

Here, the reduction sensitization is a method of adding a reduction sensitizer to a silver halide emulsion, pAg1 called silver ripening.
No. 7, a method of growing or aging in a low pAg atmosphere, or a method of growing or aging in a high pH atmosphere of pH 8 to 11 called high pH aging can be selected. Also, two or more methods can be used in combination.

The method of adding a reduction sensitizer is a preferable method because the level of reduction sensitization can be finely adjusted.

Known reduction sensitizers are stannous salts, ascorbic acid and its derivatives, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid, silane compounds and borane compounds. For the reduction sensitization of the present invention, these known reduction sensitizers can be selected and used, or two or more kinds of compounds can be used in combination. As reduction sensitizers, stannous chloride, thiourea dioxide, dimethylamine borane, ascorbic acid and its derivatives are preferred compounds. Since the addition amount of the reduction sensitizer depends on the emulsion production conditions, it is necessary to select the addition amount, but the range of 10 ^-7 to 10 ^-3 mol is suitable per mol of silver halide.

The reduction sensitizer is dissolved in water or a solvent such as alcohols, glycols, ketones, esters and amides and added during grain growth. It may be added to the reaction vessel in advance, but it is preferable to add it at an appropriate time during grain growth. Further, a reduction sensitizer may be added in advance to the water solubility of the water-soluble silver salt or the water-soluble alkali halide, and the silver halide grains may be precipitated using these aqueous solutions. Further, it is also a preferable method to add the solution of the reduction sensitizer in several times as the grains grow, or to continuously add the solution for a long time.

The silver halide emulsion of the present invention is preferably subjected to the above-described chemical sensitization alone or in combination, and as described above, it is preferable to use gold sensitization and sulfur sensitization in combination. In the sensitization, it is more preferable to perform the chemical sensitization in the presence of at least one cyanine dye represented by the general formula (I) and / or at least one cyanine dye represented by the general formula (II). In addition, a nitrogen-containing heterocyclic compound which is known to increase fog sensitivity by suppressing fog in the process of chemical sensitization called complex chemical sensitization aid, which forms a complex compound with silver, is added. It is particularly preferable that the compound is also present for chemical sensitization. As such a nitrogen-containing heterocyclic compound, azaindenes or mercapto-substituted azoles are preferable, and tetrazaindene compounds (for example, 4-hydroxy-6-methyl-1,3,3
a, 7-Tetrazaindene, 4-hydroxy-5,6-
Trimethylene-1,3,3a, 7-tetrazaindene etc.) or a 5-mercaptotetrazole compound (for example, 5-mercapto-1-phenyltetrazole, 1-
(3-Acetylamino) phenyl-5-mercaptotetrazole, 1- (3-methylureido) phenyl-5-
Particularly preferred are mercaptotetrazole and 5-mercapto-1-sulfophenyltetrazole.

Acid for silver during the manufacturing process of the emulsion of the present invention.
It is preferable to use an agent. What is an oxidizing agent for silver?
Has the effect of acting on metallic silver and converting it to silver ions
Refers to a compound. Especially the formation process of silver halide grains and
Very small silver particles by-produced during the chemical sensitization process
Compounds that can convert the above into silver ions are effective. here
The silver ions generated in are silver halide, silver sulfide, and selenium.
It may form a sparingly soluble silver salt such as silver halide, or silver nitrate.
A silver salt which is easily soluble in water may be formed. Oxidation for silver
The agent may be an inorganic substance or an organic substance. inorganic
Oxidizing agents include ozone, hydrogen peroxide and its addition
Thing (eg NaBO₂・ H₂O₂・ 3H₂O, 2NaC
O₃・ 3H₂O₂, Na_FourP₂O₇・ 2H₂O₂2N
a₂SO_Four・ H₂O₂・ 2H₂O), peroxy acid salt
(Eg K₂S₂O₈, K₂C₂O₆, K₂P
₂O₈), A peroxy complex compound (for example, K₂[Ti
(O₂) C₂O _Four] ・ 3H₂O, 4K₂SO_Four・ Ti
(O₂) OH / SO_Four・ 2H₂O, Na₃[VO
(O₂) (C₂H_Four)₂] ・ 6H₂O), permanganate
Salt (eg KMnO_Four), Chromates (eg, K₂
Cr₂O₇) Such as oxygenates, halogens such as iodine and bromine
Element, perhalogenate (eg potassium periodate),
High valent metal salts (eg, hexacyanoferric acid
Lithium) and thiosulfonate.

Examples of the organic oxidant include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogen (for example, N-bromosuccinimide and chloramine T). , Chloramine B). The preferred oxidant of the present invention is ozone,
Hydrogen peroxide and its adducts, halogen elements, thiosulfonate inorganic oxidants and quinones organic oxidants. It is a preferable embodiment to use the reduction sensitization and the oxidizing agent for silver in combination. It can be selected from the method of using an oxidant and then the reduction sensitization, the reverse method thereof, or the method of coexisting both. These methods can be selectively used in the grain forming step and the chemical sensitization step.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance. . That is, thiazoles, such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), etc .; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes, for example tria Theindenes, tetraazaindenes (particularly 4-hydroxy-substituted (1,
Many compounds known as antifoggants or stabilizers such as 3,3a, 7) tetraazaindenes), pentaazaindenes, etc. can be added. For example, U.S. Pat. Nos. 3,954,474 and 3,982,9
No. 47 and Japanese Patent Publication No. 52-28660 can be used. One of the preferred compounds is JP-A-6
There are compounds described in 3-212932. Antifoggants and stabilizers are used at various times before particle formation, during particle formation, after particle formation, during the water washing step, during dispersion after water washing, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added depending on the purpose. Addition during emulsion preparation to exert the original antifogging and stabilizing effects, in addition to controlling the crystal habit of grains, reducing the grain size, reducing the solubility of grains, controlling chemical sensitization, It can be used for various purposes such as controlling the arrangement of dyes.

The light-sensitive material of the present invention comprises a light-sensitive silver halide emulsion having a grain size, a grain size distribution, a halogen composition,
Two or more kinds of emulsions having at least one characteristic of grain shape and sensitivity can be mixed and used in the same layer.

The fogged silver halide grains described in US Pat. No. 4,082,553 and the fogged grains described in US Pat. No. 4,626,498 and JP-A-59-214852 are fogged. The prepared silver halide grains and colloidal silver can be preferably used in the photosensitive silver halide emulsion layer and / or the substantially non-photosensitive hydrophilic colloid layer.
The fogged silver halide grain inside or on the surface means a silver halide grain capable of developing uniformly (non-imagewise) regardless of the unexposed portion and exposed portion of the light-sensitive material. . A method for preparing a silver halide grain whose inside or surface is fogged is described in US Pat. No. 4,626,498 and JP-A-59-214852.

The silver halide forming the inner core of a core / shell type silver halide grain having a fogged grain inside may have the same halogen composition or different halogen compositions. As the silver halide whose inside or surface is fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The grain size of these fogged silver halide grains is not particularly limited, but the average grain size is 0.01 to 0.7.
The thickness is preferably 5 μm, particularly preferably 0.05 to 0.6 μm. Also,
The grain shape is not particularly limited, and may be regular grains or polydisperse emulsion, but monodisperse (at least 95% of the weight or the number of silver halide grains is within ± 40% of the average grain size). (Having a particle size of 1).

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a fine grain of silver halide which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the development process, and it is preferable that it is not fogged in advance. .

The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and if necessary, silver chloride and / or
Alternatively, it may contain silver iodide. Preferred is one containing 0.5 to 10 mol% of silver iodide.

The fine grain silver halide preferably has an average grain size (average value of the equivalent circle diameters of the projected area) of 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm.

Fine grain silver halide can be prepared in the same manner as in the case of ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be chemically sensitized,
Also, spectral sensitization is not necessary. However, prior to adding this to the coating liquid, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, mercapto-based compound or zinc compound in advance. Colloidal silver can be preferably contained in this fine grain silver halide grain-containing layer.

The silver coating amount of the light-sensitive material of the present invention was 6.0 g.
/ M ² or less is preferably 1.0 g / m ² or more, and most preferably 4.5 g / m ² or less.

Known photographic additives that can be used in the present invention are also described in the above-mentioned three Research Disclosures, and the relevant portions are shown in Table 1 below.

In order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat. No. 4,411,98
It is preferable to add a compound which can be immobilized by reacting with formaldehyde described in No. 7 and No. 4,435,503 to the light-sensitive material.

The light-sensitive material of the present invention can be incorporated into US Pat.
0,454, 4,788,132, JP-A-62.
It is preferable to incorporate the mercapto compounds described in JP-A-18539 and JP-A-1-283551.

The light-sensitive material of the present invention can be incorporated into Japanese Patent Laid-Open No. 1-1060
No. 52, it is preferable to contain a compound which releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof regardless of the amount of developed silver produced by the development processing.

International Publication WO88 /
No. 04794, dyes or EP 317,308A dispersed by the method described in JP-A-1-502912.
U.S. Pat. No. 4,420,555, JP-A-1-259.
It is preferable to incorporate the dye described in No. 358.

Various color couplers can be used in the present invention, specific examples of which are described in Research Disclosure No. 17643, VII-CG, and No. 17643. 307105, VII-C to G.

Examples of yellow couplers include US Pat. Nos. 3,933,501 and 4,022,620.
Issue No. 4,326,024, No. 4,401,75
No. 2, No. 4,248,961, Japanese Patent Publication No. 58-107.
39, British Patent Nos. 1,425,020 and 1,4
76,760, U.S. Pat. Nos. 3,973,968, 4,314,023, 4,511,649,
Those described in European Patent No. 249,473A and the like are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619 and 4,351,897 are preferred.
No., EP 73,636, US Pat. No. 3,06
No. 1,432, No. 3,725,067, Research
Disclosure No. 24220 (June 1984)
Mon.), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, 61-72238 and 60.
-35730, 55-118034, 60-1
Those described in US Pat. No. 8,5951, US Pat. Nos. 4,500,630, 4,540,654, 4,556,630, International Publication WO88 / 04795 and the like are particularly preferable.

Examples of cyan couplers include phenol-type and naphthol-type couplers, and US Pat.
No. 52,212, No. 4,146,396, No. 4,
No. 228,233, No. 4,296,200, No. 2,369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826,
No. 3,772,002, No. 3,758,308
No. 4,433,011, No. 4,327,17
No. 3, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A, No. 249,453A, U.S. Patent Nos. 3,446,622 and 4,333,999.
Issue No. 4,775,616, No. 4,451,55
No. 9, No. 4,427, 767, No. 4, 690, 8
No. 89, No. 4,254,212, No. 4,296,
Those described in JP-A No. 199 and JP-A No. 61-42658 are preferable.

Typical examples of polymerized dye-forming couplers are shown in US Pat. Nos. 3,451,820 and 4,084.
No. 0,211, No. 4,367,282, No. 4,4
09,320, 4,576,910, British Patent 2,102,137, European Patent 341,188A and the like.

As couplers in which the color forming dye has an appropriate diffusibility, US Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,570,
Those described in West German Patent (Publication) No. 3,234,533 are preferable.

Colored couplers for correcting unnecessary absorption of color forming dyes are Research Disclosure N.
o. 17643, Item VII-G, ibid. Of 307105
Section VII-G, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-39413, U.S. Pat. No. 4,004,929.
No. 4,138,258, British Patent No. 1,14.
Those described in 6,368 are preferable. Further, a coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in US Pat. No. 4,774,181 and a reaction with a developing agent described in US Pat. No. 4,777,120. It is also preferable to use a coupler having as a leaving group a dye precursor group capable of forming a dye.

Compounds releasing a photographically useful residue upon coupling are also preferably used in the present invention.
DIR couplers that release development inhibitors are described in RD.
17643, Item VII-F and No. 307105, V
Patents described in the section II-F, JP-A-57-151944
No. 57-154234, No. 60-184248.
Nos. 63-37346, 63-37350, and U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferable.

As a coupler capable of releasing a nucleating agent or a development accelerator imagewise during development, British Patent No. 2,092
7,140, 2,131,188, JP-A-59
Those described in Nos. 157638 and 59-170840 are preferable. Further, JP-A-60-107029, JP-A-60-252340, JP-A-1-44940 and JP-A-1-4940.
Compounds releasing a fog agent, a development accelerator, a silver halide solvent and the like by an oxidation-reduction reaction with an oxidized product of a developing agent described in JP-A-45687 are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,427.
Competitive couplers described in U.S. Pat. No. 4,283,4
No. 72, No. 4,338,393, No. 4,310,
No. 618 and the like, multiequivalent couplers, JP-A-60-18.
5950, DI described in JP-A-62-24252, etc.
R redox compound-releasing coupler, DIR coupler-releasing coupler, DIR coupler-releasing redox compound or DIR redox-releasing redox compound, coupler releasing a dye that recolors after separation described in European Patent Nos. R.K. D. N
o. 11449, 24241, JP-A-61-2012
47, etc., bleaching accelerator releasing couplers, US Pat. No. 4,555,477, etc., ligand releasing couplers, JP-A-63-75747, leuco dye releasing couplers, US Pat. , 774,181, and the like, which release a fluorescent dye.

The coupler used in the present invention can be introduced into the photographic material by various known dispersion methods.

Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027.

Specific examples of the high-boiling organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (for example, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, Decyl phthalate, bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate), phosphoric acid or phosphone Acid esters (eg triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2)
-Ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenylphosphonate), benzoic acid esters (e.g. 2-ethylhexylbenzoate), dodecylbenzoate, 2
-Ethylhexyl-p-hydroxybenzoate), amides (e.g. N, N-diethyldodecane amide, N,
N-diethyllaurylamide, N-tetradecylpyrrolidone), alcohols or phenols (eg isostearyl alcohol, 2,4-di-tert-amylphenol), aliphatic carboxylic acid esters (eg bis (2-ethylhexyl)) Sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate), aniline derivatives (eg N, N-dibutyl-2-butoxy-5-te).
rt-octylaniline), hydrocarbons (eg paraffin, dodecylbenzene, diisopropylnaphthalene)
And so on. The auxiliary solvent has a boiling point of about 3
An organic solvent having a temperature of 0 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like. To be

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,3.
63, West German Patent Application (OLS) No. 2,541,274
And No. 2,541,230.

In the photographic light-sensitive material of the present invention, phenethyl alcohol, JP-A-63-257747 and JP-A-62-2 are used.
No. 72248, and 1,2-benzisothiazolin-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol described in JP-A No. 1-80941. It is preferable to add various preservatives or antifungal agents such as-(4-thiazolyl) benzimidazole.

The present invention can be applied to various photographic light-sensitive materials. Typical examples are color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers.

Suitable supports that can be used in the present invention are, for example, those described in RD. No. 17643, page 28, ibid.
No. 18716, page 647, right column to page 648, left column, and ibid. 307105, page 879.

In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, and 18 μm or less.
m or less is more preferable, and 16 μm or less is particularly preferable.
The film swelling speed T1 / 2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness means the film thickness measured at 25 ° C. and 55% relative humidity (2 days), and the film swelling rate T1 /
2 can be measured according to a method known in the art. For example, A Green (A. Gre
en) et al. in Photographic Science and Engineering (Photogr. Sci. En.
g. ), Vol. 19, No. 2, pp. 124-129, it can be measured by using a swellometer (swelling meter) of the type, and T1 / 2 was treated with a color developer at 30 ° C. for 3 minutes and 15 seconds. 90% of the maximum swollen film thickness that reaches at time is the saturated film thickness,
It is defined as the time required to reach 1/2 of the saturated film thickness.

The film swelling speed T1 / 2 can be adjusted by adding a film-hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling rate is calculated from the maximum swollen film thickness under the above-mentioned conditions by the formula:
It can be calculated according to (maximum swollen film thickness-film thickness) / film thickness.

The light-sensitive material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. This back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, surface active agent and the like. The swelling ratio of this back layer is 150.
~ 500% is preferred.

The light-sensitive material according to the present invention has the RD.
No.17643, pages 28 to 29, No. 18716, 651 left column to right column, and No. 307105, pages 880 to 881 can be developed by a usual method. The color developing solution used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. As the color developing agent, aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N diethylaniline and 3-methyl. -4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-
Methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-methoxyethylaniline, 4-amino-3-methyl-N
-Methyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- ( 2-hydroxypropyl) aniline, 4-amino-3-ethyl-N-ethyl
-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-propyl-N- (3-hydroxypropyl) aniline, 4-amino-3-propyl-N-methyl-N- (3- Hydroxypropyl) aniline, 4-amino-3-methyl-N-methyl-N
-(4-hydroxybutyl) aniline, 4-amino-3-methyl
-N-ethyl-N- (4-hydroxybutyl) aniline, 4-amino-3-methyl-N-propyl-N- (4-hydroxybutyl) aniline, 4-amino-3-ethyl-N-ethyl-N -(3-Hydroxy-2-methylpropyl) aniline, 4-amino-3-methyl
-N, N-bis (4-hydroxybutyl) aniline, 4-amino
-3-methyl-N, N-bis (5-hydroxypentyl) aniline, 4-amino-3-methyl-N- (5-hydroxypentyl) -N
-(4-hydroxybutyl) aniline, 4-amino-3-methoxy-N-ethyl-N- (4-hydroxybutyl) aniline, 4-amino-3-ethoxy-N, N-bis (5-hydroxypentyl)
Aniline, 4-amino-3-propyl-N- (4-hydroxybutyl) aniline, and their sulfates, hydrochlorides or p-
Examples thereof include toluene sulfonate. Among these, especially 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 4-amino-3-methyl-N-ethyl
-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline, and their hydrochlorides, p-toluenesulfonates or sulfates are preferred. . Two or more of these compounds can be used in combination depending on the purpose.

The amount of the aromatic primary amine developing agent used is preferably 0.0002 mol to 0.2 mol, and more preferably 0.001 mol to 1 liter of the color developing solution.
It is 0.1 mol.

The color developer contains a pH buffering agent such as an alkali metal carbonate, borate or phosphate 5-sulfosalicylate, a chloride salt, a bromide salt, an iodide salt, a benzimidazole compound, a benzoic acid salt. It generally contains a development inhibitor such as a thiazole or a mercapto compound or an antifoggant. In addition, hydroxylamine, diethylhydroxylamine, etc. may be used, if necessary.
Hydroxylamines represented by the general formula (I) of No. 144446, sulfites, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides,
Various preservatives such as triethanolamine and catechol sulfonic acids, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye forming couplers and competitive couplers. , Various developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and various chelating agents represented by phosphonocarboxylic acids, for example, ethylenediamine. Tetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid,
Representative examples thereof include nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof. . Of the above,
As the preservative, substituted hydroxylamine is most preferable, and among them, those having an alkyl group substituted with a water-soluble group such as a sulfo group, a carboxy group or a hydroxyl group as a substituent are preferable. The most preferable example is N, N-bis (2-sulfoethyl) hydroxylamine and its alkali metal salt. Further, a compound having biodegradability is preferable as the chelating agent. An example of this is JP-A-6
3-146998, JP-A-63-199295, JP-A-63-267750, JP-A-63-267751.
JP-A-2-229146 and JP-A-3-18684.
No. 1, German Patent 3739610, European Patent 468325
Examples thereof include chelating agents described in No. It is preferable that the processing solution in the color developing solution replenishing tank or the processing tank is shielded with a liquid agent such as a high-boiling point organic solvent to reduce the contact area with air. Liquid paraffin is most preferable as the liquid shield agent. It is particularly preferable to use it as a replenisher. The processing temperature of the color developer in the present invention is 20 to 55 ° C, preferably 30 to 55 ° C. The processing time is 20 seconds to 5 minutes, preferably 3 for the light-sensitive material for photography.
It is 0 seconds to 3 minutes and 20 seconds. It is more preferably 40 seconds to 2 minutes and 30 seconds, and for printing materials, 10 seconds to 1 minute 20 seconds, preferably 10 seconds to 60 seconds, and more preferably 10 seconds to 40 seconds.

When the reversal process is carried out, the black and white development is usually carried out before the color development. In this black-and-white developing solution, a known black-and-white developing agent such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol is used alone. Alternatively, they can be used in combination. The color developing solution and the black and white developing solution generally have a pH of 9 to 12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per square meter of the light-sensitive material, and 500 liters or less by reducing the bromide ion concentration in the replenishing solution. You can also
When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area of the treatment tank with the air. The contact area between the photographic processing liquid and air in the processing tank can be represented by the aperture ratio defined below.
That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷ [volume of treatment liquid (cm ³ )] The above aperture ratio is preferably 0.1 or less, and more preferably 0.001 to 0.05. Is. As a method for reducing the aperture ratio in this way, in addition to providing a cover such as a floating lid on the surface of the photographic processing liquid in the processing tank, a method using a movable lid described in JP-A-1-82033 is disclosed. The slit development processing method described in 63-216050 can be mentioned. Reducing the aperture ratio is not limited to both the color development and black and white development steps, but also the subsequent steps such as bleaching, bleach-fixing,
It is preferably applied in all steps such as fixing, washing with water, and stabilization. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out. As the bleaching agent, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. A typical bleaching agent is an iron (III) complex salt,
For example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, glycol etherdiaminetetraacetic acid, JP-A-4
No. 121739, a bleaching agent including a 1,3-propylenediaminetetraacetic acid iron complex salt in the lower right column of the fourth page to the upper left column of the fourth page, and a carbamoyl-based bleaching agent described in JP-A-4-73647. Bleaching agents, bleaching agents having a heterocycle described in JP-A-4-174432, bleaching agents described in European Patent Publication No. 520457, including N- (2-carboxyphenyl) iminodiacetic acid ferric complex salts. Japanese Patent Application No. 3-252775 including ethylenediamine-N-2-carboxyphenyl-N, N ', N'-ferric acetic acid
Bleaching agent, bleaching agent described in EP-A-501479, bleaching agent described in JP-A-4-127145,
The ferric aminopolycarboxylic acid salts or salts thereof described on page (11) of JP-A-3-144446 are preferably used. The organic aminocarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution.
The pH of the bleaching solution or bleach-fixing solution using these organic aminocarboxylic acid iron (III) complex salts is usually 4.0 to 8, but it is also possible to process at a lower pH in order to speed up the processing.

These bleaching processes are preferably carried out immediately after color development, but in the case of reversal processes, they are generally carried out via a conditioning bath (which may be a bleaching promoting bath). These adjusting baths may contain an image stabilizer described later. In the present invention, in addition to the bleaching agent, the desilvering bath is described in JP-A-3-144446 (1).
2) Rehalogenating agents, pH buffers and known additives described on page, aminopolycarboxylic acids, organic phosphonic acids and the like can be used. Further, in the present invention, various bleaching accelerators can be added to the bleaching solution or its prebath. Examples of such bleaching accelerators include, for example, US Pat. No. 3,893,858 and German Patents 1, 2
90,821, British Patent No. 1,138,842.
Specification, JP-A-53-95630, research
Compounds having a mercapto group or a disulfide group described in Disclosure No. 17129 (July 1978 issue), thiazolidine derivatives described in JP-A No. 50-140129, described in US Pat. No. 3,706,561. Thiourea derivative of JP-A-58-16235
Iodide described in German Patent 2,748,43
The polyethylene oxides described in No. 0 specification, the polyamine compounds described in JP-B-45-8836, and the like can be used. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photography. Particularly preferred are mercapto compounds as described in British Patent 1,138,842 and JP-A-2-190856.

In addition to the above compounds, the bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. A particularly preferred organic acid has an acid dissociation constant (p
Ka) is 2 to 5.5, and dibasic acid is particularly preferable. The organic acid is specifically acetic acid as a monobasic acid,
Propionic acid, hydroxyacetic acid and the like are preferable, and more preferable dibasic acids include succinic acid, glutaric acid, maleic acid, fumaric acid, malonic acid, adipic acid and the like. Most preferred are succinic acid, glutaric acid and maleic acid.

The total time of the desilvering process is preferably as short as possible in the range where desilvering failure does not occur. Preferred time is 1 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The treatment temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C. In the preferable temperature range, the desilvering rate is improved, and the stain generation after the processing is effectively prevented. The processing solution having a bleaching ability of the present invention is particularly preferably subjected to aeration during processing because the photographic performance is kept extremely stable. Means known in the art can be used for the aeration, and blowing of air into the processing liquid having a bleaching ability or absorption of air using an ejector can be performed. At the time of blowing air, it is preferable to discharge the air into the liquid through an air diffusing tube having fine pores. Such an air diffuser is widely used as an aeration tank in activated sludge treatment. Regarding aeration, Z-121, Eusing Process C-41 3rd edition (1982), Eastman Kodak Company, BL-1 to BL
-The items described on page 2 can be used. In the processing using the processing solution having the bleaching ability of the present invention, it is preferable that the stirring is intensified, and the practice is disclosed in JP-A-3-3384.
The contents described on page 8, upper right column, line 6 to lower left column, line 2 of Japanese Patent Publication No. 7 can be used as they are.

In the desilvering process, it is preferable that the stirring is strengthened as much as possible. Specific examples of the method for strengthening stirring include a method in which a jet of a processing solution is made to collide with the emulsion surface of a light-sensitive material described in JP-A-62-183460, and JP-A-62-1834.
A method of increasing the stirring effect using the rotating means of No. 61, and further moving the photosensitive material while bringing the emulsion surface into contact with the wiper blade provided in the liquid to make the emulsion surface turbulent, thereby further improving the stirring effect. Examples thereof include a method for improving the method and a method for increasing the circulation flow rate of the entire processing solution. Such a stirring improving means is effective in any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film and, as a result, increases the desilvering rate. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting action of the bleaching accelerator. The automatic developing machine used for the light-sensitive material of the present invention is disclosed in JP-A-60-191257, JP-A-60-191258, and JP-A-60-191258.
It is preferable to have the photosensitive material conveying means described in 60-191259. As described in the above-mentioned JP-A-60-191257, such a conveying means can remarkably reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the performance deterioration of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The processing solution having the bleaching ability of the present invention is
The overflow solution after use in the treatment can be recovered, the components can be added to modify the composition, and then the overflow solution can be reused. Such usage is usually called regeneration, but the present invention can also favor such regeneration. For details of the reproduction, see Fuji Film Processing Manual issued by Fuji Photo Film Co., Ltd., Fuji Color Negative Film, CN-16 processing (revised August 1990), pp. 39-.
The matters described on page 40 can be applied. The kit for adjusting the processing solution having the bleaching ability of the present invention may be a liquid or a powder, but when the ammonium salt is excluded, most of the raw materials are supplied as a powder, and since the hygroscopicity is low,
Makes powder easier. From the viewpoint of reducing the amount of waste liquid, the regenerating kit is preferably a powder because it can be added directly without using excess water.

Regarding the regeneration of the processing solution having a bleaching ability,
In addition to the aeration mentioned above, "Basics of photographic engineering-silver salt photography-" (edited by the Photographic Society of Japan, published by Corona Publishing Co., 1979)
Year)) etc. can be used. Specifically, in addition to electric field regeneration, there is a method for regenerating bleaching solution with bromic acid, zincic acid, bromine, bromine precursor, persulfate, hydrogen peroxide, hydrogen peroxide using catalyst, bromic acid, ozone, etc. Can be mentioned.
In electrolytic regeneration, the cathode and the anode are put in the same bleaching bath, or the anode bath and the cathode bath are regenerated by using a diaphragm to separate the baths. The fixing solution can be reprocessed at the same time. The fixing solution and the bleach-fixing solution are regenerated by electrolytically reducing accumulated silver ions. Other,
It is also preferable to remove accumulated halogen ions with an anion exchange resin in order to maintain the fixing performance. Ion exchange or ultrafiltration is used to reduce the amount of washing water used, and it is particularly preferable to use ultrafiltration.

The light-sensitive material of the present invention is generally subjected to a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, and further, the rinsing water temperature, the number of rinsing tanks (the number of stages), the replenishment system such as countercurrent and forward flow, and various other conditions. It can be set in a wide range. Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is as follows.
e Society of MotionPicture and Television Engineers
It can be determined by the method described in Volume 64, P. 248 to 253 (May 1955 issue). According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In the processing of the color light-sensitive material of the present invention, the method of reducing calcium ion and magnesium ion described in JP-A-62-288838 can be used very effectively as a solution to such a problem. In addition, JP-A-57
-8,542 isothiazolone compounds, siabendazoles, chlorinated fungicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc. Hiroshi Horiguchi "Chemistry of Antibacterial and Antifungal Agents" (1986) Sankyo Publishing "Sterilization, sterilization and antifungal technology of microorganisms" edited by the Society for Hygiene Technology (1982) Industrial Technology Association, "Antibacterial and Antifungal Encyclopedia" edited by Japan Society for Antibacterial and Antifungal (1986)
It is also possible to use the bactericide described in.

Rinsing water in processing the light-sensitive material of the present invention
The pH is 4-9, preferably 5-8. The washing water temperature and the washing time can be variously set depending on the characteristics of the light-sensitive material, the use, etc., but in general, it is 20 seconds to 10 minutes at 15 to 45 ° C., preferably
A range of 30 seconds to 5 minutes at 25-40 ° C is selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilization treatment, all known methods described in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345 can be used.

In the stabilizing solution, compounds that stabilize the dye image, such as formalin, benzaldehydes such as m-hydroxybenzaldehyde, formaldehyde bisulfite adduct, hexamethylenetetramine and its derivatives, hexahydrotriazine and its derivatives, Examples include N-methylol compounds such as dimethylol urea and N-methylol pyrazole, organic acids and pH buffering agents. The addition amount of these compounds is preferably 0.001 to 0.02 mol per liter of the stabilizing solution, but the lower the free formaldehyde concentration in the stabilizing solution is, the less the formaldehyde gas is scattered, which is preferable. From this point of view, examples of the dye image stabilizer include m-hydroxybenzaldehyde, hexamethylenetetramine, N-methylolpyrazole, N-methylolazoles described in JP-A-4-270344, N, N'-bis (1 , 2,4-Triazol-1-ylmethyl) piperazine etc.
Azolylmethylamines described in 13753 are preferred. Particularly, azoles such as 1,2,4-triazole described in JP-A-4-359249 (corresponding to European Patent Publication No. 519190A2) and 1,4-bis (1,2,4)
The combined use of azolylmethylamine and its derivatives such as -triazol-1-ylmethyl) piperazine is preferable because of high image stability and low formaldehyde vapor pressure. In addition, if necessary, ammonium compounds such as ammonium chloride and ammonium sulfite, metal compounds such as Bi and Al, optical brighteners, hardeners, US Pat.
It is also preferable to contain an alkanolamine described in JP-A-86,583 or a preservative that can be contained in the fixing solution or the bleach-fixing solution, for example, a sulfinic acid compound described in JP-A-1-231510. .

Various surfactants may be contained in the washing water and the stabilizing solution in order to prevent unevenness of water droplets when the processed light-sensitive material is dried. Among these, it is preferable to use a nonionic surfactant, and an alkylphenol ethylene oxide adduct is particularly preferable. Octyl, nonyl, dodecyl and dinonylphenol are particularly preferable as the alkylphenol, and 8 to 14 are particularly preferable as the number of moles of ethylene oxide added. Further, it is also preferable to use a silicon-based surfactant having a high defoaming effect.

It is preferable to add various chelating agents to the washing water and the stabilizing solution. Preferred chelating agents include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N, N'-trimethylenephosphonic acid and diethylenetriamine-N, N,
Examples thereof include organic phosphonic acids such as N ', N'-tetramethylenephosphonic acid, and hydrolyzates of maleic anhydride polymers described in European Patent 345,172A1.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic processor, etc., when the above processing solutions are concentrated by evaporation,
In order to correct the concentration by evaporation, it is preferable to replenish an appropriate amount of water or a correction solution or a processing replenishing solution. The specific method for replenishing water is not particularly limited, but among them, a monitor water tank different from the bleaching tank described in JP-A-1-254959 and 1-254960 is installed, and water in the monitor water tank is installed. The amount of water vaporized in the bleaching tank is calculated from the amount of water vaporized in the bleaching tank, and the bleaching tank is replenished with water in proportion to the amount of water vaporized.
Nos. 3,249,644, 3,249,645 and 3,249,646, the evaporation correction method using a liquid level sensor and an overflow sensor are preferable.
As the water for correcting the evaporation of each treatment liquid, tap water may be used, but deionized water or sterilized water which is preferably used in the above washing step is preferably used.

The various processing solutions in the present invention are used at 10 ° C to 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality to improve the stability of the processing liquid. be able to.

In the present invention, each processing solution can be commonly used for processing two or more kinds of photosensitive materials. For example,
By treating the color negative film and the color paper with the same treatment liquid, the cost of the treatment machine can be reduced and the treatment can be simplified.

[0147]

[Table 1]

[0148]

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

Example 1 Preparation of emulsion (a) (comparative example) 1200 ml of gelatin aqueous solution (gelatin 28
g, NaCl 4.0 g, N, N′-dimethylimidazoline-2-thione (containing 3.2 ml of 1% aqueous solution) is added], the temperature is set to 52 ° C., and 200.0 ml of AgNO ₃ aqueous solution is added with stirring ( (Including 32.9 g of AgNO ₃ ) and N
200.0 ml of aCl aqueous solution (containing 114.1 g of NaC) was added and mixed for 24 minutes. After adding 4.2 × 10 ⁻⁴ mol of the thiosulfonic acid compound, 523.0 ml of AgNO ₃ aqueous solution (containing 156.9 g of AgNO ₃ ) and 523.0 ml of NaCl aqueous solution (containing 54.0 g of NaCl) were heated at 52 ° C. While maintaining, the mixture was added and mixed over 26 minutes and 09 seconds. Subsequently, an AgBr fine grain emulsion described below was added in an amount of 1.3 × 10 ⁻³ mol and ripened for 10 minutes. Then, the temperature was lowered to 35 ° C., and desalting and washing with water were carried out in the usual way. The average equivalent spherical diameter of the obtained silver halide grains is 1.0.
It was a cube of μm. Preparation of AgBr fine grain emulsion 1200 ml of gelatin aqueous solution (M3 gelatin 2
4g, containing 0.09g KBr, pH 3.0),
While stirring at a temperature of 23 ° C., an AgNO ₃ aqueous solution 240.
0 ml (AgNO ₃ 60.0 g, M3 gelatin 2.0 g,
1M HNO ₃ (including 1.0 ml) and KBr aqueous solution 24
0.0 ml (KBr 42.0 g, M3 gelatin 2.0 g,
1M KOH (including 1.0 ml) at 90 cc / min for 2 minutes 40
Simultaneous mixed addition was performed for 2 seconds. After stirring for 30 seconds, pH 4.
0, adjusted to pBr 3.2. The obtained AgBr fine grain emulsion had an average equivalent spherical diameter of 0.04 μm.

Preparation of Emulsion (b) (Comparative Example) The below-mentioned emulsion (c) containing 164 g of AgNO ₃ corresponding to silver bromide was added to 1950 cc of water, and the temperature was 55 ° C. and pA.
g was maintained at 8.9 and pH at 5.0. Then 0.32
126 cc of a KI aqueous solution of M was quantitatively added for 5 minutes, and subsequently 206 cc of a 1.9 M AgNO ₃ aqueous solution and a KBr aqueous solution were added over 36 minutes so as to keep the pAg at 8.9.
After this, desalting was carried out by a conventional flocculation. The obtained silver iodobromide emulsion was a tabular grain having an average equivalent circle diameter of 2.1 μm, an average thickness of 0.30 μm and an average aspect ratio of 7,
Grains having an aspect ratio of 4 or more occupied 80% or more of the total projected area. Preparation of emulsion (c) (core emulsion of emulsion (b)) Aqueous solution 12 containing 6.2 g of gelatin and 6.4 g of KBr.
Stirring while keeping 00cc at 60 ℃, 1.9M AgN
An O ₃ aqueous solution (8 cc) and a 1.7 M KBr aqueous solution (9.6 cc) were added with a double jet for 45 seconds. After adding 38 g of gelatin, the temperature was raised to 75 ° C. and aging was carried out for 20 minutes in the presence of NH ₃ . After neutralization with HNO _3, while accelerating the flow rate while keeping the pAg of the AgNO ₃ solution 405cc of KBr aqueous solution of 1.9M to 8.22 (at the end of flow rate at the start 10
Double) and added for 87 minutes. Thereafter, this emulsion was cooled to 35 ° C. and desalted by a conventional flocculation method. The obtained silver bromide emulsion was a tabular grain having an average equivalent circular diameter of 2.0 μm, an average thickness of 0.25 μm and an average aspect ratio of 8.

Preparation of emulsion (d) (invention) 1200 ml of gelatin aqueous solution (gelatin 18.
0 g, pH 4.3) is added, the temperature is brought to 45 ° C.,
While stirring, 12.0 ml of AgNO ₃ aqueous solution (AgNO ₃
2.40g) and 12.0ml NaCl solution (Na
Cl (containing 0.83 g) was simultaneously added and mixed at 24 ml / min. After stirring for 1 minute, AgNO ₃ aqueous solution 19.0 m
1 (containing 0.38 g of AgNO ₃ ) and KBr aqueous solution 1
9.0 ml (containing 0.27 g of KBr) was simultaneously added and mixed at 30 ml / min. After stirring for 1 minute, 36.0 ml of AgNO ₃ aqueous solution (containing 7.20 g of AgNO ₃ ) and Na.
36.0 ml of Cl aqueous solution (including 2.48 g of NaCl)
Was mixed at 48 ml / min. Next, add 20.0 ml of NaCl aqueous solution (including NaCl 2.0) to adjust the pH.
Was set to 4.8. After ripening at 70 ° C. for 16 minutes, 0.997 mol of AgCl fine grain emulsion described below was added in an amount of Ag and ripening was performed for 35 minutes. Further, AgB used in the preparation of Emulsion A
The fine grain emulsion r was added in an amount of 0.003 mol and ripened for 6 minutes. Next, the temperature is lowered to 35 ° C.
The emulsion was washed with water by the precipitation washing method. Then, an aqueous gelatin solution was added to bring the temperature to 40 ° C., the pH of the emulsion was 6.4, and pCl 2.
Adjusted to 8. The obtained AgClBr grain emulsion had an average equivalent spherical diameter of 1.03 μm and an aspect ratio of 7. Preparation of AgCl fine particle emulsion 1200 ml of gelatin aqueous solution (24 g of gelatin having an average molecular weight of 30,000 (hereinafter referred to as M3 gelatin), NaC)
1 0.5 g, pH 3.0) was added, and the temperature was 23 ° C.
900.0 ml of AgNO ₃ aqueous solution (Ag
NO ₃ 225.0g, M3 gelatin 9.0g, 1M
HNO ₃ (containing 2.3 ml) and NaCl aqueous solution 900.
0 ml (NaCl 77.4 g, M3 gelatin 9.0 g,
(Containing 2.3 ml of 1 M KOH) was simultaneously mixed and added at 90 cc / min for 10 minutes. After stirring for 30 seconds, pH 4.
0, adjusted to pCl 1.7. The obtained AgCl fine grain emulsion had an average equivalent spherical diameter of 0.06 μm.

Next, the three kinds of silver halide emulsions thus prepared were treated at 60 ° C., pH 6.20 and pAg.
Emulsions (a) -1 to (a) -6, (b) -1 to (b) -7 and (d) -1 to (d) were subjected to the following chemical sensitization under the condition of 8.40. ) -15 was prepared.

First, the cyanine dyes shown in Table 2 were added to each emulsion at 40 ° C. in an amount corresponding to 85% of the saturated adsorption amount, but the emulsions (a) -6, (b) -6 and ( d)-
In No. 6, each cyanine dye was added in an amount corresponding to 42.5% of the saturated adsorption amount. 10 minutes later, silver 1
Per mol of 3.0 × 10 ⁻³ mol of potassium thiocyanate, 6 × 10 ⁻⁶ mol of potassium chloroaurate, 1 × 10 ⁻⁵ mol of sodium thiosulfate, and the selenium sensitizer shown in Chemical formula 17 below. 3 × 10 ^-6 mol per mol of silver halide was added, the temperature was raised and ripening was carried out at 60 ° C., and the ripening time was adjusted so that the sensitivity of 1/100 second exposure was maximized. Emulsion (b)
-7 and (d) -7 contain 135 per mol of silver halide.
mg 4-hydroxy-6-methyl-1,3,3a, 7-
Tetrazaindene (TAI) was added to emulsion (d) -8 in an amount of 12 mg of 1- (3-acetylaminophenyl) -5-mercaptotetrazole (APM) per mol of silver halide.
T) was added 3 minutes before the addition of the chemical sensitizer.

[0154]

[Table 2]

[0155]

[Chemical 16]

[0156]

[Chemical 17]

After the chemical sensitization, the following compounds were added to the triacetyl cellulose film support having an undercoat layer together with the protective layer by the simultaneous extrusion method so that the amount of silver was 0.5 g / m ^2. Samples 1 to 28 were prepared by coating the above color sensitized emulsion. (1) Emulsion layer-Emulsion ... The above-mentioned color-sensitized emulsion-Compound 1 represented by the following structural formula shown in Chemical formula 18 below-Tricresyl phosphate-Stabilizer 4-hydroxy-6-methyl-1, 3,3
a, 7-Tetrazaindene ・ Coating aid sodium dodecylbenzenesulfonate (2) Protective layer ・ Polymethylmethacrylate fine particles ・ 2,4-dichloro-6-hydroxy-s-triazine sodium salt ・ Gelatin

[0158]

[Chemical 18]

These samples were exposed for sensitometry (1/100 second) and subjected to the following rapid color development processing.

(Processing step) Processing time Processing temperature Color development 45 seconds 38 ℃ Bleach 30 seconds 38 ℃ Settlement 45 seconds 38 ℃ Stable (1) 20 seconds 38 ℃ stable (2) 20 seconds 38 ℃ stable (3) 20 seconds 38 ℃ Dry 30 seconds 60 ℃ * Stability was set to the countercurrent method from (3) to (1).

The composition of the processing liquid is shown below. (Color developer) Ethylenediaminetetraacetic acid 3.0 g 4,5-Dihydroxybenzene-1,3-disulphonic acid 2-sodium salt 0.3 g Potassium carbonate 30.0 g Sodium chloride 5.0 g Disodium-N, N-bis (Sulfonatoethyl) hydroxylamine 6.0 g 4- [N-ethyl-N- (β-hydroxylethyl) amino] -2-methylaniline sulfate 5.0 g Water was added to 1.0 liter pH (hydroxylation Adjusted with potassium and sulfuric acid) 10.00

(Bleaching Solution) 1,3-Diaminopropanetetraacetic acid ammonium ferric acid monohydrate 140 g 1,3-Diaminopropanetetraacetic acid 3 g Ammonium bromide 80 g Ammonium nitrate 15 g Hydroxyacetic acid 25 g Acetic acid (98%) 40 g Water was added. 1.0 liter pH (adjusted with aqueous ammonia and acetic acid) 4.3

(Fixer) Ethylenediaminetetraacetic acid disodium salt 15 g Ammonium sulfite 19 g Imidazole 15 g Ammonium thiosulfate (70 WT%) 280 ml Water was added to 1.0 liter pH (adjusted with ammonia water and acetic acid) 7.4

(Stabilizing Solution) Sodium p-toluenesulfinate 0.03 g Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization: 10) 0.2 g Ethylenediamon tetraacetic acid disodium salt 0.05 g 1,2, 4-triazole 1.3 g 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 g Water was added to 1.0 liter pH (adjusted with ammonia water and acetic acid) 8.5

The density of the treated sample was measured with a green filter.

The sensitivity was defined by the reciprocal of the exposure amount that gives a density of fog + 0.1, and was expressed as a relative value with the value of Sample 1 as 100. The sensitivity values are shown in Table 3 below. It can be seen from Table 3 that this emulsion has high sensitivity.

[0167]

[Table 3]

Example 2 On a subbed cellulose triacetate film support,
Each layer having the composition shown below was applied in multiple layers to prepare a sample as a multilayer color light-sensitive material. (Photosensitive layer composition) The main materials used for each layer are classified as follows; ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin Curing agent ExS: Sensitizing dye The numbers corresponding to the respective components indicate the coating amount expressed in units of g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

(Sample 100) First layer (antihalation layer) Black colloidal silver Silver 0.09 Gelatin 1.30 ExM-1 0.12 ExF-1 2.0 × 10 ^-3 Solid disperse dye ExF-2 0.030 Solid disperse dye ExF-3 0.040 HBS- 1 0.15 HBS-2 0.02

Second layer (intermediate layer) ExC-2 0.04 Polyethyl acrylate latex 0.20 Gelatin 1.04

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Silver chlorobromide emulsion A Silver 0.25 Silver chlorobromide emulsion B Silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-6 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87

Fourth Layer (Medium-Sensitivity Red Sensitive Emulsion Layer) Silver Chlorobromide Emulsion C Silver 0.70 ExS-1 3.5 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.1 × 10 ^-4 ExC-1 0.13 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.015 ExC-6 0.0070 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.75

Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver chlorobromide emulsion D Silver 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.10 ExC-3 0.045 ExC-6 0.020 ExC-7 0.010 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.050 Gelatin 1.10

Sixth layer (intermediate layer) Cpd-1 0.090 Solid disperse dye ExF-4 0.030 HBS-1 0.050 Polyethyl acrylate latex 0.15 Gelatin 1.10

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Silver chlorobromide emulsion E Silver 0.15 Silver chlorobromide emulsion F Silver 0.10 Silver chlorobromide emulsion G Silver 0.10 ExS-4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73

Eighth Layer (Medium-Sensitivity Green Sensitive Emulsion Layer) Silver Chlorobromide Emulsion H Silver 0.80 ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-6 8.4 × 10 ^-4 ExC-8 0.010 ExM-2 0.10 ExM-3 0.025 ExY-1 0.018 ExY-4 0.010 ExY-5 0.040 HBS-1 0.13 HBS-3 4.0 × 10 ^-3 Gelatin 0.88

Ninth layer (high-sensitivity green-sensitive emulsion layer) Silver chlorobromide emulsion I Silver 1.25 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExC-1 0.010 ExM-1 0.020 ExM-4 0.025 ExM-5 0.040 Cpd-3 0.040 HBS-1 0.25 Polyethyl acrylate latex 0.15 Gelatin 1.00

10th layer (yellow filter layer) Yellow colloidal silver Silver 0.015 Cpd-1 0.16 Solid disperse dye ExF-5 0.060 Solid disperse dye ExF-6 0.060 Oil-soluble dye ExF-7 0.010 HBS-1 0.60 Gelatin 0.70

Eleventh layer (low-sensitivity blue-sensitive emulsion layer) Silver chlorobromide emulsion J Silver 0.09 Silver chlorobromide emulsion K Silver 0.09 II-4 8.6 × 10 ^-4 ExC-8 7.0 × 10 ^-3 ExY-1 0.050 ExY-2 0.73 ExY-4 0.020 Cpd-2 0.10 Cpd-3 4.0 × 10 ^-3 HBS-1 0.32 Gelatin 1.20

12th layer (high-sensitivity blue-sensitive emulsion layer) Silver chlorobromide emulsion X Silver 1.00 (manufactured in this example) II-4 4.0 × 10 ^-4 ExY-2 0.10 ExY-3 0.10 ExY-4 0.010 Cpd -2 0.10 Cpd-3 1.0 x 10 ^-3 HBS-1 0.070 Gelatin 0.70

Thirteenth layer (first protective layer) UV-1 0.19 UV-2 0.075 UV-3 0.065 HBS-1 5.0 × 10 ^-2 HBS-4 5.0 × 10 ^-2 gelatin 1.2

14th layer (second protective layer) Silver chloride emulsion L Silver 0.10 H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.15 B-3 0.05 S- 1 0.20 Gelatin 0.70

Further, in order to improve the storability, processability, pressure resistance, antifungal / bacterial resistance, antistatic property and coating property of each layer, W-1 to W-3, B-4 to B- 6, F-1 ~ F
-17, and iron salt, lead salt, gold salt, platinum salt, palladium salt, iridium salt, and rhodium salt.

[0184]

[Table 4]

In Table 4, (1) Emulsions J, K, and X were reduction-sensitized at the time of grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-91938. (2) Emulsions A to I were prepared according to the examples of JP-A-3-237450.
Gold sensitization, sulfur sensitization and selenium sensitization are performed in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate. (3) Preparation of tabular grains is described in US Pat. No. 5,264,3
It is prepared according to the example of No. 37.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 shown below was dispersed by the following method. That is, water 21.7
3 ml of 5% aqueous solution of p-octylphenoxyethoxyethoxyethaneethanesulfonate and 5 g of 5% aqueous solution of p-octylphenoxypolyoxyethylene ether (polymerization degree: 10) (0.5 g) were put in a 700 ml pot mill, and the dye was added. 5.0 g of ExF-2 and 500 ml of zirconium oxide beads (diameter 1 mm) were added to disperse the contents for 2 hours. A BO type vibrating ball mill manufactured by Chuo Koki was used for this dispersion. After the dispersion, the contents were taken out, added to 8 g of a 12.5% gelatin aqueous solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the dye fine particles was 0.44 μm.

In the same manner, solid dispersions of ExF-3, ExF-4 and ExF-6 were obtained. The average particle diameters of the dye fine particles were 0.24 μm, 0.45 μm and 0.52 μm, respectively.
ExF-5 is a microprecipitation described in Example 1 of European Patent Application Publication (EP) 549,489A.
It was dispersed by the dispersion method. The average particle size was 0.06 μm.

[0188]

[Chemical 19]

[0189]

[Chemical 20]

[0190]

[Chemical 21]

[0191]

[Chemical formula 22]

[0192]

[Chemical formula 23]

[0193]

[Chemical formula 24]

[0194]

[Chemical 25]

[0195]

[Chemical formula 26]

[0196]

[Chemical 27]

[0197]

[Chemical 28]

[0198]

[Chemical 29]

[0199]

[Chemical 30]

[0200]

[Chemical 31]

[0201]

[Chemical 32]

[0202]

[Chemical 33]

[0203]

[Chemical 34]

(Preparation of Samples 101 to 125) Sample 100
In the preparation of Example 12, the emulsion X of the twelfth layer (high-sensitivity blue-sensitive emulsion layer) was added to the color sensitized emulsions (a) -1 to (a) -1 prepared in Example 1.
(A) -6, (b) -1 to (b) -7, (d) -1 to
Cyanine dye (II-4) added to the emulsion of the 11th layer (low-sensitivity blue-sensitive emulsion layer) using (d) -12.
Was changed to the same cyanine dye as that used in the 12th layer, and Samples 101 to 125 were prepared in exactly the same manner.

These samples 101 to 125 were exposed to blue sensitometric exposure (1/100 second) to obtain the sample of Example 1
The rapid color development processing shown in was carried out.

For the characteristic curve of the yellow color image, the toe sensitivity is expressed as a relative value with the value of Sample 101 being 100, and the results are shown in Table 5.

Using this sample, the storability was evaluated under the conditions of temperature of 50 ° C., humidity of 80% and 2 days. The storability was evaluated on the characteristic curve of a magenta color image using the sensitivity defined by the reciprocal of the exposure amount that gives a density 1.0 higher than the fog density. The sensitivity of the sample 101 at this time is 10
The sensitivity of other samples when subjected to the storage treatment was evaluated with a relative value of 0, and the results are shown in Table 5.

[0208]

[Table 5]

From Table 5, it can be seen that by using the emulsion of the present invention, the effect of providing high sensitivity can be obtained even in the rapid processing, and the storage stability can be further improved.

As described above (Examples 1 and 2), the silver halide photographic light-sensitive material of the present invention exhibits excellent photographic sensitivity.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] February 9, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0045

[Correction method] Change

[Correction content]

Among the cyanine dyes represented by the general formula (II), more preferred dyes are phenyl groups in which V ₂ is substituted with a chlorine atom, a bromine atom, a methoxy group, an ethoxy group, a methyl group or an ethyl group. Or represents a bromine atom or forms a benzene ring by linking with V ₁ or V ₃ ;
Particularly preferred is when ₂ is a phenyl group substituted with the above-mentioned substituent or a bromine atom.

Claims (4)

[Claims] 1. A tabular silver halide grain in which two parallel major planes are {100} faces, an aspect ratio is 2 or more, and an average silver chloride content of the grain is 50 mol% or more is halogenated. The silver halide emulsion is characterized by occupying 50% or more of the total projected area of silver grains, and at least one cyanine dye having a structure represented by the general formula (I) or / and a structure represented by the general formula (II) A silver halide emulsion characterized by being spectrally sensitized with at least one cyanine dye. General formula (I) In the formula, Z ₁ represents an oxygen atom, a sulfur atom or a selenium atom, and Z ₂ represents a sulfur atom or a selenium atom. W ₁ , W
₃ , W ₄ and W ₆ represent a hydrogen atom. W ₂ represents a bromine atom or an aryl group having a total carbon number of 9 or less, and when Z ₁ represents an oxygen atom, W ₂ may combine with W ₁ or W ₃ to form a benzene ring. W ₅ is a bromine atom or an aryl group having a total carbon number of 9 or less, an alkyl group having a carbon number of 3 to 6, an alkoxy group having a carbon number of 3 to 6, an optionally substituted phenoxy group having a total carbon number of 9 or less, In addition to the optionally substituted phenylthio group having 8 or less carbon atoms, when Z ₁ represents an oxygen atom, it may be linked with W ₄ or W ₆ to form a benzene ring. R ₁ and R ₂ may be the same or different and each represents an optionally substituted alkyl group or alkenyl group having 10 or less carbon atoms, and at least one of R _{1 and} R ₂ is a sulfo group or a carboxy group. Is a group having X ₁ represents a counter ion necessary for neutralizing the electric charge. n ₁ represents 0 or 1, and is 0 in the case of an inner salt. General formula (II) In the formula, Y ₁ and Y ₂ may be the same or different and each represents a sulfur atom or a selenium atom. V ₁ and V ₃ represent a hydrogen atom. V ₂ is a chlorine atom, a bromine atom or an aryl group having a total carbon number of 9 or less, an alkyl group having a carbon number of 3 to 6, an alkoxy group having a carbon number of 3 to 6, an optionally substituted phenoxy group having a total carbon number of 9 or less. The group represents an optionally substituted phenylthio group having a total carbon number of 8 or less, and may be linked to V ₁ or V ₃ to form a benzene ring. V ₅ represents connecting with V ₄ or V ₆ to form a benzene ring.
R ₃ and R _{4, which} may be the same or different, each represents an optionally substituted alkyl group or alkenyl group having 10 or less carbon atoms, and at least one of R _{3 and} R ₄ has a sulfo group. Is. X ₂ represents a counter ion necessary for neutralizing the charge. n ₂ represents 0 or 1,
It is 0 in the case of an inner salt. 2. A silver halide photographic light-sensitive material characterized in that at least one silver halide emulsion layer provided on a support contains the silver halide emulsion according to claim 1. 3. The silver halide photographic light-sensitive material according to claim 2, wherein the tabular silver halide grains are sensitized with gold and sulfur. 4. The tabular silver halide grains are present in the presence of at least one cyanine dye having a structure represented by formula (I) and / or at least one cyanine dye having a structure represented by formula (II). The silver halide photographic light-sensitive material according to claim 2, which is sensitized with gold and sulfur.