JP2002099053A - Silver halide photographic photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the sensitivity and storage stability of a silver halide photographic photosensitive material. SOLUTION: The silver halide photographic photosensitive material has at least one silver halide emulsion layer on a support. Particles of the silver halide adsorbing a sensitizing dye in a plurality of layers, are included in the emulsion layer. The reduction potential of the dye in the first layer of the particle is nobler than the one in the second layer or more from which 0.5 V subtracted.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic material using a spectrally sensitized silver halide photographic emulsion.

[0002]

2. Description of the Related Art Hitherto, great efforts have been made to increase the sensitivity of silver halide photographic light-sensitive materials. In a silver halide photographic emulsion, the sensitizing dye adsorbed on the surface of the silver halide grains absorbs light incident on the photographic material and transmits the light energy to the silver halide grains to obtain photosensitivity. Therefore, in the spectral sensitization of silver halide, the light energy transmitted to the silver halide can be increased by increasing the light absorptivity per unit grain surface area of the silver halide grains, thereby increasing the spectral sensitivity. It is believed that sensitivity is achieved. In order to improve the light absorptance on the surface of the silver halide grains, the amount of the spectral sensitizing dye adsorbed per unit grain surface area may be increased. However, the amount of sensitizing dye adsorbed on the surface of silver halide grains is limited, and it is difficult to adsorb more dye chromophore than single-layer saturated adsorption (ie, single-layer adsorption). Therefore,
At present, the absorptance of individual silver halide grains for incident light quanta in the spectral sensitization region is still low.

A method proposed to solve these points is described below. P.B. Gilman, Jr. et al., Photographic Science and Engine Nearing (Photographic Science and).
Engineering, Vol. 20, No. 3, No. 97 (1976), a cationic dye was adsorbed on the first layer, and an anionic dye was adsorbed on the second layer using electrostatic force. GB Bird et al., In U.S. Pat. No. 3,622,316, adsorb multiple dyes onto silver halide in multiple layers and apply them to Forster (Ford).
sensitized by the contribution of the (ster) -type excitation energy transfer.

[0004] Sugimoto et al., JP-A-63-138,341.
Nos. 64-84 and 244, spectral sensitization was performed by energy transfer from the luminescent dye. R. Steiger et al., Photographic Science and Engine Nearing (Photographic Science and)
Engineering, Vol. 27, No. 2, No. 59, 1983 (1983), an attempt was made to spectrally sensitize a gelatin-substituted cyanine dye by energy transfer. Conducted spectral sensitization by energy transfer from a cyclodextrin-substituted dye in JP-A-61-251842. Also, Richard Parton et al., European Patent 0985964A1, European Patent 0985965A1, European Patent 0985966A1, European Patent 0988565A.
In No. 1, multilayer adsorption was performed using a combination of a cationic dye and an anionic dye, and an attempt was made to increase the sensitivity by transferring energy from the second-layer dye to the first-layer dye.

However, in these methods, the degree to which the sensitizing dye is adsorbed in multiple layers on the surface of silver halide grains is actually insufficient, and the effect of improving the sensitivity is extremely small.

[0006] Yamashita et al. In Japanese Patent Application Laid-Open No. 10-239789 have realized multi-layer adsorption using a cation dye having an aromatic group and an anion dye to increase the sensitivity. A so-called linked dye, which has two chromophores that are not separately conjugated but linked by a covalent bond, is capable of bringing a dye portion not adsorbed to silver halide and an adsorbed dye portion into close proximity by a covalent bond. This is a promising method for efficiently transmitting light absorption energy to silver halide to enhance the sensitivity, and for enhancing the stability of the second layer dye. For the linking dye,
For example, U.S. Pat. Nos. 2,393,351 and 2,425,
772, 2,518,732, 2,521,9
44, 2,592,196, European Patent 565,0
No. 83, etc. However, these were not aimed at improving the light absorption rate. GB Bird (GBB.
Bird), A.L. Borr
or) et al., U.S. Pat. Nos. 3,622,317 and 3,9
No. 76,493, linked sensitizing dye molecules having a plurality of cyanine chromophores are adsorbed to increase the light absorption,
Sensitization was achieved by the contribution of energy transfer. Ukai, Okazaki and Sugimoto disclose in JP-A-64-91134 that at least one of a substantially non-adsorbing cyanine, merocyanine and hemicyanine dye containing at least two sulfo groups and / or carboxyl groups is halogenated. It was proposed to couple to a spectral sensitizing dye that could be adsorbed on silver halide.

Further, L. C. Bishwakarma (L.
C. Vishwakarma) is disclosed in JP-A-6-57235.
In the above, a method of synthesizing a linked dye by a dehydration condensation reaction of two dyes was described. Further, Japanese Patent Application Laid-Open No. 6-27
No. 578 shows that the linked dye of monomethine cyanine and pentamethine oxonol has red sensitivity. In this case, the emission of oxonol and the absorption of cyanine do not overlap, and the Forster type excitation energy between the dyes is eliminated. -Spectral sensitization due to migration does not occur, and high sensitivity cannot be expected due to the condensing action of the linked oxonol.

[0008] Also, R. L. Parton (RL
(Parton et al.) In European Patent No. 887,770 A1 reported that a compound in which a merocyanine dye was linked to a cyanine dye by a linking group containing a heteroatom was used to enhance sensitization, but the effect of improving light absorption was not sufficient.

Also, M. Roberts (MR.
Roberts et al. In US Pat. No. 4,950,587 proposed spectral sensitization with cyanine dye polymers. On the other hand, in order to provide a high quality silver halide photographic light-sensitive material, it is required that the performance of the light-sensitive material does not change over a long period of time. However, in a photographic material in which a sensitizing dye is multi-layer-adsorbed on the surface of silver halide grains by the above-described method to increase the sensitivity, there is a problem that the performance such as sensitivity and fog may change during storage. Was.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic emulsion having high sensitivity and excellent storage stability and a photographic material using the same.

[0011]

(1) In a silver halide photographic material having at least one photosensitive silver halide emulsion layer on a support, a sensitizing dye is adsorbed to the emulsion layer in multiple layers. It contains silver halide grains, and the reduction potential of the first dye of the grains is determined from the value of the reduction potential of the second or more dyes.
A silver halide photographic material characterized by being nobler than a value obtained by subtracting 0.5 V. Preferably, the reduction potential of the first-layer dye is lower than the value of the reduction potential of the second-layer or higher dye. (2) The reduction potential of the first-layer dye is more noble than the value obtained by subtracting 0.2 V from the reduction potential of the second-layer or higher dye, and the reduction potential of the first-layer dye is lower than the second-layer dye. The silver halide photographic material as described in (1), which is lower than the value of the potential. (3) containing silver halide grains having a spectral absorption maximum wavelength of less than 500 nm and a light absorption intensity of 60 or more, or a spectral absorption maximum wavelength of 500 nm or more and a light absorption intensity of 100 or more.
The silver halide photographic material according to (1) or (2). (4) When the maximum value of the spectral absorption by the sensitizing dye is Amax, the wavelength interval between the shortest wavelength and the longest wavelength that indicates 50% of Amax is 120 nm or less (1), (1). 2),
Or the silver halide photographic light-sensitive material according to (3). (5) When the maximum value of the spectral sensitivity by the sensitizing dye is Smax, the wavelength interval between the shortest wavelength and the longest wavelength, which indicates 50% of Smax, is 120 nm or less (1), (2) ),
The silver halide photographic material according to (3) or (4). (6) The silver halide photographic light-sensitive material as described in (1), (2), (3), (4) or (5), which contains a dye having at least one aromatic group. (7) comprising a sensitizing dye having a basic nucleus fused to three or more rings (1), (2), (3), (4), (5), or (6)
The silver halide photographic light-sensitive material as described above. (8) In the silver halide emulsion, tabular grains having an aspect ratio of 2 or more account for 50% (area) of all silver halide grains in the emulsion.
(1), (2), characterized in that the emulsion is present
The silver halide photographic material according to (3), (4), (5), (6) or (7). (9) The excitation energy of the second-layer dye is transferred to the first-layer dye with an efficiency of 10% or more.
A silver halide photographic material as described in (1), (2), (3), (4), (5), (6), (7) or (8). (10) The first- and second-layer dyes both exhibit J-band absorption (1), (2), (3), (4), (5), (6),
The silver halide photographic material according to (7), (8) or (9). (11) silver halide grains characterized by having a silver halide adsorbing compound other than the sensitizing dye (1), (2), (3),
The silver halide photographic material according to (4), (5), (6), (7), (8), (9), or (10).

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The present invention relates to a photographic material having high sensitivity and excellent storage stability containing silver halide grains having sensitizing dyes adsorbed in multiple layers.

Methods for increasing the light absorption of a silver halide emulsion include a method of adsorbing more dye chromophore on the grain surface, a method of increasing the molecular extinction coefficient of the dye, and a method of reducing the dye occupation area. Any of these methods may be used, but preferably a method in which the dye chromophore is further adsorbed on the particle surface. here,
The state in which the dye chromophore is more adsorbed on the grain surface means that more bound dye is present in the vicinity of the silver halide grains and does not include the dye present in the dispersion medium. Even when the dye chromophore is covalently linked to the substance adsorbed on the particle surface, the effect of increasing the light absorption intensity is long when the linking group is long and the dye chromophore is present in the dispersion medium. It is not considered small and more adsorption. In so-called multilayer adsorption, in which a dye chromophore is adsorbed more than once on a grain surface, it is necessary that spectral sensitization is caused by a dye that is not directly adsorbed on the grain surface. It is necessary to transfer the excitation energy from the unadsorbed dye to the dye directly adsorbed on the particles. Therefore, if the transmission of the excitation energy needs to occur in more than 10 steps, the final transmission efficiency of the excitation energy becomes low, which is not preferable. One example is a case where most of the dye chromophore is present in a dispersion medium, such as a polymer dye as disclosed in JP-A-2-113239, and transmission of excitation energy is required in 10 or more steps. In the present invention, the number of dye coloring stages per molecule is preferably from 1 to 3, more preferably from 1 to 2.

The chromophore described herein means an atomic group that is the main cause of the absorption band of molecules described in the Dictionary of Physical and Chemical Sciences (4th edition, Iwanami Shoten, 1987), pp.985-986. Any atomic group is possible, such as an atomic group having an unsaturated bond such as C = C and N = N.

For example, cyanine dyes, styryl dyes, hemicyanine dyes, merocyanine dyes, trinuclear merocyanine dyes, tetranuclear merocyanine dyes, rhodacyanine dyes, complex cyanine dyes, complex merocyanine dyes, allopolar dyes, oxonol dyes, hemioxonol dyes, squarium Dye, croconium dye,
Azamethine dye, coumarin dye, arylidene dye, anthraquinone dye, triphenylmethane dye, azo dye, azomethine dye, spiro compound, metallocene dye,
Fluorenone dye, fulgide dye, perylene dye, phenazine dye, phenothiazine dye, quinone dye, indigo dye, diphenylmethane dye, polyene dye, acridine dye, acridinone dye, diphenylamine dye,
Examples include quinacridone dyes, quinophthalone dyes, phenoxazine dyes, phthaloperylene dyes, porphyrin dyes, chlorophyll dyes, phthalocyanine dyes, and metal complex dyes. Preferably, cyanine dye, styryl dye, hemicyanine dye, merocyanine dye, trinuclear merocyanine dye, tetranuclear merocyanine dye, rhodacyanine dye, complex cyanine dye, complex merocyanine dye, allopolar dye, oxonol dye, hemioxonol dye, squarium dye, Croconium dye,
And polymethine chromophores such as azamethine dyes.
More preferably, a cyanine dye, a merocyanine dye, or 3
Nuclear merocyanine dyes, tetranuclear merocyanine dyes and rhodacyanine dyes, particularly preferred are cyanine dyes, merocyanine dyes and rhodacyanine dyes, and most preferred are cyanine dyes.

For details of these dyes, see FM Harmer, "Heterocyclic Compounds-Cyanine Soybeans and Related.
Compounds (Heterocyclic Compounds-Cyanine Dyes a
nd Related Compounds), John Wiley & Sons, New York, London, 1964, DM Sturmer (DMStu
rmer), Heterocyclic Compounds-Special topics in heterocyclic Chemistry
terocyclic chemistry) ", Chapter 18, Section 14, Section 4
82-515. Preferred general formulas of the dyes include general formulas described in U.S. Pat. No. 5,994,051 at pages 32 to 36, and U.S. Pat.
7, 236, pp. 30-34. Also, preferred cyanine dyes, merocyanine dyes,
The general formula for rhodacyanine dyes is described in US Pat.
No. 694, columns 21-22 (XI), (XII) and (XIII) (however, the number of n12, n15, n17 and n18 is not limited, and is an integer of 0 or more (preferably 4 or more). Below)).

The adsorption of the dye chromophore to the silver halide grains is preferably at least 1.5 layers, more preferably 1.7 layers.
More than two layers, particularly preferably two or more layers. Although there is no particular upper limit, the number is preferably 10 or less, more preferably 5 or less.

In the present invention, the state in which the chromophore is further adsorbed on the surface of the silver halide grains is defined as the sensitizing dye added to the emulsion, the dye having the smallest area occupied by the dye on the surface of the silver halide grains. The reached saturated adsorption amount per unit surface area is defined as a more saturated coating amount, and the state in which the amount of adsorption of the dye chromophore per unit area is larger than the one more saturated coating amount. The number of adsorbed layers means the amount of adsorption based on the amount of one-layer saturated coating. Here, in the case of a dye in which dye chromophores are linked by a covalent bond, the dye occupied area of each dye in a non-linked state can be used as a reference.
The dye occupied area can be determined from an adsorption isotherm indicating the relationship between the concentration of free dye and the amount of adsorbed dye, and the particle surface area. Adsorption isotherms are described, for example, by A. Hers.
z) et al. Adsorption from Aquas Solution
eous Solution) Advances Inn
Chemistry Series (Advances in C
Chemistry Series) No. 17,173
Page (1968).

The amount of the sensitizing dye adsorbed on the emulsion grains is determined by separating the emulsion adsorbed with the dye into a centrifugal separator to separate the emulsion grains and the supernatant aqueous gelatin solution, and measuring the unadsorbed dye concentration by measuring the spectral absorption of the supernatant. Subtracting from the amount of dye added to determine the amount of adsorbed dye, and drying the precipitated emulsion particles, dissolving a certain weight of the precipitate in a 1: 1 mixture of aqueous sodium thiosulfate and methanol, and performing spectral absorption measurement Can be used to determine the amount of the adsorbed dye. When a plurality of types of sensitizing dyes are used, the adsorption amount of each dye can be determined by a technique such as high performance liquid chromatography. A method for determining the amount of dye adsorbed by quantifying the amount of dye in the supernatant is described in, for example, Journal of Physical Chemistry (W. West) et al.
Physical Chemistry) Vol. 56, 1
054 (1952). However, under conditions where the amount of dye added is large, even unadsorbed dye may precipitate, and the method of quantifying the dye concentration in the supernatant may not always obtain the correct amount of dye. On the other hand, if the method of measuring the amount of dye adsorbed by dissolving the precipitated silver halide particles, the emulsion particles have an overwhelmingly high sedimentation speed, so that the particles and the sedimented dye can be easily separated, and the dye adsorbed on the particles Only the quantity can be measured accurately. This method is the most reliable as a method for obtaining the dye adsorption amount. The amount of the photographically useful compound adsorbed on the particles can be measured in the same manner as the sensitizing dye. However, since the absorption is small in the visible light region, a quantitative method by high performance liquid chromatography is preferable to a quantitative method by spectral absorption.

As an example of a method for measuring the surface area of a silver halide grain, there is a method in which a transmission electron micrograph is taken by a replica method and the shape and size of each grain are obtained and calculated. In this case, the thickness of the tabular grains is calculated from the length of the shadow of the replica. Examples of a method for taking a transmission electron micrograph include, for example, “Electron Microscope Sample Techniques” edited by the Kanto Chapter of the Electron Microscopy Society of Japan, Seikodo Shinkosha 19
70th edition, Butterworth (Butterworth)
s), London, 1965, PB Hirsch et al., Electron Microscope of Chin Crystal (Electron).
Microscopy of ThinCrysta
ls).

Other methods include, for example, the journal of AM Kragin et al.
Of Photographic Science (The Jo
urnal of Photographic Sci
ence, Vol. 14, p. 185 (1966), Transactions of the Fara by JF Paddy.
day Society, Vol. 60, page 1325 (1
964), S. Boyer et al., Journal de Chimie Ph.
ysique et de Physicochimi
e biologice, Vol. 63, p. 1123 (1963), W. Wes
t) et al. of Journal of Physical Chemistry
Istry) Volume 56, 1054 pages (1952)
), H. Sauvenier
r) Editing, E. Klein et al. International Colloquium (International)
al Coloquium), Liege (Lieg)
e), 1959, "Scientific Photograph.
hy)) can be referred to. The dye occupation area can be determined experimentally for each case by the above method, but the molecular occupation area of a commonly used sensitizing dye is approximately 80%.
Since in the vicinity Å ^2, simply all of the dye can also be estimated roughly the number of adsorption layers a dye occupation area as 80 Å ² for.

In the present invention, when the dye chromophore is adsorbed on the silver halide grains in multiple layers, the reduction potential of the so-called first-layer dye chromophore directly adsorbed on the silver halide grains is the second layer. From the value of the reduction potential of the above dye chromophore, 0.5
It is more noble than V minus it. Preferably, the reduction potential of the dye chromophore of the first layer is more noble than a value obtained by subtracting 0.2 V from the value of the reduction potential of the dye chromophore of the second layer or more. More preferably, the reduction potential of the dye chromophore of the first layer is more noble than a value obtained by subtracting 0.2 V from the value of the reduction potential of the dye chromophore of the second layer or more, and the dye chromophore of the second layer or more Is lower than the reduction potential of

When the dye chromophores are linked by a covalent bond, the reduction potential of each of the dye chromophores adsorbed on the particle surface or the compound corresponding to the dye chromophore linked thereto is measured to obtain 1 Layer or 2
It can be the reduction potential of the dye in the layer. Examples of the compound corresponding to the dye chromophore include a compound in which a linking group is changed to an alkylsulfonic acid group.

Although various methods can be used for measuring the reduction potential and the oxidation potential, preferably, the measurement is performed by phase discrimination type second harmonic AC polarography, and accurate values can be obtained. . The method for measuring the potential by the phase discrimination type second harmonic AC polarography is described in Journal of Imaging Science (Journ).
al of Imaging Science), 3rd
0, page 27 (1986).

In the present invention, the light absorption intensity is the light absorption area intensity of the sensitizing dye per unit particle surface area,
The optical density Log when the amount of light incident on the unit surface area of the particles is I ₀ and the amount of light absorbed by the sensitizing dye on the surface is I.
(I ₀ / (I ₀ −I)) is defined as a value integrated with respect to the wave number (cm ⁻¹ ). Integration range from 5000 cm ^-1 to 35
Up to 000 cm ^-1 .

The silver halide photographic emulsion according to the present invention has a light absorption intensity of 100 or more and a spectral absorption maximum wavelength of 500 in the case of grains having a spectral absorption maximum wavelength of 500 nm or more.
In the case of a particle having a particle diameter of less than nm, it is preferable that the silver halide particle having a light absorption intensity of 60 or more contains at least 1/2 of the total projected area of the silver halide particle. In addition, the spectral absorption maximum wavelength is 50
In the case of particles of 0 nm or more, the light absorption intensity is preferably 150 or more, more preferably 170 or more, and particularly preferably 200 or more, and the spectral absorption maximum wavelength is 500 n.
m, the light absorption intensity is preferably 90
Or more, more preferably 100 or more, particularly preferably 1
20 or more. There is no particular upper limit, but preferably 200
0 or less, more preferably 1000 or less, particularly preferably 500 or less. Also, the spectral absorption maximum wavelength is 500n
m, the spectral absorption maximum wavelength is 350 n
m or more.

As an example of a method for measuring the light absorption intensity,
Can use a microspectrophotometer.
You. Microspectrophotometer measures the absorption spectrum of a small area
Device that can measure the transmission spectrum of a single particle.
Noh. Of the absorption spectrum of one particle by microspectroscopy
For the measurement, see Yamashita et al.'S report (The Photographic Society of Japan, 199
6th Annual Meeting Abstracts, p. 15)
Can be. From this absorption spectrum, the absorption per particle
Although light intensity is required, the light passing through the particles is
Absorbed on two sides of the surface
Absorption intensity per particle obtained by the method described above.
It can be obtained as の of the yield strength. At this time,
The interval for integrating the absorption spectrum is
5000cm ^-1From 35000cm^-1But on the experiment
Is 500 cm before and after the section with absorption by the sensitizing dye^-1About
It may be the integral of the section including the degree. Also, the light absorption intensity increases.
The strength of the dye and the number of adsorbed molecules per unit area
These values are determined uniquely, and the oscillator strength and color of the sensitizing dye
Converted to light absorption intensity by calculating the amount of element adsorbed and particle surface area
You can do it. The oscillator strength of the sensitizing dye is
Solution area intensity (optical density x cm^-1Value proportional to
Can be obtained experimentally as
The absorption area intensity of the dye is A (optical density × cm^-1), Sensitizing color
B (mol / mol Ag) and particle surface area
C (m^Two / MolAg), the light absorption is given by the following equation:
The strength can be determined within an error range of about 10%. 0.156 × A × B / C Even if the light absorption intensity is calculated from this equation, it is based on the above-mentioned definition.
The light absorption intensity (Log (I₀ / (I₀ −
I))) is the wave number (cm^-1) And real)
The same value is obtained. Dye chromophores in the second or higher layer
Is preferably a luminescent dye. Types of luminescent dyes
Has a skeleton structure of the dye used for the dye laser.
One is preferred. These are, for example, Mitsuo Maeda, laser
Research, Vol. 8, p. 694, p. 803, p. 958 (19
80) and Volume 9, p. 85 (1981), and F.S.
ehaefer, "Dye Lasers", Springer (1973)
It is arranged in.

Further, it is preferable that the maximum absorption wavelength of the dye chromophore of the first layer in the silver halide photographic light-sensitive material is longer than the maximum absorption wavelength of the dye chromophore of the second layer or more. Further, it is preferable that the emission of the dye chromophore of the second layer or more overlaps with the absorption of the dye chromophore of the first layer. Also,
The dye chromophore in the first layer preferably forms a J-aggregate. Further, in order to have absorption and spectral sensitivity in a desired wavelength range, it is preferable that the dye chromophores of the second layer or more also form J-aggregates. The energy transfer efficiency of the excitation energy of the second-layer dye to the first-layer dye is preferably 30% or more, more preferably 60%, and particularly preferably 90% or more. The efficiency of energy transfer from the second-layer dye to the first-layer dye can be determined as spectral sensitization efficiency when the second-layer dye is excited / spectral sensitization efficiency when the first-layer dye is excited.

The meanings of the terms used in the present invention are described below. Dye occupied area: occupied area per dye molecule. It can be determined experimentally from the adsorption isotherm. In the case of a dye in which a dye chromophore is linked by a covalent bond, the area occupied by the dye in an unlinked state is used as a reference. 80 for simplicity
Å ² . Single-layer saturated coating amount: The amount of dye adsorbed per unit particle surface area at the time of one-layer saturated coating. Reciprocal of the smallest dye occupied area among the added dyes. Multilayer adsorption: A state in which the amount of dye chromophore adsorbed per unit particle surface area is larger than the one-layer saturation coverage. Number of adsorbed layers: the amount of dye chromophore adsorbed per unit particle surface area based on the saturated coating amount per layer.

In order to enhance the interaction between the first-layer dye and the second-layer dye, electrostatic interaction, van der Waals interaction, hydrogen bonding, and It is preferable to utilize site bonds and their complex interaction forces. The main interaction between the dyes in the second layer is preferably a van der Waals interaction between the dye chromophores. It is also preferred to utilize coordination bonds and their complex interactions. 1 for the total adsorption energy of the second layer dye
Although it is difficult to actually determine the ratio of the interaction energy between the dyes in the second layer and the second layer, it can be estimated by using a computer chemistry technique such as a molecular force field calculation. Further, experimentally, the aggregation energies of the second-layer dye molecules and the first-layer dye molecules and the second-layer dye molecules were measured, and 100
× Cohesive energy of first-layer dye and second-layer dye molecules / (2
It can also be estimated as (the cohesive energy between the dye molecules of the first layer and the dye molecules of the first and second layers). The cohesive energy can be determined, for example, using the method of Matsubara and Tanaka et al. (Journal of the Photographic Society of Japan, 52: 395, 1989).

In the emulsion containing silver halide photographic emulsion grains having a light absorption intensity of 60 or 100 or more, the maximum value Amax of the spectral absorption by the sensitizing dye and the shortest value showing 50% of the maximum value Smax of the spectral sensitivity, respectively. The interval between the wavelength and the longest wavelength is preferably 120 nm or less, more preferably 100 nm or less. 80% of Amax and Smax
The interval between the shortest wavelength and the longest wavelength indicating
It is at least 100 nm, preferably at most 100 nm, more preferably at most 80 nm, particularly preferably at most 50 nm. Further, the interval between the shortest wavelength and the longest wavelength which represent 20% of Amax and Smax is preferably 180 nm or less, more preferably 150 nm or less, and particularly preferably 120 nm.
Or less, most preferably 100 nm or less. The longest wavelength showing a spectral absorption of 50% of Amax or Smax is preferably 460 nm to 510 nm, or 560 nm to 610 nm, or 640 nm to 730 nm.

When the spectral absorption maximum wavelength is less than 500 nm and the light absorption intensity is 60 or more, or when the spectral absorption maximum wavelength is 500 n
A preferred first method for realizing silver halide grains having a light absorption intensity of 100 or more at m or more is a method using the following specific dye.

For example, see JP-A-10-239789, and JP-A-10-239789.
-269,092 and 10-123650, JP-A-8-
Dyes having an aromatic group described in 328189;
A method in which a cationic dye having an aromatic group is used in combination with an anionic dye; a method using a dye having a multivalent charge described in JP-A-10-171588;
No. 4774, a method using a dye having a pyridinium group, a method described in JP-A-10-186559, a method using a dye having a hydrophobic group, and a method described in JP-A-10-186559.
197980, a method using a dye having a coordination bonding group, and Japanese Patent Application Nos. 11-63588, 11
-80141, 11-159731, 11-1
No. 59730, No. 11-171324, No. 11-22
No. 1479, No. 11-265768, No. 11-260
No. 643, No. 11-331571, No. 11-3315
No. 70, No. 11-311039, No. 11-33156
7, No. 11-3477781, Japanese Patent Application No. 2000-189.
A method using a specific dye described in No. 66 is preferable.

A particularly preferred method is a method using a dye having at least one aromatic group. Among them, preferably a positively charged dye, a dye whose charge is offset in the molecule, or a method using only a dye having no charge, or a combination of a positively and negatively charged dye, and both positive and negative In this method, at least one of the charged dyes uses a dye having at least one aromatic group as a substituent.

The aromatic group will be described in detail. Examples of the aromatic group include a hydrocarbon aromatic group and a heteroaromatic group. These are groups having a polycyclic fused ring in which hydrocarbon aromatic rings and heteroaromatic rings are fused together, or a polycyclic fused ring structure in which an aromatic hydrocarbon ring and an aromatic heterocyclic ring are combined, And may be substituted with a substituent V described below. As the aromatic ring contained in the aromatic group, preferably, benzene, naphthalene, anthracene, phenanthrene, fluorene, triphenylene, naphthacene, biphenyl, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyridine, pyrazine,
Pyrimidine, pyridazine, indolizine, indole,
Benzofuran, benzothiophene, isobenzofuran,
Examples include quinolidine, quinoline, phthalazine, naphthyridine, quinoxaline, quinoxazoline, quinoline, carbazole, phenanthridine, acridine, phenanthroline, thianthrene, chromene, xanthene, phenoxatiin, phenothiazine, phenazine and the like.

Further preferred are the above-mentioned hydrocarbon aromatic rings, particularly preferred are benzene and naphthalene, most preferred is benzene.

Examples of the dye include those described above as examples of the dye chromophore. Preferably, the dyes mentioned as examples of the polymethine dye chromophore described above are used.

More preferably, cyanine dyes, styryl dyes, hemicyanine dyes, merocyanine dyes, trinuclear merocyanine dyes, tetranuclear merocyanine dyes, rhodacyanine dyes, complex cyanine dyes, complex merocyanine dyes, allopolar dyes, oxonol dyes, hemioxonol dyes , Squarium dye, croconium dye, azamethine dye, more preferably cyanine dye, merocyanine dye, trinuclear merocyanine dye, tetranuclear merocyanine dye, rhodacyanine dye,
Particularly preferred are cyanine dyes, merocyanine dyes and rhodacyanine dyes, and most preferred are cyanine dyes.

Particularly preferred methods will be described in detail with reference to structural formulas.

That is, the following cases (1) and (2) are preferable. In (1) and (2), (2) is more preferable. (1) A method using at least one of cationic, betaine or nonionic methine dyes represented by the following general formula (I). (2) A method in which at least one of the cationic methine dyes represented by the following general formula (I) and at least one of the anionic methine dyes represented by the following general formula (II) are simultaneously used. General formula (I)

[0041]

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In the formula, Z ₁ represents an atom group necessary for forming a nitrogen-containing heterocyclic ring. However, the rings may be condensed with these. R ₁ is an alkyl group, an aryl group, or a heterocyclic group. Q ₁ represents a group necessary for the compound represented by formula (I) to form a methine dye. L ₁ and L ₂ represent a methine group. p ₁ represents 0 or 1. Where Z ₁ , R
₁ , Q ₁ , L ₁ , and L ₂ each have a substituent in which the methine dye represented by the general formula (I) becomes a cationic dye, a betaine dye, or a nonionic dye as a whole. However, when the general formula (I) is a cyanine dye or rhodacyanine dye, it preferably has a substituent that becomes a cationic dye. M ₁ represents a counter ion for charge balancing, and m ₁ represents a number of 0 or more necessary to neutralize the charge of the molecule. General formula (II)

[0043]

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In the formula, Z ₂ represents an atomic group necessary for forming a nitrogen-containing heterocyclic ring. However, the rings may be condensed with these. R ₂ is an alkyl group, an aryl group, or a heterocyclic group. Q ₂ represents a group necessary for the compound represented by the general formula (II) to form a methine dye. L ₃ and L ₄ represent a methine group. p ₂ represents 0 or 1. Where Z ₂ ,
R ₂ , Q ₂ , L ₃ and L ₄ have a substituent in which the methine dye represented by the general formula (II) as a whole becomes an anion dye. M ₂ represents a counter ion for charge balancing, and m ₂
Represents a number of 0 or more necessary to neutralize the electric charge of the molecule.

However, when the compound of the general formula (I) is used alone, R ₁ is preferably a group having an aromatic ring.

Further, the compound of the general formula (I) and the compound of the general formula (II)
When the compound of the formula ( ₁ ) is used in combination, at least one of R ₁ and R ₂ is preferably a group having an aromatic ring.
More preferably, both R ₁ and R ₂ are groups having an aromatic ring.

The cationic dye of the present invention may be any dye in which the charge of the dye excluding the counter ion is cationic, but is preferably a dye having no anionic substituent. The anionic dye of the present invention may be any dye having an anionic charge except for a counter ion, but is preferably a dye having at least one anionic substituent. The betaine dye of the present invention is a dye that has a charge in the molecule but forms an intramolecular salt, and the molecule has no charge as a whole. With the nonionic dye of the present invention,
A dye that has no charge in the molecule.

The term "anionic substituent" as used herein refers to a substituent having a negative charge, for example, a proton dissociable acidic group dissociated by 90% or more between pH 5 and 8. Specifically, for example, a sulfo group, a carboxyl group, a sulfato group,
And a phosphate group and a borate group. In addition, -CO
NHSO ₂ - group (sulfonylcarbamoyl group, a carbonyl sulfamoyl group), - CONHCO- group (carbonylation carbamoyl group), - SO ₂ NHSO ₂ - group (sulfonylsulfamoyl group), a phenolic hydroxyl group, etc.,
Depending on these pka and surrounding pH, a group from which a proton is dissociated may be mentioned. More preferably a sulfo group, a carboxyl group, -CONHSO ₂ - group, -CONHCO
— Group, —SO ₂ NHSO ₂ — group. Note that -CONH
SO ₂ — group, —CONHCO— group, —SO ₂ NHSO ₂ —
In some cases, the proton may not be dissociated due to these pka and surrounding pH, and in this case, it is not included in the anionic substituent herein. That is, when the proton is not dissociated, for example, a dye represented by the following general formula (I-1) can be regarded as a cationic dye even if two of these groups are substituted. Examples of the cationic substituent include a substituted or unsubstituted ammonium group and a pyridinium group.

The dye represented by the general formula (I) is more preferably represented by the following general formulas (I-1), (I-2) and (I-3). General formula (I-1)

[0050]

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In the general formula (I-1), L ₅ , L ₆ , L ₇ , L ₈ ,
L ₉ , L ₁₀ and L ₁₁ represent a methine group. p ₃ and p ₄
Represents 0 or 1. n ₁ represents 0, ₁ , 2, 3 or 4. Z ₃ and Z ₄ represent an atom group necessary for forming a nitrogen-containing heterocyclic ring. However, the rings may be condensed with these. R ₃ and R ₄ represent an alkyl group, an aryl group, or a heterocyclic group. M ₁ and m ₁ have the same meanings as in formula (I). However,
R ₃ , R ₄ , Z ₃ , Z ₄ , and L _{5 to} L ₁₁ have no anionic substituent when (I-1) is a cationic dye, and have an anionic substituent when (I-1) is a betaine dye Has one substituent.

Formula (I-2)

[0053]

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In the formula (I-2), L ₁₂ , L ₁₃ , L ₁₄ and L ₁₅
Represents a methine group. p ₅ represents 0 or 1. q ₁ is 0 or 1. n ₂ represents 0, 1, ₂ , 3, or 4. Z ₅ represents an atom group necessary for forming a nitrogen-containing heterocyclic ring. Z ₆
And Z ₆ ′ represent the atoms necessary for forming a heterocyclic or acyclic acidic terminal group together with (N—R ₆ ) q ₁ . However, a ring may be condensed to Z ₅ and Z ₆ and Z ₆ ′. R ₅ and R ₆ represent an alkyl group, an aryl group, or a heterocyclic group. M ₁ and m ₁ have the same meanings as in formula (I).
However, R ₅ , R ₆ , Z ₅ , Z ₆ and L _{12 to} L ₁₅ have a cationic substituent when (I-2) is a cationic dye, and (I-2)
Is a betaine dye, it has one cationic substituent and one anionic substituent, and if (I-2) is a nonionic dye, it has no cationic substituent and no anionic substituent.
General formula (I-3)

[0055]

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In the formula (I-3), L ₁₆ , L ₁₇ , L ₁₈ , L ₁₉ , L
_{20, L 21, L 22,} L 23, and L ₂₄ each represents a methine group. p
₆ and p ₇ represents 0 or 1. q ₂ is 0 or 1. n ₃
And n ₄ represents 0, 1, 2, 3, or 4. Z ₇ and Z ₉
Represents an atom group necessary for forming a nitrogen-containing heterocyclic ring.
Z ₈ and Z ₈ ′ represent a group of atoms necessary for forming a heterocycle together with (N—R ₈ ) q ₂ . However, rings may be condensed in Z ₇ , Z ₈ , Z ₈ ′, and Z ₉ . R ₇ ,
R ₈ and R ₉ represent an alkyl group, an aryl group, or a heterocyclic group. M ₁ and m ₁ have the same meanings as in formula (I). However,
R ₇ , R ₈ , R ₉ , Z ₇ , Z ₈ , Z ₉ , L _{16 to} L ₂₄ are (I-
When 3) is a cationic dye, it has no anionic substituent, and when (I-3) is a betaine dye, it has one anionic substituent.

As the anionic dye represented by the general formula (II), more preferably, the following general formula (II-1):
(II-2) and (II-3). General formula (II-1)

[0058]

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In the general formula (II-1), L ₂₅ , L ₂₆ , L ₂₇ , L
₂₈ , L ₂₉ , L ₃₀ and L ₃₁ represent a methine group. p ₈ and p ₉ represent 0 or 1. n ₅ represents 0, 1, 2, 3 or 4. Z ₁₀ and Z ₁₁ represent an atomic group necessary for forming a nitrogen-containing heterocyclic ring. However, the rings may be condensed with these. R ₁₀ and R ₁₁ represent an alkyl group, an aryl group, or a heterocyclic group. M ₂ and m ₂ have the same meanings as in formula (II). However, R ₁₀ and R _{1 1} has an anionic substituent.

Formula (II-2)

[0061]

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In the formula (II-2), L₃₂, L₃₃, L₃₄, And L
₃₅Represents a methine group. p₉Represents 0 or 1. q_ThreeIs 0 or
Represents 1. n₆Represents 0, 1, 2, 3 or 4. Z₁₂
Represents an atom group necessary for forming a nitrogen-containing heterocyclic ring.
Z₁₃And Z₁₃’Is (N-R₁₃) Q _ThreeComplex with
Elements required to form a cyclic or acyclic acidic end group
Represents a child group. Where Z₁₂, And Z₁₃And Z₁₃’Is a ring
It may be ringed. R₁₂And R₁₃Is an alkyl group, aryl
A heterocyclic group or a heterocyclic group. M_Two, M_TwoIs the general formula (II)
It is synonymous. Where R₁₂, R₁₃At least one of
Has an anionic substituent. General formula (II-3)

[0063]

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In the formula (II-3), L ₃₆ , L ₃₇ , L ₃₈ , L ₃₉ ,
_{L 40, L 41, L 42} , L 43, and L ₄₄ each represents a methine group.
p ₁₀ and p ₁₁ each represents 0 or 1. q ₄ is 0 or 1. n ₇ and n ₈ represent 0, 1, 2, 3 or 4. Z ₁₄ ,
And Z ₁₆ represent an atom group necessary for forming a nitrogen-containing heterocyclic ring. Z ₁₅ and Z ₁₅ ′ represent an atomic group necessary for forming a heterocyclic ring together with (N—R ₁₅ ) q ₄ . However, a ring may be condensed in Z ₁₄ , Z ₁₅ and Z ₁₅ ′, and Z ₁₆ . R ₁₄ , R ₁₅ and R ₁₆ represent an alkyl group, an aryl group, or a heterocyclic group. M ₂ and m ₂ have the same meanings as in formula (II). However, at least two of R ₁₄ , R ₁₅ and R ₁₆ have an anionic substituent.

However, when the compounds of the general formulas (I-1), (I-2) and (I-3) are used alone, at least one, preferably both of R ₃ and R ₄ are aromatic rings. group having, R ₅
And at least one of R ₆ , preferably a group having an aromatic ring, and at least one, preferably two, and more preferably at least three of R ₇ , R ₈ , and R _9. A group having

When the compounds of the general formulas (I-1), (I-2) and (I-3) are used in combination with the compounds of the general formulas (II-1), (II-2) and (II-3) Are the R _{3 to} R ₉ and R _{10 to} R ₉ of the combined dyes
₁₆ of at least one is a group having an aromatic ring, preferably two of a group having an aromatic ring, more preferably from three of the group having an aromatic ring, particularly preferably 4 or more Is a group having an aromatic ring.

According to the above preferred method, the light absorption intensity is 60 or more when the spectral absorption maximum wavelength is less than 500 nm, or the light absorption intensity is 1 or more when the spectral absorption maximum wavelength is 500 nm or more.
Although a silver halide grain of 00 or more can be realized, the dye in the second layer is usually adsorbed in a monomer state.
In most cases, the width will be wider than the desired absorption width and spectral sensitivity width. Therefore, in order to realize high sensitivity in a desired wavelength region, it is necessary to form a J-aggregate in the dye adsorbed in the second layer. Furthermore, since the J-aggregate has a high fluorescence yield and a small Stokes shift, it is also necessary to transfer the light energy absorbed by the second-layer dye to the first-layer dye having a close absorption wavelength by Forster-type energy transfer. preferable.

In the present invention, the dye of the second layer or more is
A dye adsorbed on silver halide grains but not directly adsorbed on silver halide. In the present invention, the J-aggregate of the dye in the second layer or more is defined as a monomer in a monomer state having no interaction between the dye chromophores, in which the absorption width of the dye adsorbed in the second layer or more is on the long wavelength side. It is defined as not more than twice the absorption width of the long wavelength side of the absorption exhibited by the dye solution. Here, the absorption width on the long wavelength side indicates an energy width between an absorption maximum wavelength and a wavelength that is longer than the absorption maximum wavelength and that exhibits absorption equal to の of the absorption maximum. It is generally known that when a J-aggregate is formed, the absorption width on the longer wavelength side becomes smaller than that in the monomer state. When adsorbed to the second layer in the monomer state,
Due to the non-uniformity of the adsorption position and the state, the absorption width becomes twice or more the absorption width on the long wavelength side in the monomer state of the dye solution.
Therefore, a J-aggregate of the dye in the second or higher layer can be defined by the above definition.

The spectral absorption of the dye adsorbed on the second or more layers is
It can be determined by subtracting the spectral absorption of the first layer dye from the total spectral absorption of the emulsion. The spectral absorption by the first-layer dye can be determined by measuring the absorption spectrum when only the first-layer dye is added. Further, by adding a dye desorbing agent to the emulsion in which the sensitizing dye is adsorbed in multiple layers to desorb the dyes in the second or more layers, the spectral absorption spectrum of the dye in the first layer can be measured. In an experiment in which a dye is desorbed from the particle surface using a dye desorbing agent, the first layer dye is usually desorbed after the second or more layers of dye have been desorbed. Spectral absorption can be determined. This makes it possible to determine the spectral absorption of the dyes in the second and higher layers. A method using a depigmenting agent is described in a report by Asanuma et al. (Journal of Physics B).
al Chemistry B), Vol. 101, pp. 2149 to 2153 (1997)).

To form a J-aggregate of a second-layer dye using a cationic dye, a betaine dye, or a nonionic dye represented by the general formula (I) and an anionic dye represented by the general formula (II) The dye to be adsorbed as the first layer and 2
It is preferable to separate and add the dye to be adsorbed to the layers after the first layer, and it is more preferable to use dyes having different structures for the first layer dye and the second layer or higher dye. It is preferable to add a cationic dye, a betaine dye, or a nonionic dye alone or a combination of a cationic dye and an anionic dye to the second or higher layer dye.

As the dye for the first layer, any dye can be used. Preferably, the dye is represented by the general formula (I) or (I)
It is a dye represented by I), and more preferably a dye represented by the general formula (I). As the second layer dye, it is preferable to use the cationic dye, the betaine dye, or the nonionic dye of the general formula (I) alone. In the case where a cationic dye and an anionic dye are used in combination as the preferred second layer dye in the same row, it is preferable that one of the two is a cationic dye of the general formula (I) or an anionic dye of the general formula (II), Further, it is preferable to include both the cationic dye of the general formula (I) and the anionic dye of the general formula (II). The ratio of the cationic dye / anionic dye as the second-layer dye is preferably from 0.5 to 2, more preferably from 0.75 to 1.33, and most preferably from 0.9 to 1.
11 range.

In the present invention, a dye other than the dye represented by the general formula (I) or (II) may be added.
The dye represented by the general formula (I) or (II) is preferably at least 50%, more preferably at least 70%, most preferably at least 90% of the total amount of the dye added.
By adding the second-layer dye in this manner, the interaction between the second-layer dyes can be enhanced while promoting rearrangement of the second-layer dyes, so that a J-aggregate can be formed.

When the dye of the formula (I) or (II) is used as the first layer dye,
Z ₁ and Z ₂ are preferably a basic nucleus substituted with an aromatic group or a basic nucleus condensed with three or more rings. When used as a second or higher layer dye, Z ₁ and Z ₂ are preferably basic nuclei condensed with three or more rings.

The number of condensed rings of the basic nucleus is, for example, 2 for the benzoxazole nucleus and 3 for the naphthoxazole nucleus. Even when the benzoxazole nucleus is substituted with a phenyl group, the number of condensed rings is 2. The basic nucleus condensed with three or more rings is not particularly limited as long as it is a polycyclic condensed heterocyclic basic nucleus condensed with three or more rings.
Cyclic condensed heterocyclic rings and tetracyclic condensed heterocyclic rings are included. As the tricyclic condensed heterocyclic ring, naphtho [2,3-
d] oxazole, naphtho [1,2-d] oxazole, naphtho
[2,1-d] oxazole, naphtho [2,3-d] thiazole, naphtho [1,2-d] thiazole, naphtho [2,1-d] thiazole, naphtho [2,3-d] imidazole, naphtho [1,2-d] imidazole, naphtho [2,1-d] imidazole, naphtho [2,3-d] selenazole, naphtho [1,2-d] selenazole, naphtho [2,1-
d] selenazole, indolo [5,6-d] oxazole, indolo [6,5-d] oxazole, indolo [2,3-d] oxazole, indolo [5,6-d] thiazole, indolo [6,5- d] thiazole, indolo [2,3-d] thiazole, benzofuro [5,6-
d] oxazole, benzofuro [6,5-d] oxazole, benzofuro [2,3-d] oxazole, benzofuro [5,6-d] thiazole, benzofuro [6,5-d] thiazole, benzofuro [2,
3-d] thiazole, benzothieno [5,6-d] oxazole,
Benzothieno [6,5-d] oxazole, benzothieno [2,3-
d] oxazole and the like. Further, as the tetracyclic condensed heterocyclic ring, preferably anthra [2,3-d] oxazole, anthra [1,2-d] oxazole, anthra [2,1-d] oxazole, anthra [2,3- d] thiazole, anthra [1,
2-d] thiazole, phenanthro [2,1-d] thiazole,
Phenanthro [2,3-d] imidazole, anthra [1,2-d]
Imidazole, anthra [2,1-d] imidazole, anthra [2,3-d] selenazole, phenanthro [1,2-d] selenazole, phenanthro [2,1-d] selenazole, carbazolo [2,3-d] Oxazole, carbazolo [3,2-d] oxazole, dibenzofuro [2,3-d] oxazole, dibenzofuro
[3,2-d] oxazole, carbazolo [2,3-d] thiazole,
Carbazolo [3,2-d] thiazole, dibenzofuro [2,3-d] thiazole, dibenzofuro [3,2-d] thiazole, benzofuro [5,6-d] oxazole, dibenzothieno [2,3-d] oxazole, Dibenzothieno [3,2-d] oxazole, tetrahydrocarbazolo [6,7-d] oxazole, tetrahydrocarbazolo [7,6-d] oxazole, dibenzothieno [2,
3-d] thiazole, dibenzothieno [3,2-d] thiazole,
Tetrahydrocarbazolo [6,7-d] thiazole and the like. More preferably, the basic nucleus condensed with three or more rings is naphtho [2,3-d] oxazole, naphtho [1,2-d] oxazole, naphtho [2,1-d] oxazole, naphtho [2,3- d] thiazole, naphtho [1,2-d] thiazole, naphtho [2,1-d]
Thiazole, indolo [5,6-d] oxazole, indolo
[6,5-d] oxazole, indolo [2,3-d] oxazole,
Indolo [5,6-d] thiazole, indolo [2,3-d] thiazole, benzofuro [5,6-d] oxazole, benzofuro [6,5-
d] oxazole, benzofuro [2,3-d] oxazole, benzofuro [5,6-d] thiazole, benzofuro [2,3-d] thiazole, benzothieno [5,6-d] oxazole, anthra [2,
3-d] oxazole, anthra [1,2-d] oxazole, anthra [2,3-d] thiazole, anthra [1,2-d] thiazole, carbazolo [2,3-d] oxazole, carbazolo [3, 2-
d] oxazole, dibenzofuro [2,3-d] oxazole,
Dibenzofuro [3,2-d] oxazole, carbazolo [2,3-d]
Thiazole, carbazolo [3,2-d] thiazole, dibenzofuro [2,3-d] thiazole, dibenzofuro [3,2-d] thiazole, dibenzothieno [2,3-d] oxazole, dibenzothieno [3,2-d] Oxazole, and particularly preferably, naphtho [2,3-d] oxazole, naphtho [1,2-d] oxazole, naphtho [2,3-d] thiazole, indolo [5,6-d] oxazole, Indolo [6,5-d] oxazole, indolo
[5,6-d] thiazole, benzofuro [5,6-d] oxazole,
Benzofuro [5,6-d] thiazole, benzofuro [2,3-d] thiazole, benzothieno [5,6-d] oxazole, carbazolo [2,3-d] oxazole, carbazolo [3,2-d] oxazole, Dibenzofuro [2,3-d] oxazole, dibenzofuro
[3,2-d] oxazole, carbazolo [2,3-d] thiazole, carbazolo [3,2-d] thiazole, dibenzofuro [2,3-
d] thiazole, dibenzofuro [3,2-d] thiazole, dibenzothieno [2,3-d] oxazole, dibenzothieno [3,2-
d] Oxazole.

Another preferable method for realizing an adsorption state in which a dye chromophore covers the surface of a silver halide grain in multiple layers is a method of forming two or more dye chromophores linked by a covalent bond by a linking group. This is a method using a dye compound having a group moiety. The dye chromophore that can be used is not particularly limited, and examples thereof include those described above for the dye chromophore. Preferably, it is the polymethine dye chromophore represented by the aforementioned dye chromophore. More preferred are cyanine dyes, merocyanine dyes, rhodacyanine dyes, oxonol dyes, particularly preferably cyanine dyes,
Rhodocyanine dyes and merocyanine dyes, most preferably cyanine dyes.

As a preferred example, see, for example,
265144, a method using a dye linked by a methine chain, JP-A-10-226758, a method using a dye linked to an oxonol dye, JP-A-10-110107, and 10-30735.
8, Nos. 10-307359 and 10-310715, the method using a linking dye having a specific structure, and a specific linking group described in Japanese Patent Application Nos. 8-31212 and 10-204306. Using linked dyes, Japanese Patent Application Nos. 11-34444 and 11-34463.
And a method using a linked dye having a specific structure described in JP-A-11-34462, and a linked dye is formed in an emulsion using a dye having a reactive group described in Japanese Patent Application No. 10-249971. And the like.

A preferable linking dye is a dye represented by the following formula (III). General formula (III)

[0078]

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In the formula, D ₁ and D ₂ represent a dye chromophore.
La represents a linking group or a single bond. q and r each represent an integer from 1 to 100. M ₃ represents a charge balancing counter ion, and m ₃ represents a number necessary to neutralize the charge of the molecule.

Next, D ₁ , D ₂ and La will be described.

The dye chromophore represented by D ₁ and D ₂ may be any one. Specifically, those described above for the dye chromophore can be used. Preferably, it is the polymethine dye chromophore represented by the aforementioned dye chromophore. Further preferred are cyanine dyes, merocyanine dyes, rhodacyanine dyes and oxonol dyes, particularly preferred are cyanine dyes, merocyanine dyes and rhodacyanine dyes, most preferred are cyanine dyes. Preferred general formulas of the dyes include general formulas described in U.S. Pat. No. 5,994,051 at pages 32 to 36, and U.S. Pat.
7, 236, pp. 30-34. Also, preferred cyanine dyes, merocyanine dyes,
The general formula for rhodacyanine dyes is described in US Pat.
No. 694, columns 21-22 (XI), (XII) and (XIII) (however, the number of n12, n15, n17 and n18 is not limited, and is an integer of 0 or more (preferably 4 or more). Below)).

In the present invention, when the linking dye represented by the general formula (III) is adsorbed on silver halide grains, D ₂
Is preferably a chromophore not directly adsorbed on silver halide. That is, the suction force of the silver halide grains of D ₂ is preferably those with sensitive than D _1. Further, order of adsorption strength to a silver halide grain is, if a D _1> La> D ₂ being most preferred.

As described above, D ₁ is preferably a sensitizing dye moiety having adsorptivity to silver halide grains.
It may be adsorbed by either physical adsorption or chemical adsorption.

D ₂ has a low adsorptivity to silver halide grains and is preferably a luminescent dye. As the kind of the luminescent dye, those having a skeleton structure of a dye used for a dye laser are preferable. These are, for example, Mao Maeda,
8, 694, 803, 958 (1980) and 9, 85 (1981), and by F. Sehaefer, "Dye Lasers", Springer (197).
3 years).

Further, the maximum absorption wavelength of D _{1 in} the silver halide photographic material is preferably longer than the maximum absorption wavelength of D ₂ . Further, it is preferable that the light emission of the D ₂ overlaps with the absorption of D _1. Further, D ₁ preferably forms a J-aggregate. Further, in order for the linked dye represented by the general formula (I) to have absorption and spectral sensitivity in a desired wavelength range, it is preferable that D ₂ also forms a J-aggregate.

The reduction potential and the oxidation potential of D ₁ and D ₂ may be any, but the reduction potential of D ₁ is more noble than the value obtained by subtracting 0.2 v from the reduction potential of D _2. Is preferred.

La is a linking group (preferably a divalent linking group)
Or represents a single bond. The linking group preferably comprises an atom or an atomic group containing at least one of a carbon atom, a nitrogen atom, a sulfur atom and an oxygen atom. Preferably, an alkylene group (eg, methylene, ethylene, propylene, butylene, pentylene), an arylene group (eg, phenylene, naphthylene), an alkenylene group (eg, ethenylene, propenylene), an alkynylene group (eg, ethinylene, propynylene), an amide group, an ester Group, sulfoamide group, sulfonate group, ureido group, sulfonyl group, sulfinyl group, thioether group, ether group, carbonyl group, -N (Va)-(Va is a hydrogen atom,
Or a monovalent substituent. Examples of the monovalent substituent include V described below. ), A heterocyclic divalent group (for example, 6-chloro-1,3,5-triazine-2,4-diyl group, pyrimidine-2,4-diyl group, quinoxaline-2,3-
Diyl group) in combination with one or more carbon atoms, having 0 to 100 carbon atoms, preferably 1 to 2 carbon atoms.
Represents a linking group of 0 or less.

The above linking group may further have a substituent represented by V described below. Further, these linking groups may contain a ring (aromatic or non-aromatic hydrocarbon ring or heterocyclic ring).

More preferably, the alkylene group has 1 to 10 carbon atoms (eg, methylene, ethylene, propylene,
Butylene), an arylene group having 6 to 10 carbon atoms (for example, phenylene, naphthylene), an alkenylene group having 2 to 10 carbon atoms (for example, for example, ethenylene, propenylene), and an alkynylene group having 2 to 10 carbon atoms (for example, Ethynylene, propynylene), ether group,
It is a divalent linking group having 1 to 10 carbon atoms formed by combining one or more of an amide group, an ester group, a sulfamide group, and a sulfonic acid ester group. They are,
It may be replaced by V described later.

La is a linking group which may perform energy transfer or electron transfer by through-bond interaction. The through-bond interaction includes a tunnel interaction and a super-exchange interaction. Among them, a through-bond interaction based on a super-exchange interaction is preferable. Through-bond and super-exchange interactions are described by Shammai Speiser.
Author, Chemical Review (Chem. Rev.) Vol. 96, No. 1960
-Interaction as defined on page 1963, 1996. Linking groups that transfer energy or electrons by such an interaction include Shammai Spacer.
Speiser), Chemical Review (Chem. Rev.) No. 96
Vol., Pp. 1967-1969, 1996.

Q and r represent an integer from 1 to 100. It is preferably an integer of 1 to 5, more preferably an integer of 1 to 2, and particularly preferably 1. q
And when r is 2 or more, a plurality of La and D ₂ contained therein may be respectively different linking groups and dye chromophores.

The dye of the general formula (III) preferably has a charge of -1 as a whole.

More preferably, in the general formula (III), D ₁ and D ₂ are each independently the following general formula (IV):
This is the time when the methine dye is represented by (V), (VI) or (VII). General formula (IV)

[0094]

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In the formula (IV), L ₄₅ , L ₄₆ , L ₄₇ , L ₄₈ , L
₄₉ , L ₅₀ and L ₅₁ represent a methine group. p ₁₂ and p ₁₃
Represents 0 or 1. n ₉ represents 0, 1, 2, 3 or 4. Z ₁₇ and Z ₁₈ represent an atomic group necessary for forming a nitrogen-containing heterocyclic ring. However, the rings may be condensed with these. M ₄ represents a charge balancing counter ion, and m ₄ represents a number of 0 or more necessary to neutralize the charge of the molecule. R17 and R18 represent an alkyl group, an aryl group, or a heterocyclic group. General formula (V)

[0096]

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In the formula (V), L ₅₂ , L ₅₃ , L ₅₄ and L ₅₅ represent a methine group. p ₁₄ represents 0 or 1. q ₅ represents 0 or 1. n ₁₀ represents 0, 1, 2, 3 or 4. Z ₁₉
Represents an atom group necessary for forming a nitrogen-containing heterocyclic ring.
Z ₂₀ and Z ₂₀ 'represents an atomic group necessary to form a (N-R ₂₀₎ q ₅ and together heterocyclic ring or an acyclic acidic terminal groups. However, a ring may be condensed to Z ₁₉ , and Z ₂₀ and Z ₂₀ ′. M ₅ represents a charge balancing counter ion, m ₅
Represents a number of 0 or more necessary to neutralize the electric charge of the molecule.
R ₁₉ and R ₂₀ represent an alkyl group, an aryl group, or a heterocyclic group. General formula (VI)

[0098]

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In the formula (VI), L ₅₆ , L ₅₇ , L ₅₈ , L ₅₉ , L
₆₀ , L ₆₁ , L ₆₂ , L ₆₃ and L ₆₄ represent a methine group. p ₁₅
And p ₁₆ represents 0 or 1. q ₆ represents 0 or 1.
n ₁₁ and n ₁₂ represent 0, 1, 2, 3 or 4. Z ₂₁ and Z ₂₃ represent an atom group necessary for forming a nitrogen-containing heterocyclic ring. Z ₂₂ and Z ₂₂ ′ represent an atomic group necessary for forming a heterocyclic ring together with (N—R ₂₂ ) q ₆ . However,
Rings may be condensed on Z ₂₁ , Z ₂₂ and Z ₂₂ ′, and Z ₂₃ . M ₆ represents a charge-balancing counter ion, and m ₆ represents a number of 0 or more required to neutralize the charge of the molecule. R ₂₁ , R ₂₂ and R ₂₃ represent an alkyl group, an aryl group, or a heterocyclic group.

Formula (VII)

[0101]

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In the formula (VII), L₆₅, L₆₆, And L₆₇Is meth
Represents a group. q₇And q₈Represents 0 or 1. n₁₃Is 0,
Represents 1, 2, 3 or 4. Z_{twenty four}And Z_{twenty four}’Is (N-R_{twenty four})
q₇Together with and Z_{twenty five}And Z_{twenty five}’Is (N−
R_{twenty five}) Q₈Together with a heterocyclic or acyclic acid
Represents the group of atoms necessary to form a terminal group. However,
Z _{twenty four}And Z_{twenty four}’And Z_{twenty five}And Z_{twenty five}’Even if the ring is fused
good. M₇Represents a charge-balancing counter ion, m₇Is the molecular charge
Represents the number of 0 or more necessary to neutralize R_{twenty four}, And R
_{twenty five}Represents an alkyl group, an aryl group, or a heterocyclic group.

D _{1 in the} general formula (III) is preferably a methine dye represented by the above-mentioned general formulas (IV), (V) and (VI), more preferably D _{1 in} the general formula (IV) This is the case for methine dyes. D _{2 in the} general formula (III) is preferably a methine dye represented by the above general formulas (IV), (V), and (VII), and more preferably, a methine dye represented by the general formula (IV),
The case of the methine dye represented by (V), particularly preferably the case of the methine dye represented by the general formula (IV).

A method using the above general formulas (I) and (II),
Among the methods using the general formula (III), the methods using the general formulas (I) and (II) are more preferable.

The following formulas (I) (including (I-1, 2, 3)), (II) (including (II-1, 2, 3)), (IV), (V),
The methine compounds represented by (VI) and (VII) will be described in detail.

In the general formulas (I) and (II), Q ₁ and Q ₂ represent groups necessary for forming a methine dye. Q ₁ and Q ₂
Can form any methine dye, but the methine dye shown as an example of the dye chromophore described above can be used.

Preferred are cyanine dyes, merocyanine dyes, rhodacyanine dyes, trinuclear merocyanine dyes, tetranuclear merocyanine dyes, allopolar dyes, hemicyanine dyes and styryl dyes. More preferred are cyanine dyes, merocyanine dyes and rhodacyanine dyes, and particularly preferred are cyanine dyes. For more information on these dyes, see FM Harme
r), Heterocyclic Compounds-Cyanine Soybeans and Related Compounds (Heterocyc
lic Compounds-Cyanine Dyes and Related Compound
s) ", John Wiley and Sons
& Sons), New York, London, 1964, DMSturmer, Heterocyclic Compound Special Topics in Heterocyclic Chemistry
lic Compounds-Special topics in heterocyclic chemi
stry) ", Chapter 18, Section 14, pages 482 to 515 and the like. Preferred general formulas of the dyes include the general formulas described in U.S. Pat. No. 5,994,051 at pages 32 to 36, and U.S. Pat.
General formulas described on pages 0 to 34 are exemplified. The general formulas of preferred cyanine dyes, merocyanine dyes and rhodacyanine dyes are described in US Pat. No. 5,340,694, Nos. 21 and 2.
Those shown in (XI), (XII), and (XIII) in column 2 (however, the numbers of n12, n15, n17, and n18 are not limited, and are integers of 0 or more (preferably 4 or less)). Can be In the general formulas (I) and (II), when a cyanine dye or rhodacyanine dye is formed by Q ₁ and Q ₂ ,
It can also be expressed by the following resonance equation. General formula (I)

[0108]

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General formula (II)

[0110]

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In the general formulas (I), (II), (IV), (V) and (VI), Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ , Z ₇ , Z ₉ , Z _{9
10, Z 11, Z 12,} Z 14, Z 16, Z 17, Z 18, Z 19,
Z ₂₁ and Z ₂₃ represent an atomic group necessary for forming a nitrogen-containing heterocyclic ring, preferably a 5- or 6-membered nitrogen-containing heterocyclic ring. However, the rings may be condensed with these. As a ring,
It may be either an aromatic ring or a non-aromatic ring. Preferable is an aromatic ring, for example, a hydrocarbon aromatic ring such as a benzene ring and a naphthalene ring, and a heteroaromatic ring such as a pyrazine ring and a thiophene ring.

Examples of the nitrogen-containing heterocyclic ring include thiazoline nucleus, thiazole nucleus, benzothiazole nucleus, oxazoline nucleus, oxazole nucleus, benzoxazole nucleus, selenazoline nucleus,
Selenazole nucleus, benzoselenazole nucleus, 3,3-dialkylindolenine nucleus (for example, 3,3-dimethylindolenine), imidazoline nucleus, imidazole nucleus, benzimidazole nucleus, 2-pyridine nucleus, 4-pyridine nucleus, 2-
Quinoline nucleus, 4-quinoline nucleus, 1-isoquinoline nucleus, 3
-Isoquinoline nucleus, imidazo [4,5-b] quinoxaline nucleus, oxadiazole nucleus, thiadiazole nucleus, tetrazole nucleus, pyrimidine nucleus and the like,
Preferably, a benzothiazole nucleus, a benzoxazole nucleus, a 3,3-dialkylindolenine nucleus (for example, 3,3
-Dimethylindolenine), benzimidazole nucleus, 2
-Pyridine nucleus, 4-pyridine nucleus, 2-quinoline nucleus, 4-
A quinoline nucleus, a 1-isoquinoline nucleus and a 3-isoquinoline nucleus, more preferably a benzothiazole nucleus, a benzoxazole nucleus, a 3,3-dialkylindolenine nucleus (for example, 3,3-dimethylindolenine), and a benzimidazole nucleus. Particularly preferred are a benzoxazole nucleus, a benzothiazole nucleus and a benzimidazole nucleus, and most preferred are a benzoxazole nucleus and a benzothiazole nucleus.

Assuming that the substituent on these nitrogen-containing heterocycles is V, the substituent represented by V is not particularly limited.
For example, a halogen atom, an alkyl group (including a cycloalkyl group and a bicycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group, an aryl group, and a heterocyclic group (also referred to as a heterocyclic group) Good), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (Including anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, aryl O group, a heterocyclic thio group, a sulfamoyl group, a sulfo group, an alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an aryl or heterocyclic azo group,
Examples include an imide group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, and a silyl group. More specifically, V represents a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom), an alkyl group [a linear, branched, or cyclic substituted or unsubstituted alkyl group. They are alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl). A cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms,
For example, cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), a bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a hydrogen atom is converted from a bicycloalkane having 5 to 30 carbon atoms) This is a monovalent group that has been removed.
For example, bicyclo [1,2,2] heptan-2-yl,
Bicyclo [2,2,2] octan-3-yl), and also a tricyclo structure having many ring structures.
An alkyl group (for example, an alkyl group of an alkylthio group) among the substituents described below also represents an alkyl group having such a concept. And an alkenyl group [which represents a linear, branched or cyclic substituted or unsubstituted alkenyl group. They include alkenyl groups (preferably substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms such as vinyl, allyl, prenyl, geranyl, oleyl), cycloalkenyl groups (preferably substituted or substituted with 3 to 30 carbon atoms or An unsubstituted cycloalkenyl group, that is, a monovalent group obtained by removing one hydrogen atom from a cycloalkene having 3 to 30 carbon atoms, for example, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl), A bicycloalkenyl group (substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent obtained by removing one hydrogen atom of a bicycloalkene having one double bond; For example, bicyclo [2,2,1] hept-2-en-1-yl, bicyclo 2,2,2] oct-2-en-4-yl). An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms such as ethynyl, propargyl, trimethylsilylethynyl group, an aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms) For example, phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), a heterocyclic group (preferably a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound) And a monovalent group obtained by removing one hydrogen atom from, more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, for example, 2-furyl, 2-thienyl, -Pyrimidinyl, 2-benzothiazolyl), cyano, hydroxyl, nitro, carboxyl, alkoxy (preferably Ku is a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, for example,
Methoxy, ethoxy, isopropoxy, t-butoxy,
n-octyloxy, 2-methoxyethoxy), an aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, for example, phenoxy,
2-methylphenoxy, 4-t-butylphenoxy, 3
-Nitrophenoxy, 2-tetradecanoylaminophenoxy), a silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, for example, trimethylsilyloxy, t-butyldimethylsilyloxy), a heterocyclic oxy group (preferably carbon A substituted or unsubstituted heterocyclic oxy group of the number 2 to 30, 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy), an acyloxy group (preferably a formyloxy group, a substituted or unsubstituted group of 2 to 30 carbon atoms) A substituted alkylcarbonyloxy group, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, for example, formyloxy, acetyloxy, pivaloyloxy, stearoyloxy,
Benzoyloxy, p-methoxyphenylcarbonyloxy), carbamoyloxy group (preferably having 1 carbon atom)
To 30 substituted or unsubstituted carbamoyloxy groups, for example, N, N-dimethylcarbamoyloxy,
N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy),
An alkoxycarbonyloxy group (preferably having 2 carbon atoms)
To 30 substituted or unsubstituted alkoxycarbonyloxy groups such as methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-
Octylcarbonyloxy), an aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, for example, phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyl Oxyphenoxycarbonyloxy), an amino group (preferably,
An amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted anilino group having 6 to 30 carbon atoms, for example, amino, methylamino, dimethylamino, anilino, N-methyl-anilino, Diphenylamino), acylamino group (preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, for example, formylamino Acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino), aminocarbonylamino group (preferably having 1 to 3 carbon atoms)
0-substituted or unsubstituted aminocarbonylamino, for example, carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino), alkoxycarbonylamino group (preferably having 2 to 30 carbon atoms) A substituted or unsubstituted alkoxycarbonylamino group, for example,
Methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino), aryloxycarbonylamino group (preferably substituted or unsubstituted having 7 to 30 carbon atoms) Aryloxycarbonylamino group, for example, phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino), sulfamoylamino group (preferably having no carbon atoms)
To 30 substituted or unsubstituted sulfamoylamino groups such as sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino), alkyl and arylsulfonylamino groups (preferably carbon Substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms, such as methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-tri Chlorophenylsulfonylamino, p-methylphenylsulfonylamino), mercapto group, alkylthio group (preferably substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, for example, methylthio, ethylthio, n-hexadecylthio), aryl Lucio group (preferably having a carbon number of 6
To 30 substituted or unsubstituted arylthio, for example, phenylthio, p-chlorophenylthio, m-methoxyphenylthio), a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, for example, , 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio), a sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, for example, N-ethylsulfamoyl, N- (3
-Dodecyloxypropyl) sulfamoyl, N, N-
Dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl, N- (N'-phenylcarbamoyl) sulfamoyl), sulfo group, alkyl and arylsulfinyl group (preferably having 1 to 30 carbon atoms) Or an unsubstituted alkylsulfinyl group, 6 to 30 substituted or unsubstituted arylsulfinyl groups, for example, methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl), alkyl and arylsulfonyl groups (preferably having 1 to 30 substituted or unsubstituted alkylsulfonyl groups, 6 to 30 substituted or unsubstituted arylsulfonyl groups such as methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl), acyl Groups (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, substituted or unsubstituted carbon group having 4 to 30 carbon atoms) A heterocyclic carbonyl group bonded to a carbonyl group by an atom, for example, acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl), aryl An oxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, for example, phenoxycarbonyl, o-chlorophenoxycarbonyl, m-
Nitrophenoxycarbonyl, pt-butylphenoxycarbonyl), alkoxycarbonyl group (preferably substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyl) Oxycarbonyl), carbamoyl group (preferably,
A substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms, for example, carbamoyl, N-methylcarbamoyl,
N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl), aryl and heterocyclic azo groups (preferably substituted or unsubstituted arylazo groups having 6 to 30 carbon atoms;
A substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms, for example, phenylazo, p-chlorophenylazo,
5-ethylthio-1,3,4-thiadiazol-2-ylazo), imide group (preferably N-succinimide, N-phthalimido), phosphino group (preferably
A substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, for example, dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), a phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms; For example, phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl), phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, for example, diphenoxyphosphinyl Oxy, dioctyloxyphosphinyloxy), phosphinylamino group (preferably substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, for example, dimethoxyphosphinylamino, dimethylaminophosphinylamino ), A silyl group (preferably having 3 carbon atoms) 0 substituted or unsubstituted silyl group, for example, represents trimethylsilyl, t- butyl dimethylsilyl, phenyldimethylsilyl), a.
Further, a ring (aromatic or non-aromatic hydrocarbon ring or heterocyclic ring. These can be further combined to form a polycyclic fused ring. For example, a benzene ring, a naphthalene ring, an anthracene ring, a quinoline ring , A phenanthrene ring,
Fluorene ring, triphenylene ring, naphthacene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran Ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, quinoline ring, carbazole ring,
Phenanthridine ring, acridine ring, phenanthroline ring, thianthrene ring, chromene ring, xanthene ring, phenoxathiin ring, phenothiazine ring, phenazine ring. ) May be condensed.

Among the above substituents V, those having a hydrogen atom may be removed and further substituted with the above groups. Examples of such a substituent include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Examples include methylsulfonylaminocarbonyl, p-methylphenylsulfonylaminocarbonyl,
Acetylaminosulfonyl and benzoylaminosulfonyl groups are exemplified.

Preferred examples of the substituent include the above-mentioned alkyl group, aryl group, alkoxy group, halogen atom, fused aromatic ring, sulfo group, carboxy group and hydroxy group.

Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ , Z ₇ , Z ₉ , Z
_{10, Z 11, Z 12,} Z 14, and more preferably an aromatic group as a substituent V on Z _16, an aromatic ring condensed.

When the methine dye represented by formula (IV), (V) or (VI) represents the chromophore represented by D ₁ in formula (III), Z ₁₇ , Z ₁₈ , The substituent V on Z ₁₉ , Z ₂₁ , and Z ₂₃ is more preferably an aromatic group or an aromatic ring condensed.

When the methine dye represented by formula (IV), (V) or (VI) represents the chromophore represented by D ₂ in formula (III), Z ₁₇ , Z ₁₈ , The substituent V on Z ₁₉ , Z ₂₁ , and Z ₂₃ is more preferably a carboxy group, a sulfo group, or a hydroxy group, and particularly preferably a sulfo group.

Z ₆ and Z ₆ ′ and (NR ₆ ) q ₁ , Z ₁₃ and Z
₁₃ 'and _{(N-R 13) q 3} , Z 20 and Z _20' and (N-R ₂₀₎
q ₅ , Z ₂₄ and Z ₂₄ ′ and (NR ₂₄ ) q ₇ , and Z ₂₅ and Z ₂₅ ′ and (NR ₂₅ ) q ₈ are taken together to form a heterocyclic or acyclic group. Represents the group of atoms necessary to form an acidic end group. The heterocyclic ring (preferably a 5- or 6-membered heterocyclic ring) may be any, but an acidic nucleus is preferred. Next, the acidic nucleus and the acyclic acidic terminal group will be described. The acidic nucleus and acyclic acid end groups can take the form of the acidic nucleus and acyclic acid end groups of any common merocyanine dye. In a preferred form Z ₆ ,
Z ₁₃ , Z ₂₀ , Z ₂₄ and Z ₂₅ are a thiocarbonyl group, a carbonyl group, an ester group, an acyl group, a carbamoyl group, a cyano group or a sulfonyl group, more preferably a thiocarbonyl group or a carbonyl group. Z ₆ ', Z ₁₃ ',
Z ₂₀ ′ and Z ₂₄ ′ represent the remaining atomic groups necessary for forming an acidic nucleus and an acyclic acidic terminal group. When forming an acyclic acidic end group, preferably a thiocarbonyl group,
Carbonyl group, ester group, acyl group, carbamoyl group, cyano group, sulfonyl group and the like.

Q ₁ , q ₃ , q ₅ , q ₇ and q ₈ are 0 or 1
However, it is preferably 1.

The acidic nucleus and the acyclic acidic terminal group referred to herein are described, for example, in James, “Theory of the Photographic Process” (The Theory).
Theory of the Photograph
ic Process) 4th edition, Macmillan Publishing Company, 1
977, pp. 198-200. Here, the acyclic acidic terminal group means an acidic, that is, electron-accepting terminal group that does not form a ring. The acidic nucleus and the acyclic acidic end group are, specifically,
U.S. Pat. Nos. 3,567,719, 3,575,86
No. 9, No. 3, 804, 634, No. 3, 837, 862
No. 4,002,480,4,925,777
No. 3,167,546, U.S. Pat.
No. 4,051, U.S. Pat. No. 5,747,236 and the like.

The acidic nucleus forms a heterocycle (preferably a 5- or 6-membered nitrogen-containing heterocycle) consisting of carbon, nitrogen and / or chalcogen (typically oxygen, sulfur, selenium and tellurium) atoms. And more preferably a 5- or 6-membered nitrogen-containing heterocyclic ring composed of carbon, nitrogen and / or chalcogen (typically oxygen, sulfur, selenium and tellurium) atoms. Specifically, for example, the following nuclei can be mentioned.

2-pyrazolin-5-one, pyrazolidin-3,5 dione, imidazoline-5-one, hydantoin, 2 or 4-thiohydantoin, 2-iminooxazolidine-4-one, 2-oxazoline-5-one,
2-thiooxazolidin-2,5-dione, 2-thiooxazoline-2,4 dione, isoxazoline-5-one, 2-thiazoline-4-one, thiazolidine-4-one, thiazolidine-2,4 dione, rhodanine, thiazolidine-2,4-dithione, Isorhodanine, indan-1,3-dione, thiophen-3-one, thiophen-3-one-1,1, dioxide, indoline-2
-On, indoline-3-one, 2-oxoindazolinium, 3-oxoindazolinium, 5,7-dioxo6,7 dihydrothiazolo [3,2-a] pyrimidine, cyclohexane-1,3-dione, 3,4 Dihydroisoquinolin-4-one, 1,3-dioxane-4,6 dione, barbituric acid, 2-thiobarbituric acid, chroman-2,4 dione, indazolin-2-one, pyrido [1,2-a] pyrimidine-1,3 dione , Pyrazolo [1,5-b] quinazolone, pyrazolo [1,5-a]
Benzimidazole, pyrazolopyridone, 1, 2, 3,
4-tetrahydroquinoline-2,4-dione, 3-oxo-2,3-dihydrobenzo [d] thiophene-1,1
Dioxide, 3-dicyanomethine-2,3-dihydrobenzo [d] thiophen-1,1-dioxide nucleus.

Further, the carbonyl group or the thiocarbonyl group forming these nuclei is substituted at the active methylene position of the acidic nucleus to form a nucleus having an exomethylene structure, and a raw material for an acyclic acidic terminal group. A nucleus having an exomethylene structure substituted at the active methylene position of an active methylene compound having a structure such as ketomethylene or cyanomethylene.

The acidic nucleus and the acyclic acidic terminal group may be substituted or condensed with the substituent or ring represented by the substituent V described above.

Z ₆ and Z ₆ ′ and (NR ₆ ) q ₁ , Z ₁₃ and Z
₁₃ 'and _{(N-R 13) q 3} , Z 20 and Z _20' and (N-R ₂₀₎
As q ₅ , Z ₂₄ and Z ₂₄ ′ and (N—R ₂₄ ) q ₇ , and Z ₂₅ and Z ₂₅ ′ and (N—R ₂₅ ) q ₈ , preferably, hydantoin, 2 or 4-thiohydantoin, 2-oxazoline 5-one, 2-thiooxazoline-2,4 dione, thiazolidine-2,4 dione, rhodanine, thiazolidine-2,4 dithione, barbituric acid, 2-thiobarbituric acid, more preferably hydantoin, 2 or 4- Thiohydantoin, 2-oxazoline-5-one, rhodanine, barbituric acid, 2-thiobarbituric acid. Particularly preferred are 2- or 4-thiohydantoin, 2-oxazolin-5-one, rhodanine and barbituric acid.

Z₈And Z₈’And (N-R₈) Q_Two, Z_FifteenWhen
Z_Fifteen’And (N-R_Fifteen) Q_Four, And Z_{twenty two}And Z_{twenty two}’And (N-
R_{twenty two}) Q₆ As the heterocyclic ring formed by
Z₆And Z₆’And (N-R₆) Q₁ , Z₁₃And Z₁₃’And (N-
R₁₃) Q_Three, Z₂₀And Z₂₀’And (N-R₂₀) Q_Five, Z_{twenty four}And Z
_{twenty four}’And (N-R_{twenty four}) Q₇, And Z_{twenty five}And Z_{twenty five}’And (N-R
_{twenty five}) Q₈ The same ones mentioned in the description of heterocycle
Can be Preferably, the aforementioned Z ₆And Z₆’And (N-R₆) Q₁
 , Z₁₃And Z₁₃’And (N-R₁₃) Q_Three, Z₂₀And Z₂₀'When
(NR₂₀) Q_Five, Z_{twenty four}And Z_{twenty four}’And (N-R_{twenty four}) Q₇,
And Z_{twenty five}And Z_{twenty five}’And (N-R_{twenty five}) Q₈In the description of the heterocycle
Solid nuclei with oxo or thioxo groups removed
It is.

More preferably, the aforementioned Z₆And Z₆'When
(NR₆) Q₁ , Z₁₃And Z₁₃’And (N-R₁₃) Q_Three, Z
₂₀And Z₂₀’And (N-R₂₀) Q_Five, Z_{twenty four}And Z_{twenty four}’And (N-
R_{twenty four}) Q ₇, And Z_{twenty five}And Z_{twenty five}’And (N-R_{twenty five}) Q₈Concrete
An oxo group or a thioxo group from the acidic nucleus
Except for

More preferably, hydantoin, 2- or 4-thiohydantoin, 2-oxazoline-5-one,
2-thiooxazoline-2,4 dione, thiazolidine-2,4 dione, rhodanine, thiazolidine-2,4
Dithione, barbituric acid, 2-thiobarbituric acid is obtained by removing an oxo group or a thioxo group, particularly preferably hydantoin, 2 or 4-thiohydantoin, 2-oxazoline-5-one, rhodanine, barbituric acid, Oxo group from 2-thiobarbituric acid,
Or those excluding a thioxo group, most preferably 2
Or 4-thiohydantoin, 2-oxazoline-5-one, or rhodanine from which an oxo group or a thioxo group is removed.

Q ₂ , q ₄ and q ₆ are 0 or 1,
Preferably it is 1.

R₁, R_Two, R_Three, R_Four, R_Five, R₆, R₇,
R₈, R₉, R_Ten, R₁₁, R₁₂, R₁₃, R₁₄, R_Fifteen,
R₁₆, R₁₇, R₁₈, R₁₉, R₂₀, R_{twenty one}, R_{twenty two}, R_{twenty three}, R
_{twenty four}, And R _{twenty five}Is an alkyl group, an aryl group, and a heterocyclic group
Specifically, for example, carbon atoms 1 to 18,
Preferably 1 to 7, particularly preferably 1 to 4 unsubstituted
Alkyl groups (eg, methyl, ethyl, propyl, iso
Propyl, butyl, isobutyl, hexyl, octyl,
Dodecyl, octadecyl), 1 to 18 carbon atoms, preferred
Or 1 to 7, particularly preferably 1 to 4, substituted alkyl
A group such as an alkyl substituted with the aforementioned V as a substituent
Groups. Preferably an aralkyl group (e.g.
Jyl, 2-phenylethyl), unsaturated hydrocarbon group (eg,
Allyl group), hydroxyalkyl group (for example, 2-
Droxyethyl, 3-hydroxypropyl), carboxy
A silalkyl group (eg, 2-carboxyethyl, 3-ca)
Ruboxoxypropyl, 4-carboxybutyl, carboxy
Methyl), an alkoxyalkyl group (for example, 2-methoxy)
Ciethyl, 2- (2-methoxyethoxy) ethyl),
Leyloxyalkyl groups (eg, 2-phenoxyethyl,
2- (1-naphthoxy) ethyl), alkoxycarboni
Alkyl group (for example, ethoxycarbonylmethyl, 2-
Benzyloxycarbonylethyl), aryloxy
Bonylalkyl group (for example, 3-phenoxycarbonyl
Ropyl), acyloxyalkyl group (eg, 2-acetyl
Loxyethyl), an acylalkyl group (eg, 2-ace
Tylethyl), carbamoylalkyl group (eg, 2-
Ruphorinocarbonylethyl), sulfamoylalkyl
Groups (eg, N, N-dimethylsulfamoylmethyl),
Sulfoalkyl group (for example, 2-sulfoethyl, 3-s
Rufopropyl, 3-sulfobutyl, 4-sulfobutyl,
2- [3-sulfopropoxy] ethyl, 2-hydroxy
-3-sulfopropyl, 3-sulfopropoxyethoxy
Ethyl), sulfoalkenyl group, sulfatoalkyl group
(For example, 2-sulfatoethyl group, 3-sulfatotope
Ropyl, 4-sulfatobutyl), heterocyclic-substituted alkyl
Group (for example, 2- (pyrrolidin-2-one-1-yl)
Tyl, tetrahydrofurfuryl), alkylsulfonyl
Carbamoylalkyl group (for example, methanesulfonylcar
Bamoylmethyl group), acylcarbamoylalkyl group
(For example, acetylcarbamoylmethyl group), acylsul
Famoylalkyl groups (eg acetylsulfamoyl
Methyl group), alkylsulfonylsulfamoylal
A kill group (eg, methanesulfonylsulfamoylmethy
), Having 6 to 20 carbon atoms, preferably having 6 carbon atoms
10, more preferably an unsubstituted aryl having 6 to 8 carbon atoms
(Eg, phenyl group, naphthyl group), carbon number 6
To 20, preferably 6 to 10 carbon atoms, more preferably
Or a substituted aryl group having 6 to 8 carbon atoms (for example,
Examples of the above-mentioned V-substituted aryl groups are given as examples.
It is. Specifically, p-methoxyphenyl group, p-methyl
Phenyl group, p-chlorophenyl group and the like.
You. ), Having 1 to 20 carbon atoms, preferably 3 to 1 carbon atoms.
0, more preferably an unsubstituted heterocyclic group having 4 to 8 carbon atoms
(For example, 2-furyl, 2-thienyl, 2-pyridyl
Group, 3-pyrazolyl, 3-isoxazolyl, 3-iso
Thiazolyl, 2-imidazolyl, 2-oxazolyl, 2
-Thiazolyl, 2-pyridazyl, 2-pyrimidyl, 3-
Pyrazyl, 2- (1,3,5-triazolyl), 3- (1,2,4-
Triazolyl), 5-tetrazolyl), having 1-2 carbon atoms
0, preferably 3 to 10, more preferably carbon
A substituted heterocyclic group having a prime number of 4 to 8 (for example,
The above-mentioned heterocyclic group substituted by V is exemplified. Concrete
Typically, a 5-methyl-2-thienyl group, 4-methoxy-2
-Pyridyl group and the like. ).

R ₁ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ are preferably groups having an aromatic ring.
Examples of the aromatic ring include a hydrocarbon aromatic ring and a heteroaromatic ring, which are furthermore a hydrocarbon aromatic ring and a polycyclic fused ring in which the heteroaromatic rings are fused together, or an aromatic hydrocarbon ring. And a polycyclic fused ring in which is combined with an aromatic heterocyclic ring, and may be substituted with the aforementioned substituent V or the like. As the aromatic ring, those described as examples of the aromatic ring in the above description of the aromatic group are preferable.

The group having an aromatic ring is represented by -Lb-A
₁Can be represented by Here, Lb represents a single bond.
Or a linking group. A₁Represents an aromatic group
You. As the linking group for Lb, preferably, for example, the aforementioned La or the like.
Examples include the linking groups described above. A ₁Good as an aromatic group for
More preferably, those described as examples of the aromatic group described above are used.
You.

Preferably, as the alkyl group having a hydrocarbon aromatic ring, an aralkyl group (for example, benzyl,
-Phenylethyl, naphthylmethyl, 2- (4-biphenyl) ethyl), aryloxyalkyl group (for example, 2
-Phenoxyethyl, 2- (1-naphthoxy) ethyl,
2- (4-biphenyloxy) ethyl, 2- (o, m or p-halophenoxy) ethyl, 2- (o, m or p-methoxyphenoxy) ethyl), an aryloxycarbonylalkyl group (3-phenoxycarbonylpropyl, 2- (1-naphthoxycarbonyl) ethyl) and the like. Examples of the alkyl group having a heteroaromatic ring include 2- (2-pyridyl) ethyl and 2- (4-
Pyridyl) ethyl, 2- (2-furyl) ethyl, 2-
(2-thienyl) ethyl and 2- (2-pyridylmethoxy) ethyl are exemplified. 4 as a hydrocarbon aromatic group
-Methoxyphenyl, phenyl, naphthyl, biphenyl and the like. Examples of the heteroaromatic group include a 2-thienyl group, 4-chloro-2-thienyl, 2-pyridyl, and 3-pyrazolyl.

More preferred are the above-mentioned alkyl groups having a substituted or unsubstituted hydrocarbon aromatic ring or heteroaromatic ring. Particularly preferred are the above-mentioned alkyl groups having a substituted or unsubstituted hydrocarbon aromatic ring.

R ₂ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R
Preferred as ₁₅ and R ₁₆ are groups having an aromatic ring. Both R ₁₀ and R ₁₁ and at least one of R ₁₂ and R ₁₃ and at least one of R ₁₄ , R ₁₅ and R ₁₆ have an anionic substituent. R ₂ preferably has an anionic substituent. Examples of the aromatic ring include a hydrocarbon aromatic ring and a heteroaromatic ring.
Further, it may be a hydrocarbon aromatic ring, a polycyclic fused ring in which heteroaromatic rings are fused together, or a polycyclic fused ring in which an aromatic hydrocarbon ring and an aromatic heterocycle are combined, It may be replaced by V or the like. As the aromatic ring, those described as examples of the aromatic ring in the above description of the aromatic group are preferable.

The group having an aromatic ring is represented by -Lc-A
_TwoCan be represented by Here, Lc represents a single bond.
Or a linking group. A_TwoRepresents an aromatic group
You. As the linking group for Lc, preferably, for example, the aforementioned La or the like.
Examples include the linking groups described above. A _TwoGood as an aromatic group for
More preferably, those described as examples of the aromatic group described above are used.
You. Lc or A_TwoHas at least one anionic
It is preferred that the substituent is substituted.

Preferably, the alkyl group having a hydrocarbon aromatic ring is an aralkyl group substituted by a sulfo group, a phosphate group, or a carboxyl group (eg, 2-sulfobenzyl, 4-sulfobenzyl, 4-sulfophenethyl) , 3-phenyl-3-sulfopropyl, 3-phenyl-2-sulfopropyl, 4,4-diphenyl-3-sulfobutyl, 2- (4'-sulfo-4-biphenyl) ethyl, 4-phosphobenzyl), sulfo Aryloxycarbonylalkyl group (3-sulfophenoxycarbonylpropyl) substituted with a group, a phosphate group or a carboxyl group, an aryloxyalkyl group substituted with a sulfo group, a phosphate group, or a carboxyl group (for example, 2- (4-
Sulfophenoxy) ethyl, 2- (2-phosphophenoxy) ethyl, 4,4-diphenoxy-3-sulfobutyl), and the like. Examples of the alkyl group having a heteroaromatic ring include 3- (2-pyridyl) -3-sulfopropyl, 3- (2-furyl) -3-sulfopropyl, and 2- (2-thienyl) -2-sulfopropyl. Propyl and the like. Examples of the hydrocarbon aromatic group include a sulfo group, a phosphate group, and an aryl group substituted with a carboxyl group (eg, 4-sulfophenyl and 4-sulfonaphthyl). Examples of the heteroaromatic group include a sulfo group and a phosphate group. Or a heterocyclic group substituted with a carboxyl group (for example, 4
-Sulfo-2-thienyl group, 4-sulfo-2-pyridyl group) and the like.

More preferred are the above-mentioned alkyl groups having a hydrocarbon aromatic ring or a heteroaromatic ring substituted with the above-mentioned sulfo group, phosphate group and / or carboxyl group. An alkyl group having a hydrocarbon aromatic ring substituted with an acid group or a carboxyl group. Most preferably, 2-sulfobenzyl, 4
-Sulfobenzyl, 4-sulfophenethyl, 3-phenyl-3-sulfopropyl, 4-phenyl-4-sulfobutyl.

Formula (IV), (V), (VI) or (VII)
Is a chromophore represented by D ₁ in the general formula (III), R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ ,
_{R 21, R 2 2, R} 23, R 24, and preferably above unsubstituted alkyl group as a substituent represented by R _25, a substituted alkyl group (e.g., carboxyalkyl group, sulfoalkyl group, an aralkyl group, aryl Loxyalkyl group).

Formula (IV), (V), (VI) or (VII)
Is a methine dye represented by the formula (III):_TwoRepresented by
R represents a chromophore₁₇, R₁₈, R₁₉, R₂₀,
R_{twenty one}, R _{twenty two}, R_{twenty three}, R_{twenty four}, And R_{twenty five}And a substituent represented by
Is preferably an unsubstituted alkyl group or a substituted alkyl group.
And more preferably an alkyl having an anionic substituent.
Kill group (for example, carboxyalkyl group, sulfoalkyl
Group), more preferably a sulfoalkyl group.
You.

L ₁ , L ₂ , L ₃ , L ₄ , L ₅ , L ₆ , L ₇ ,
_{L 8, L 9, L 10} , L 11, L 12, L 13, L 14, L 15,
_{L 16, L 17, L 18} , L 19, L 20, L 21, L 22, L 23, L
₂₄ , L ₂₅ , L ₂₆ , L ₂₇ , L ₂₈ , L ₂₉ , L ₃₀ , L ₃₁ ,
_{L 32, L 33, L 34} , L 35, L 36, L 37, L 38, L 39, L
_{40, L 41, L 42,} L 43, L 44, L 45, L 46, L 47,
_{L 48, L 49, L 50} , L 51, L 52, L 53, L 54, L 55, L
_{56, L 57, L 58,} L 59, L 60, L 61, L 62, L 63,
L ₆₄ , L ₆₅ , L ₆₆ and L ₆₇ each independently represent a methine group. The methine group represented by L _{1 to} L ₆₇ may have a substituent, and examples of the substituent include the aforementioned V.
For example, a substituted or unsubstituted alkyl group having 1 to 15, preferably 1 to 10, particularly preferably 1 to 5 carbon atoms (eg, methyl, ethyl, 2-carboxyethyl), a substituted or unsubstituted carbon atom Number 6 to 20, preferably 6 to 15, more preferably 6 to 1
0 aryl group (for example, phenyl, o-carboxyphenyl), substituted or unsubstituted, having 3 to 20 carbon atoms, preferably 4 to 15 carbon atoms, more preferably 6 to 1 carbon atoms.
0 heterocyclic group (for example, N, N-dimethylbarbituric acid group), halogen atom (for example, chlorine, bromine, iodine, fluorine), having 1 to 15 carbon atoms, preferably 1 to 1 carbon atom
0, more preferably an alkoxy group having 1 to 5 carbon atoms (eg, methoxy, ethoxy), 0 to 15 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 4 to 1 carbon atoms.
0 amino group (eg, methylamino, N, N-dimethylamino, N-methyl-N-phenylamino, N-methylpiperazino), having 1 to 15 carbon atoms, preferably 1 carbon atom
To 10, more preferably an alkylthio group having 1 to 5 carbon atoms (eg, methylthio, ethylthio), an arylthio group having 6 to 20, preferably 6 to 12, and more preferably 6 to 10 carbon atoms (eg, phenylthio, p-methylphenylthio) and the like. Further, a ring may be formed with another methine group, or Z _{1 to} Z
₂₅ and R _{1 to} R ₂₅ may form a ring.

L ₁ , L ₂ , L ₃ , L ₄ , L ₅ , L ₆ , L ₁₀ , L
_{11, L 12, L 13,} L 16, L 17, L 23, L 24, L 25,
_{L 26, L 30, L 31} , L 32, L 33, L 36, L 37, L 43, L
_{44, L 45, L 46,} L 50, L 51, L 52, L 53, L 56,
L ₅₇ , L ₆₃ and L ₆₄ are preferably unsubstituted methine groups.

N₁, N_Two, N_Three, N_Four, N_Five, N₆, N₇,
n₈, N₉, N_Ten, N₁₁, N₁₂, And n₁₃Are independent
Represents 0, 1, 2, 3 or 4. Preferably 0, 1,
2, 3, more preferably 0, 1, 2, and especially
It is preferably 0 or 1. n ₁, N_Two, N_Three, N_Four, N_Five,
n₆, N₇, N₈, N₉, N_Ten, N₁₁, N₁₂, And n₁₃Is 2
In the above case, the methine group is repeated but need not be the same.
Absent.

P ₁ , p ₂ , p ₃ , p ₄ , p ₅ , p ₆ , p ₇ ,
_{p 8, p 9, p 10} , p 11, p 12, p 13, p 14, p 15, and p ₁₆ each independently represents 0 or 1. Preferably 0
It is.

M ₁ , M ₂ , M ₃ , M ₄ , M ₅ , and M ₆ can be used to indicate the presence of a cation or an anion when necessary to neutralize the ionic charge of the dye. It is included in. Typical cations include hydrogen ions (H ⁺ ), inorganic cations such as alkali metal ions (eg, sodium ion, potassium ion, lithium ion), alkaline earth metal ions (eg, calcium ion), and ammonium ions (eg, Ammonium ion, tetraalkylammonium ion, triethylammonium ion, pyridinium ion, ethylpyridinium ion, 1,8-diazabicyclo [5.4.0]-
Organic ions such as 7-undecenium ion). The anion may be either an inorganic anion or an organic anion, and may be a halogen anion (for example, a fluorine ion, a chloride ion, an iodine ion), a substituted arylsulfonate ion (for example, p-toluenesulfonic acid ion, p- Chlorobenzenesulfonic acid ion), aryldisulfonic acid ion (for example, 1,3-benzenesulfonic acid ion, 1,5-naphthalenedisulfonic acid ion,
2,6-naphthalenedisulfonic acid ion), alkyl sulfate ion (for example, methyl sulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, acetate ion, trifluoromethanesulfonic acid ion Is mentioned. Further, another dye having a charge opposite to that of the ionic polymer or the dye may be used. When CO ₂ ⁻ and SO ₃ ⁻ have a hydrogen ion as a counter ion, they can be expressed as CO ₂ H and SO ₃ H.

M ₁ , m ₂ , m ₃ , m ₄ , m ₅ , and m ₆ represent a number of 0 or more necessary to balance the electric charge, preferably a number of 0 to 4, more preferably 0 to 4. It is a number from 0 to 1 and 0 when a salt is formed in the molecule.

Next, only specific examples of the dyes used in the particularly preferred technique, which are described in detail in the description of the embodiments of the invention, are shown below. Of course, the present invention is not limited to these.

Specific examples of the compound represented by the general formula (I) (including the lower conceptual structure) of the present invention.

[0150]

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[0151]

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Specific examples of the compound represented by the general formula (II) (including the lower conceptual structure) of the present invention.

[0153]

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[0154]

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Specific examples of the compound represented by formula (III) of the present invention.

[0156]

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The dye of the present invention is FM Hammer.
(FMHarmer), Heterocyclic Compounds
Cyanine soybeans and related compounds
(Heterocyclic Compounds-Cyanine Dyes and Related C
ompounds) ", John Willy and Sons
n Wiley & Sons)-New York, London, 1
964, DMSturmer, Heterocyclic Compounds-Special Topics in Heterocyclic Chemistry (H
eterocyclic Compounds-Special topics in heterocycl
ic chemistry ", Chapter 18, Section 14, 482-515, John Wiley and Sons (John Wi
ley & Sons)-New York, London, 197
7th year, "Rodd's Chemistry of Carbon Compounds"
2nd.Ed.vol.IV, partB, 1977, Chapter 15, Chapter 369
422, Elsevier Science Public
Company Inc. (Elsevier Science Publishing Com
pany Inc.), New York, and the above-mentioned patents and literatures (cited for describing specific examples) and the like.

In the present invention, not only the sensitizing dye of the present invention but also other sensitizing dyes other than the present invention may be used or used in combination. Preferred examples of the dye used include a cyanine dye, a merocyanine dye, a rhodocyanine dye, a trinuclear merocyanine dye, a tetranuclear merocyanine dye, an allopolar dye, a hemicyanine dye, and a styryl dye. More preferred are cyanine dyes, merocyanine dyes and rhodacyanine dyes, and particularly preferred are cyanine dyes. For more information on these dyes, see FMHarmer, Heterocyclic Compounds-Cyanine Soybeans and Related.
Compounds (Heterocyclic Compounds-Cyanine Dyes a
nd Related Compounds), John Wiley & Sons-New York,
London, 1964, D.M.
M. Sturmer), Heterocyclic Compounds-Special topics in Heterocyclic Compounds-Special topics i
n heterocyclic chemistry) ", Chapter 18, Section 14,
482 to 515 and the like. Preferred dyes include US Pat. No. 5,994,051 No. 32
And sensitizing dyes represented by the general formulas and specific examples described in US Pat. No. 5,747,236, pages 30 to 39. The general formulas of preferred cyanine dyes, merocyanine dyes and rhodacyanine dyes are described in U.S. Pat.
(XII), (XIII) (where n1
The number of 2, n15, n17, and n18 is not limited and is an integer of 0 or more (preferably 4 or less). ).

One of these sensitizing dyes may be used.
Two or more types may be used, and representative examples of two or more types (for the purpose of supersensitization) are described in U.S. Pat.
977,229, 3,397,060, 3,5
22,052, 3,527,641, 3,61
7,293, 3,628,964 and 3,66
6,480, 3,672,898, 3,67
9,428, 3,303,377, 3,76
9,301, 3,814,609, 3,83
7,862 and 4,026,707, British Patent 1,
No. 344,281, No. 1,507,803, Shoko 4
3-49336, 53-12375, JP-A-52
No. 110618, 52-109925 and the like.

In addition to the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization.

Supersensitizers useful in the spectral sensitization of the present invention (for example, pyrimidylamino compounds, triazinylamino compounds, azolium compounds, aminostyryl compounds, aromatic organic acid formaldehyde condensates, azaindene compounds, cadmium salts) And combinations of supersensitizers and sensitizing dyes are described, for example, in US Pat. No. 3,511,66.
No. 4, No. 3,615,613, No. 3,615,632
Nos. 3,615,641, 4,596,767
Nos. 4,945,038 and 4,965,182
Nos. 4,965,182 and 2,933,390
Nos. 3,635,721 and 3,743,510
Nos. 3,617,295, 3,635,721, etc., and the method described in the above-mentioned patent is also preferable as to its use.

It has been recognized that the timing at which the sensitizing dye of the present invention (and other sensitizing dyes and supersensitizers) is added to the silver halide emulsion of the present invention has been useful. During the preparation of the emulsion. For example, US Pat. Nos. 2,735,766 and 3,6
28,960, 4,183,756, 4,22
5,666, JP-A-58-184142, 60-
As disclosed in, for example, Japanese Patent No. 196749, the stage before silver halide grain formation step and / or before desalting, the period during and / or after desalting and before the start of chemical ripening,
As disclosed in JP-A-58-113920 and the like, at any time during the process immediately before or during the process of chemical ripening, or at any time before the emulsion is coated before the emulsion is coated after the chemical ripening. May be. Also, U.S. Pat.
As disclosed in US Pat. No. 5,666, JP-A-58-7629, etc., the same compound may be used alone or in combination with a compound having a different structure, for example, during the particle forming step and during the chemical ripening step or during the chemical ripening step. It may be added separately after completion, or before or after chemical ripening or during the process and after completion, and may be added by changing the kind of compound and compound combination to be added separately. May be.

The addition amount of the sensitizing dye of the present invention (the same applies to other sensitizing dyes and supersensitizers) varies depending on the shape and size of silver halide grains. ^Per mol of 1 × 10 ^-6 to 8 × 10 ^-3 mol. For example, when the silver halide grain size is 0.2 to 1.3 μm, the addition amount is preferably 2 × 10 ^{−6 to} 3.5 × 10 ⁻³ mol per mol of silver halide, and is preferably 7.5. An addition amount of × 10 ^{−6 to} 1.5 × 10 ⁻³ mol is more preferable. However, as described above, when the sensitizing dye of the present invention is adsorbed in multiple layers, an amount necessary for the multilayer adsorption is added.

In the present invention, the photographic emulsion controlling the light-sensitive mechanism includes any of silver bromide, silver iodobromide, silver chlorobromide, silver iodide, silver iodochloride, silver iodobromochloride and silver chloride as silver halide. Although a halogen composition on the outermost surface of the emulsion may contain iodine of 0.1 mol% or more, more preferably 1 mol% or more, particularly preferably 5 mol% or more, a stronger multilayer adsorption structure can be constructed. The particle size distribution may be wide or narrow, but narrower is more preferable. The silver halide grains of a photographic emulsion are those having regular crystals such as cubic, octahedral, tetradecahedral, or rhombic dodecahedron, or irregular such as spherical, plate-like, etc. (Irregular) crystal form,
It may have a higher-order plane ((hkl) plane) or a mixture of grains of these crystal forms, but is preferably a tabular grain, and the tabular grain will be described in detail below. Journal of I for particles with higher planes
See pages 247 to 254 of Maging Science, Vol. 30 (1986). Further, the silver halide photographic emulsion used in the present invention may contain the above-mentioned silver halide grains singly or in combination.
The silver halide grains may have different phases between the inside and the surface layer, may have a multiphase structure having a bonding structure, may have a localized phase on the grain surface, or may have a uniform grain as a whole. May consist of phases. They may be mixed. These various emulsions may be either a surface latent image type in which a latent image is mainly formed on the surface or an internal latent image type in which a latent image is formed inside a grain.

In the present invention, tabular silver halide grains having a halogen composition of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, and silver iodochloride are preferably used. The tabular grains preferably have a main surface of (100) or (111). Tabular grains having a (111) major surface, hereinafter referred to as (111) tabular, usually have triangular or hexagonal faces. Generally, the more uniform the distribution, the higher the proportion of tabular grains having more hexagonal faces. The hexagonal monodispersed flat plate is described in Japanese Patent Publication No. 5-61205.

Tabular grains having a (100) plane as a main surface,
The (100) flat plate also has a rectangular or square shape. In this emulsion, grains having an adjacent side ratio of less than 5: 1 are called tabular grains. In silver chloride or tabular grains containing a large amount of silver chloride, (100) tabular grains originally have higher stability on the main surface than (111) tabular grains. In the case of a (111) flat plate, it is necessary to stabilize the (111) main surface.
-80660, JP-A-9-80656 and U.S. Pat. No. 5,298,388.

The following patents disclose silver chloride or the (111) flat plate having a high silver chloride content used in the present invention. U.S. Patent No. 4,414,306, U.S. Patent No. 4,400,463, U.S. Patent No. 4,713,323
No. 4,783,398; U.S. Pat.
No. 491, U.S. Pat. No. 4,983,508, U.S. Pat.
No. 804621, US Pat. No. 5,389,509, US Pat. No. 5,217,858, US Pat. No. 5,460,934.

The silver bromide (111) tabular grains used in the present invention are described in the following patents. U.S. Pat. No. 4,425,425, U.S. Pat. No. 4,425,426,
U.S. Pat. No. 4,443,426; U.S. Pat. No. 4,439,520
No. 4,414,310; U.S. Pat.
048, U.S. Pat. No. 4,647,528, U.S. Pat.
No. 6,650,012, U.S. Pat. No. 4,672,027, U.S. Pat. No. 4,678,745, U.S. Pat. No. 4,684,607,
U.S. Pat. No. 4,593,964, U.S. Pat.
6, U.S. Pat. No. 4,722,886, U.S. Pat.
5617, U.S. Patent No. 4,755,456, U.S. Patent No. 4,806,461, U.S. Patent No. 4,801,522, U.S. Patent No. 4,835,322, U.S. Patent No. 4,839,268,
U.S. Pat. No. 4,914,014, U.S. Pat.
5, U.S. Pat. No. 4,977,074, U.S. Pat.
No. 5,350, U.S. Pat. No. 5,061,609, U.S. Pat. No. 5,061,616, U.S. Pat. No. 5,068,173, U.S. Pat. No. 5,132,203, U.S. Pat.
No. 5,334,469, U.S. Pat.
No. 495, US Pat. No. 5,358,840, US Pat.
372927.

The (100) flat plate used in the present invention is described in the following patents. US Patent No. 43
No. 86156, US Pat. No. 5,275,930, US Pat. No. 5,292,632, US Pat. No. 5,314,798, US Pat. No. 5,320,938, US Pat. No. 5,319,635.
No. 5,356,764, European Patent No. 5699.
No. 71, EP 737887, JP-A-6-308
648, JP-A-9-5911.

The silver halide emulsion used in the present invention has a higher surface area / absorbing sensitizing dye disclosed in the present invention.
Tabular silver halide grains having a high volume ratio are preferred, and the aspect ratio is preferably 2 or more, more preferably 5 or more, and particularly preferably 8 or more. There is no upper limit,
Preferably it is 1000 or less, more preferably 500 or less. The thickness of the tabular grains is preferably less than 0.2 μm, more preferably less than 0.1 μm, even more preferably less than 0.07 μm.

The expression that the aspect ratio is 2 or more means that silver halide grains having an aspect ratio (equivalent circle diameter of silver halide grains / grain thickness) of 2 or more are obtained by projecting all silver halide grains in the emulsion. It means that 50% or more of the area exists. Preferably at least 70%, particularly preferably at least 85
% Of the emulsion. The following technology is applied to prepare such high aspect ratio and thin tabular grains. The tabular grains of the present invention desirably have a uniform dislocation dose distribution between grains. The emulsion of the present invention contains 10 per grain.
Silver halide grains containing at least 10 dislocation lines account for 10% of all grains.
It preferably accounts for 0 to 50% (number), more preferably 100 to 70%, particularly preferably 10 to 50%.
It accounts for 0 to 90%. If it is less than 50%, it is not preferable in terms of homogeneity between particles.

In the present invention, when obtaining the ratio of the particles containing dislocation lines and the number of dislocation lines, it is preferable to directly observe the dislocation lines for at least 100 particles.
More preferably 200 particles or more, particularly preferably 300 particles
Observe for more than particles.

Gelatin is advantageously used as a protective colloid used in preparing the emulsion of the present invention and as a binder for other hydrophilic colloid layers, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives ;
Polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylimidazole, etc. Can be used. Examples of gelatin include lime-processed gelatin, acid-processed gelatin and Bull. Soc. Sci.
Photo. Japan. No. 16. P30 (196
Enzyme-treated gelatin as described in 6) may be used, and hydrolysates or enzymatic degradation products of gelatin can also be used. The emulsion of the present invention is washed with water for desalting,
It is preferable to use a newly prepared protective colloid dispersion. The washing temperature can be selected according to the purpose, but 5 ° C ~ 50
It is preferable to select in the range of ° C. The pH at the time of washing can be selected according to the purpose, but is preferably selected from 2 to 10. More preferably, it is in the range of 3 to 8. The pAg at the time of washing can be selected according to the purpose, but is preferably selected from 5 to 10.
The method for washing can be selected from noodle washing, dialysis using a semipermeable membrane, centrifugal separation, coagulation sedimentation, and ion exchange. In the case of the coagulation sedimentation method, a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative, and the like can be selected.

When preparing the emulsion of the present invention, for example, during grain formation,
In the desalting step, at the time of chemical sensitization, the presence of a metal ion salt before coating is preferable depending on the purpose. In the case of doping the grains, it is preferable to add them at the time of grain formation, when modifying the grain surface or when using as a chemical sensitizer, after grain formation and before the end of chemical sensitization. A method of doping the entire grain and a method of doping only the core part or only the shell part of the grain can be selected. For example, Mg, Ca, Sr, Ba, Al,
Sc, Y, La, Cr, Mn, Fe, Co, Ni, C
u, Zn, Ga, Ru, Rh, Pd, Re, Os, I
r, Pt, Au, Cd, Hg, Tl, In, Sn, P
b and Bi can be used. These metals can be added in the form of ammonium salts, acetates, nitrates, sulfates, phosphates, hydroxides, or salts that can be dissolved at the time of particle formation, such as six-coordinate complex salts and four-coordinate complex salts. For example,
CdBr ₂ , CdCl ₂ , Cd (NO ₃ ) ₂ , Pb (NO
₃ ) ₂ , Pb (CH ₃ COO) ₂ , K ₃ [Fe (C
N) ₆ ], (NH ₄ ) ₄ [Fe (CN) ₆ ], K ₃ IrC
_{l 6, (NH 4) 3} RhCl 6, K 4 Ru (CN) 6 and the like. The ligand of the coordination compound can be selected from halo, aquo, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo, and carbonyl. These may be used alone or in combination of two or more metal compounds.

The metal compound is preferably added after being dissolved in water or a suitable organic solvent such as methanol or acetone. To stabilize the solution, a method of adding an aqueous solution of hydrogen halide (eg, HCl, HBr) or an alkali halide (eg, KCl, NaCl, KBr, NaBr) can be used. Further, if necessary, an acid or an alkali may be added. The metal compound can be added to the reaction vessel before the formation of the particles or during the formation of the particles. A water-soluble silver salt (eg, AgNO ₃ ) or an aqueous alkali halide solution (eg, NaCl, K)
(Br, KI) and continuously during the formation of silver halide grains. Further, a solution independent of the water-soluble silver salt and alkali halide may be prepared and added continuously at an appropriate time during grain formation. It is also preferable to combine various addition methods.

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

The silver halide grains of the present invention may be subjected to at least one of sulfur sensitization, selenium sensitization, gold sensitization, palladium sensitization or noble metal sensitization and reduction sensitization in any step of the production process of a silver halide emulsion. Can be applied. It is preferable to combine two or more sensitization methods. Various types of emulsions can be prepared depending on the step of chemical sensitization. There are a type in which a chemical sensitizing nucleus is embedded in the grain, a type in which the chemical sensitizing nucleus is embedded in a position shallow from the grain surface, and a type in which a chemical sensitizing nucleus is formed on the surface. In the emulsion of the present invention, the location of the chemical sensitization nucleus can be selected according to the purpose. Generally, the case where at least one type of chemical sensitization nucleus is formed near the surface is preferred. One of the chemical sensitizations that can be preferably performed in the present invention is chalcogen sensitization and noble metal sensitization alone or in combination, and is described by TH James, The Photographic Process, Fourth Edition, Macmillan. Published by the company
1977, (TH James, The Theo)
ry of the Photographic Pr
ocess, 4th ed, Macmillan, 19
77) can be carried out using active gelatin as described on pages 67-76, and can also be performed by Research Disclosure, 120, April 1974, 12008; Research Disclosure, 34, 6 June 1975.
Moon, 13452, U.S. Patent Nos. 2,642,361, 3,297,446, and 3,772,031,
Nos. 3,857,711 and 3,901,714,
Nos. 4,266,018 and 3,904,4
No. 15, and pAg 5-10, pH 5-8 and temperature 30-30 as described in GB 1,315,755.
At 80 ° C., it can be sulfur, selenium, tellurium, gold, platinum, palladium, iridium or a combination of these sensitizers. 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 palladium salt or a tetravalent salt. Preferred palladium compounds are represented by R2 PdX6 or R2 PdX4. Here, R represents a hydrogen atom, an alkali metal atom or an ammonium group. X represents a halogen atom, and represents a chlorine, bromine or iodine atom.

Specifically, K_TwoPdCl_Four, (NH_Four)_Two
PdCl₆, Na_TwoPdCl_Four, (NH_Four)_TwoPdCl_Four,
Li_TwoPdCl_Four, Na_TwoPdCl₆Or K_TwoPdBr_Four
Is preferred. Gold and palladium compounds
It is preferable to use in combination with an anoate or selenocyanate.
Good. Hypo- and thiourea-based compounds as sulfur sensitizers
, Rhodanine compound and US Pat. No. 3,857,7
Nos. 4,266,018 and 4,05
Using a sulfur-containing compound described in US Pat.
be able to. Chemical sensitization in the presence of so-called chemical sensitization aids
You can feel it. Azai is a useful chemical sensitization aid
Chemicals like denden, azapyridazine and azapyrimidine
In the process of academic sensitization, fog is suppressed and sensitivity is increased.
The compound known as is used. Chemical sensitization aid
Examples of fillers are described in U.S. Pat. Nos. 2,131,038 and
No. 3,411,914, No. 3,554,757,
No. 58-126526 and the above-mentioned "Photograph" by Duffin
Emulsion Chemistry ", pp. 138-143. Book
The emulsion of the present invention is preferably used in combination with gold sensitization. Gold sensitization
The preferred amount of the agent is 1.times.10.sup.6 per mol of silver halide.
^-Four~ 1 × 10^-7Mole, more preferably 1 × 1
0 ^-Five~ 5 × 10^-7Is a mole. Palladium compounds preferred
New area is 1 × 10^-3From 5 × 10^-7It is. Thiocyan
The preferred range of the compound or selenocyan compound is
5 × 10^-2From 1 × 10^-6It is. Halogenation of the present invention
The preferred amount of sulfur sensitizer used for silver particles is halogenated
1 × 10 per mole of silver halide^-Four~ 1 × 10^-7Mole,
More preferred is 1 × 10^-Five~ 5 × 10^-7In mole
You. Selenium is a preferred sensitizing method for the emulsion of the present invention.
There is sensitization. In selenium sensitization, known unstable cell
A colloidal metal selenium
Selenoureas (e.g., N, N-dimethylselenourea
Element, N, N-diethylselenourea), selenoketones,
Selenium compounds such as selenoamides can be used.
Wear. Selenium sensitization is sulfur sensitization or precious metal sensitization or
May be preferable to use in combination with both.
You.

During the grain formation of the silver halide emulsion of the present invention,
It is preferable to perform reduction sensitization after grain formation and before or during chemical sensitization, or after chemical sensitization. Here, reduction sensitization refers to a method of adding a reduction sensitizer to a silver halide emulsion, a method of growing or ripening in a pAg 1 to 7 low pAg atmosphere called silver ripening, or a pH 8 to 10 called high pH ripening. Either a method of growing or ripening in a high pH atmosphere of 11 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. Examples of the reduction sensitizer include stannous salts, ascorbic acid and derivatives thereof, amines and polyamines, hydrazine derivatives, formamidine sulfinic acid,
Silane compounds and borane compounds are known. For the reduction sensitization of the present invention, these known reduction sensitizers can be selected and used, and two or more 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 an appropriate range is from 10 ^-7 to 10 ^-3 mol per mol of silver halide. The reduction sensitizer is dissolved in water or an organic 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 a method of adding at an appropriate time during the particle growth is preferable. Alternatively, a reduction sensitizer may be added in advance to the water solubility of a water-soluble silver salt or a water-soluble alkali halide, and silver halide grains may be precipitated using these aqueous solutions. It is also a preferred method to add the solution of the reduction sensitizer in several portions as the grains grow, or to add the solution continuously for a long time.

During the production process of the emulsion of the present invention, an acid for silver is used.
It is preferable to use an agent. The oxidizing agent for silver is
Has the effect of converting to silver ions by acting on metallic silver
Refers to a compound. Especially the formation process of silver halide grains and
Extremely small silver particles by-produced during chemical sensitization
Is a compound that can be converted into a silver ion. here
The silver ions generated in, for example, silver halide, sulfide
May form silver salts that are hardly soluble in water such as silver and silver selenide.
And may form a silver salt easily soluble in water such as silver nitrate.
No. The oxidizing agent for silver can be inorganic or organic.
There may be. As the inorganic oxidizing agent, for example, Ozo
Hydrogen peroxide and its adducts (eg, NaBO)_Two
・ H_TwoO_Two・ 3H_TwoO, 2NaCO_Three・ 3H_TwoO_Two, N
a_FourP_TwoO₇・ 2H_TwoO_Two, 2Na_TwoSO_Four・ H_TwoO_Two・ 2H
_TwoO), peroxyacid salts (eg, K_TwoS _TwoO₈, K_TwoC_Two
O₆, K_TwoP_TwoO₈), Peroxy complex compounds (eg, K
_Two[Ti (O_Two) C_TwoO_Four] ・ 3H_TwoO, 4K_TwoSO_Four・ Ti
(O_Two) OH ・ SO_Four・ 2H_TwoO, Na_Three[VO (O_Two)
(C_TwoH_Four)_Two] ・ 6H_TwoO), permanganate (e.g.
For example, KMnO_Four), Chromates (eg, K_TwoCr
_TwoO₇Oxyacids, such as iodine and bromine, such as iodine and bromine
Element, perhalate (for example, potassium periodate)
), High valent metal salts (eg, hexacyano
Potassium ferrate) and thiosulfonates.

Examples of the organic oxidizing agent include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogen (for example, N-
Bromsuccinimide, chloramine T, chloramine B)
Is given as an example.

Preferred oxidizing agents of the present invention are inorganic oxidizing agents such as ozone, hydrogen peroxide and its adducts, halogen elements, thiosulfonates, and organic oxidizing agents such as quinones.
It is a preferred embodiment to use the above-described reduction sensitization and an oxidizing agent for silver in combination. The method can be selected from a method of performing reduction sensitization after using an oxidizing agent, a method reverse thereto, or a method of coexisting the two simultaneously. These methods can be selectively used in both the grain formation step and the chemical sensitization step.

The photographic emulsion used in the present invention contains various silver halide-adsorbing compounds for the purpose of preventing fogging during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. It can be contained.
The silver halide-adsorbing compound is preferably represented by the general formula (VII
It is a compound represented by I).

[0184]

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Here, Z ₂₆ in the general formula (VIII) is-
A heterocyclic residue in which at least one selected from SO ₃ M ₈ , —COOR ₂₆ , —OH and —NHR ₂₇ is directly or indirectly bonded (preferably a directly bonded heterocyclic residue), for example, an oxazole ring; Thiazole ring, imidazole ring,
Selenazole ring, triazole ring, tetrazole ring, thiadiazole ring, oxadiazole ring, pentazole ring, pyrimidine ring, thiazine ring, triazine ring, thiodiazine ring, or a ring bonded to another carbon ring or hetero ring (for example, benzothiazole ring Benzotriazole ring, benzimidazole ring, benzoxazole ring, benzoselenazole ring, naphthoxazole ring, triazaindolizine ring, diazaindolizine ring, tetraazaindolizine ring).

Preferred Z ₂₆ is an imidazole ring,
Examples include a tetrazole ring, a benzimidazole ring, a benzothiazole ring, a benzoxazole ring, and a triazal ring.

In formula (VIII), M ₈ is a hydrogen atom,
Represents an alkali metal atom, a quaternary ammonium group or a quaternary phosphonium group. R ₂₆ represents a hydrogen atom, an alkali metal atom or C 1 to 6 alkyl carbon, R ₂₇
Is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, -COR
₂₈ represents a -COOR ₂₈ or -SO ₂ R _28, R ₂₈ represents a hydrogen atom, an aliphatic group or an aromatic group, may have these groups further substituted.

Among the mercapto heterocyclic compounds represented by the general formula (VIII), preferred are those represented by the general formula (IX)
And (X).

[0189]

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[0190]

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In formula (IX), Y and W each independently represent a nitrogen atom or CR ₂₉ (R ₂₉ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group). shown, R ₃₀ is, -SO ₃ M _8, -
An organic residue substituted with at least one selected from the group consisting of COOM ₈ , —OH and —NHR ₂₇ , specifically, an alkyl group having 1 to 20 carbon atoms (eg, methyl, ethyl, propyl, Hexyl, dodecyl, okitadecyl), an aryl group having 6 to 20 carbon atoms (eg, phenyl,
Naphthyl), and L ₆₈ is -S-, -O-, -N (-)
-, - CO -, - SO- and -SO ₂ - represents a linkage group or a single bond selected from the group consisting of. n14 is 0 or 1
It is.

These alkyl groups and aryl groups include
Further, for example, a halogen atom (for example, F, Cl, B
r), an alkoxy group (eg, methoxy, methoxyethoxy), an aryloxy group (eg, phenoxy), an alkyl group (when R ₂₇ is an aryl group), an aryl group (when R ₂₇ is an alkyl group), an amide group (eg, acetamide ,
Benzoylamino), carbamoyl group (eg, unsubstituted carbamoyl, phenylcarbamoyl, methylcarbamoyl), sulfonamide group (eg, methanesulfonamide, phenylsulfonamide), sulfamoyl group (eg, unsubstituted sulfamoyl, methylsulfamoyl, phenylsulfamoyl) ), A sulfonyl group (eg, methylsulfonyl, phenylsulfonyl), a sulfinyl group (eg, methylsulfinyl, phenylsulfinyl), a cyano group, an alkoxycarbonyl group (eg, methoxycarbonyl), an aryloxycarbonyl group (eg, phenoxycarbonyl), and a nitro group. It may be substituted by another substituent.

Here, the substituent of R ₃₀ —SO ₃ M ₈ , —CO
OM _8, may be different even with the same when the -OH and -NHR ₂₇ there are two or more.

R ₂₇ and M ₈ have the same meanings as those represented by formula (VIII).

Next, in the general formula (X), X represents a sulfur atom, an oxygen atom or —NR ₃₁ —, and R ₃₁ is a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Represents

In the present invention, X is particularly preferably a sulfur atom.

L₆₉Is -CONR₃₂-, -NR₃₂CO-,
SO_TwoNR₃₂-, -NR₃₂SO_Two-, -OCO-, -C
OO-, -S-, -NR₃₂-, -CO-, -SO-,-
OCOO-, -NR₃₂CONR₃₃-, -NR₃₂COO
-, -OCONR₃₂-, -NR ₃₂SO_TwoNR₃₃-Or
Represents a single bond, R₃₂, R₃₃Are each a hydrogen atom,
Or unsubstituted alkyl group, or substituted or unsubstituted
Represents an aryl group.

R ₃₀ and M ₈ represent the same as those represented by formulas (VIII) and (IX), and n14 represents 0 or 1.

Further, as the substituents of the alkyl group and the aryl group represented by R ₂₉ , R ₃₁ , R ₃₂ and R ₃₃ , the same substituents as those described for the substituent of R ₃₀ can be mentioned.

In the general formulas (IX) and (X), R ₃₀ is-
Those of SO ₃ M ₈ and —COOM ₈ are preferred.

The formulas (VIII) and (I) used in the present invention
Preferred specific examples of the compounds represented by X) and (X) are shown below.

[0202]

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[0203]

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The compounds represented by formulas (VIII), (IX) and (X) are known and can be synthesized by the methods described in the following documents.

US Pat. Nos. 2,585,388;
541,924, JP-B-42-21,842, JP-A-53-50,169, British Patent No. 1,275,70.
No. 1, D. A. Berges et al., "Journal of Heterocyclic Chemistry" (DA Berge).
set. al. , “Journal of Hete
rocyclic Chemistry ") Vol. 15 9
No. 81 (1978), "The Chemistry of Heterocyclic Chemistry", Imidazole and Derivatives, Part I ("The Chemis
try of Heterocyclic Chemist
ry "Imidazole and Derivative
es part I), pages 336-9, Chemical Abstract,
58, 7921 (1963), p. 394; Hogarth, "E. Hoggarth" Journal of Ch.
Chemical Society ") 1116-7 pages (1
949); R. Saudler, W.C. Caro, "Organic Functional Group Prevation, Academic Press (SR Saudle)
r, W.S. Karo, “Organic Function
nal Group Preparation "Aca
Demic Press, pages 312-5, (1968)
M. Shamdom et al. (M. Champdon, et.a.
l. ,), Burtan, de la Société simik
De France (Bulletin de la Soc)
ie, Chimique de France), 7
23 (1954); A. Shirley, D. W. Array, Journal of the America Chemical Society (DA Shirley, DW Alle)
y, J. et al. Amer. Chem. Soc. ), 79, (4
922 (1954) A. Ball W. Marchwald, Berichte (A. Wohl, W. Marchwald, Be)
r. ) (German Chemistry), vol. 22, p. 568 (188)
9) Journal of American Chemical Society (J. Amer. Chem. Soc.), 44, 1
Pages 502 to 10 U.S. Pat. No. 3,017,270, British Patent No. 940,169, JP-B-49-8,334.
No. JP-A-55-59463, Advanced in Heterocyclic Chemistry (Advanced)
in Heterocyclic Chemistr
y), West German Patent No. 2,716,707, The Chemistry of Heterocyclic Compounds, Imidazole and Derivatives (The Chem)
istryof Heterocyclic Comp
sounds imidazoleand Deriva
ives) Vol 1, p. 385, Organic
Synthesis (Org. Synth) IV. , 569 (1
963), Bellitzte (Ber.) 9, 465 (197)
6), Journal of American Chemical Society (J. Amer, Chem. Soc.) 45,
2390 (1923), JP-A-50-89034, JP-A-53-28426, JP-A-55-21007, and JP-B-40.
-28496.

The compound represented by formula (VIII), (IX) or (X) is a silver halide emulsion layer or a hydrophilic colloid layer (for example, an intermediate layer, a surface protective layer, a yellow filter layer, an antihalation layer). To be contained.

It is preferable that the compound is contained in the silver halide emulsion layer or an adjacent layer.

The amount of addition is preferably 1 × 10
^-Five~ 1 × 10^-1g / m^Two, More preferably 5 × 10^-Five~
1 × 10^-2g / m^TwoParticularly preferably 1 × 10^-Four~ 5x
10 ^-3g / m^TwoIt is.

The method of adding this compound to an emulsion may be in accordance with the usual method of adding a photographic emulsion additive. For example, it can be dissolved in methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water or a mixed solvent thereof and added as a solution.

The compounds represented by the general formulas (VIII), (IX) and (X)
The compound represented by the formula (1) can be added and used in any step of the production process of the photographic emulsion, or can be added and used at any stage after the preparation of the emulsion and immediately before coating.
In the preferred addition step in the present invention, it is effective to add during the chemical ripening step after completion of silver halide grain formation.

The compound represented by formula (VIII), (IX) or (X) is usually a tellurium-sensitized silver halide 1
It is used in an amount of 1 × 10 ^-6 mol to 1 × 10 ^-1 mol, preferably 1 × 10 ^-5 mol to 8 × 10 ^-3 mol, per mol. As the silver halide-adsorbing substance, a compound represented by the general formula (XI) is also preferably used.

[0212]

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In the formula, R ₃₄ and R ₃₅ represent an aliphatic group or an aromatic group, and R ₃₄ and R ₃₅ may form a ring.

The compound of formula (XI) will be described in detail. The aliphatic group represented by R ₃₄ or R ₃₅ has 1 to 1 carbon atoms.
8, which represents an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aralkyl group, for example, methyl group, ethyl group, n-propyl group, i-propyl group, i-butyl group, t-pentyl And n-hexyl, m-decyl, allyl, 3-pentenyl, propargyl, cyclohexyl, benzyl, phenethyl and the like. The aromatic group represented by R _34, R ₃₅ are such as monocyclic or condensed-ring aryl group, and a phenyl group, a naphthyl group having 6 to 20 carbon atoms.

R ₃₄ and R ₃₅ may be the same or different. Further, when R ₃₄ and R ₃₅ form a ring, -SS-
And a 5- or 6-membered ring.

The aliphatic group and aromatic group represented by R ₃₄ and R ₃₅ may be substituted. Examples of the substituent include the following. These may be replaced by a plurality of different ones. Representative substituents include a carboxyl group, an alkyloxycarbonyl group (eg, ethoxycarbonyl), an aryloxycarbonyl group (eg, phenoxycarbonyl), an amino group, a substituted amino group (eg, ethylamino, dimethylamino), a hydroxy group ,
Alkoxy groups (eg, methoxy), aryloxy groups (eg, phenoxy), acyl groups (eg, acetyl), acylamino groups (eg, acetamido), ureido groups, nitro groups, sulfonyl groups (eg, phenylsulfonyl), sulfo groups, Mercapto group, alkylthio group (for example, methylthio), cyano group, phosphono group, sulfamoyl group (for example, unsubstituted sulfamoyl, N, N
Dimethylsulfamoyl), carbamoyl groups (eg, unsubstituted carbamoyl, N, N-diethylcarbamoyl), alkyl groups (eg, ethyl), aryl groups (eg, phenyl), heterocycles (eg, morpholino),
It is a halogen atom (for example, Cl, Br). Preferred specific examples of the compound represented by the general formula (XI) used in the present invention are shown below.

[0219]

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[0218]

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The compound of the formula (XI) may be added at the time of chemical sensitization from the preparation of silver halide to the end of chemical sensitization. The amount of the compound of formula (XI) to be added may be appropriately adjusted depending on the silver halide to be used, the timing of addition, etc., and is preferably 10 ^-6 to 10 ^-1 mol, preferably 5 × 10 ^-1 mol, per mol of silver halide. ^{-6 to} 5 × 10
^-2 moles may be used. The compound of the general formula (XI) can be dissolved in water or an organic solvent miscible with water (for example, methanol), or added in the form of a fine dispersion in a gelatin solution or the like. Further, as the silver halide-adsorbing substance, a compound represented by formula (XII) is also preferably used.

[0220]

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Z ₂₇ represents an alkyl group (1 to 18 carbon atoms), an aryl group (6 to 18 carbon atoms), or a heterocyclic group, and may be substituted. Examples of the substituent include a lower aliphatic group such as a methyl group, an ethyl group and a vinyl group, an aryl group such as a phenyl group, an alkoxy group having 1 to 8 carbon atoms, a halogen atom such as chlorine, a nitro group, an amino group, and a carbamoyl. Group, sulfamoyl group, carboxyl group and the like. M
₉ represents a metal cation, an organic cation, or a hydrogen atom, and the metal cation is preferably a sodium ion or a potassium ion, and the organic cation is preferably an ammonium ion, a guanidium ion, or the like. General formula (XII)
Preferred specific examples of the compound represented by are shown below.

[0222]

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[0223]

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The compound contained in the general formula (XII) can be synthesized by a generally well-known method. For example, it can be synthesized by reacting sulfonyl chloride with sodium sulfide or reacting the corresponding sodium sulfinate with sulfur. On the other hand, these compounds can be easily obtained as commercial products. Formula (XII) addition amount of the compound represented by the per mol of silver halide 10 ^-2 mol or less, preferably 10 ^-8 - 3 × 10 ^-3, particularly preferably 10 ^-7 -
10 ^-3 mol. The timing of addition may be any of the step of forming grains, the step of desalting, the step of chemical sensitization, or the time immediately before coating.
Antifoggants and stabilizers are used at various times before, during and 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 according to the purpose. In addition to exhibiting the original antifogging and stabilizing effects by adding during emulsion preparation, it controls the crystal wall of the grains, reduces the grain size, reduces the solubility of the grains, controls the chemical sensitization,
It can be used for various purposes such as controlling the arrangement of dyes.

The light-sensitive material produced by using the silver halide emulsion obtained in the present invention can be prepared by forming a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer on a support. It is sufficient that at least one layer is provided, and there is no particular limitation on the number and order of the silver halide emulsion layer and the non-photosensitive layer. A typical example is a silver halide photographic light-sensitive material having at least one color-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. The light-sensitive layer is a unit light-sensitive layer having color sensitivity to any of blue light, green light, and red light. In a multilayer silver halide color photographic light-sensitive material, a unit light-sensitive layer is generally used. Of the red-sensitive layer in order from the support side,
A green color sensitive layer and a blue color sensitive layer are provided 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 layers of the same color sensitivity.

A non-light-sensitive layer such as an intermediate layer of each layer may be provided between the above-mentioned silver halide light-sensitive layers and as the uppermost layer and the lowermost layer.

The intermediate layer is described in JP-A-61-43748.
No. 59-113438, No. 59-113440
Couplers and DIR compounds as described in JP-A Nos. 61-20037 and 61-20038 may be contained, and a color mixture inhibitor may be contained as usually used.

As described in West German Patent No. 1,121,470 or British Patent No. 923,045, a plurality of silver halide emulsion layers constituting each unit photosensitive layer may be composed of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer. A two-layer constitution of an emulsion layer can be preferably used. Usually, it is preferable to arrange them so that the light sensitivity decreases sequentially toward the support, and a non-photosensitive layer may be provided between the respective halogen emulsion layers. Also,
JP-A-57-112751, 62-200350
As described in JP-A-62-206541 and JP-A-62-206543, a low-speed emulsion layer may be provided on the side farther from the support and a high-speed emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support,
For example, a low-sensitivity blue-sensitive layer (BL) / a high-sensitivity blue-sensitive layer (BH) / a high-sensitivity green-sensitive layer (GH) / a low-sensitivity green-sensitive layer (GL) / a high-sensitivity red-sensitive layer (RH) / Low-sensitivity red-sensitive layer (RL) or BH / BL / GL / GH / R
H / RL, or BH / BL / GH / GL / RL /
They can be installed in the order of RH.

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. JP-A-56-25738 and JP-A-62-6393.
As described in the specification of JP-A No. 6, a blue-sensitive layer / GL / RL / GH / RH can be provided in this order from the farthest side from the support.

As described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is a layer having a lower sensitivity than the middle layer. Further, there is an arrangement in which a silver halide emulsion layer having a low sensitivity is disposed and three layers having different sensitivities are sequentially reduced in sensitivity toward a support. Even when such three layers having different sensitivities are used, as described in JP-A-59-202264, a medium-speed emulsion layer / They may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer.

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.

In the case of four or more layers, the arrangement may be changed as described above.

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

The above-mentioned various additives are used in the light-sensitive material according to the present invention. In addition, various additives can be used according to the purpose.

These additives are described in more detail in Research Disclosure Item 17643 (1978).
Item 18716 (January 1979)
Jan.) and Item 308119 (December 1989), and the relevant portions are summarized in the table below.

Additive type RD17643 RD18716 RD308119 1 Chemical sensitizer page 23, page 648, right column, page 996 2 Sensitivity enhancer Same as above 3 Spectral sensitizer, page 23-24, page 648, right column-996 right-998 right Super strong Sensitizer Page 649 Right column 4 Brightener 24 Page 647 Page Right column 998 Right 5 Antifoggant, Page 24 to 25 Page 649 Right column 998 Right to 1000 Right and Stabilizer 6 Light absorber, 25 to 26 649 Page right column to 1003 left to 1003 right Filter dye, page 650 Left column UV absorber 7 Stain inhibitor 25 page right column 650 left to right column 1002 right 8 Dye image stabilizer 25 page 1002 right 9 Hardener 26 page 651 Page left column 1004 right to 1005 left 10 Binder page 26 Same as above 1003 right to 1004 right 11 Plasticizer, lubricant 27 page 650 Page right column 1006 left to 1006 right 12 Coating aid, page 26 to 27 Same as above 1005 left to 1006 left Surfactant 13 Static Page 27 Same as above 1006 right to 1007 left Inhibitor 14 matting agent 1008 left to 1009 left Also to prevent deterioration of photographic performance due to formaldehyde gas For this purpose, it is preferable to add a compound which can react with formaldehyde described in U.S. Pat. Nos. 4,411,987 and 4,435,503 and can be fixed to the photosensitive material.

In the present invention, various color couplers can be used, and specific examples thereof are described in Research Disclosure No. 17643, VII-CG and N
o. 307105, VII-CG.

As the yellow coupler, for example, US Pat. Nos. 3,933,501 and 4,022,620
No. 4,326,024 and 4,401,75
No. 2, No. 4,248,961, Japanese Patent Publication No. 58-107
No. 39, British Patent Nos. 1,425,020 and 1,4
No. 76,760; U.S. Pat. Nos. 3,973,968; 4,314,023; 4,511,649;
Those described in EP 249,473A and the like are preferred.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferable, and US Pat. Nos. 4,310,619 and 4,351,897.
No. 3,073,636; U.S. Pat.
No. 1,432, No. 3,725,067, Research
Disclosure No. 24220 (June 1984
), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, JP-A-61-72238, and JP-A-60-72238.
No. 35730, No. 55-118034, No. 60-18
No. 5,951, U.S. Pat. Nos. 4,500,630, 4,540,654, 4,556,630, and WO 88/04795 are particularly preferred.

Examples of the cyan coupler include phenol couplers and naphthol couplers.
No. 52,212, No. 4,146,396, No. 4,
Nos. 228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162, 2,895,826,
No. 3,772,002 and No. 3,758,308
No. 4,334,011, No. 4,327,17
3, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A and 249,453A, U.S. Patent Nos. 3,446,622, and 4,333,999.
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,
199 and JP-A-61-42658 are preferred.

Typical examples of polymerized dye-forming couplers are described in US Pat. Nos. 3,451,820 and 4,082.
No. 0,211, No. 4,367,282, No. 4,4
09,320, 4,576,910, British Patent 2,102,137 and European Patent 341,188A.
No.

Examples of couplers in which a coloring dye has an appropriate diffusibility include US Pat. No. 4,366,237, British Patent No. 2,125,570, and European Patent No. 96,570.
Those described in West German Patent (Published) No. 3,234,533 are preferred.

A colored coupler for correcting unnecessary absorption of a coloring dye is described in Research Disclosure No.
No. 17643, section VII-G; VII of 307105-
Section G, U.S. Pat. No. 4,163,670, JP-B-57-
39413, U.S. Pat. Nos. 4,004,929 and 4,138,258, British Patent 1,146,368.
Those described in the above item are preferred. Also, U.S. Pat.
A coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in No. 4,181,
It is also preferable to use a coupler having a dye precursor group capable of forming a dye by reacting with a developing agent described in U.S. Pat. No. 4,777,120 as a leaving group.

Compounds which release a photographically useful residue upon coupling can also be preferably used in the present invention.
The DIR coupler releasing the development inhibitor is the RD1 described above.
No. 7643, VII-F and the same No. 307105, VII-
Patent described in section F, JP-A-57-151944,
Preferred are those described in JP-A-57-154234, JP-A-60-184248, JP-A-63-37346, JP-A-63-37350 and U.S. Pat. Nos. 4,248,962 and 4,782,012.

As a coupler which releases a nucleating agent or a development accelerator in the form of an image at the time of development, British Patent No. 2,099
7,140,2,131,188, JP-A-59
Preferred are those described in JP-A-157638 and JP-A-59-170840. Also, JP-A-60-107029, JP-A-60-252340, JP-A-1-44940 and JP-A-1-44940.
Also preferred are compounds capable of releasing a fogging agent, a development accelerator, a silver halide solvent and the like by an oxidation-reduction reaction with an oxidized form of a developing agent described in JP-A-45687.

Other compounds that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,427.
No. 4,283,4.
No. 72, No. 4,338,393, No. 4,310,
No. 618, etc .;
No. 5950, Japanese Patent Application Laid-Open No. 62-24252, and the like.
R redox compound-releasing couplers, DIR coupler-releasing couplers, DIR coupler-releasing redox compounds or DIR redox-releasing redox compounds, couplers which release dyes that discolor after release as described in EP 173,302A and EP 313,308A , RD. No. 1
Bleaching accelerator releasing couplers described in US Pat. Nos. 4,5, 1449, 24241, and JP-A-61-201247.
55,477, etc., couplers releasing leuco dyes described in JP-A-63-75747, and couplers releasing fluorescent dyes described in U.S. Pat. No. 4,774,181. .

The coupler used in the present invention can be introduced into a light-sensitive material by various known dispersion methods. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in, for example, US Pat. No. 2,322,027. Specific examples of the high-boiling organic solvent having a boiling point at normal pressure of 175 ° C. or higher 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-tert-amylphenyl)
Phthalates, bis (2,4-di-tert-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate); phosphoric acid or phosphonic acid esters (e.g., triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenyl phosphonate); benzoic acid esters (for example, 2-ethylhexyl benzoate) , Dodecyl benzoate, 2-
Ethylhexyl-p-hydroxybenzoate); amides (for example, N, N-diethyldodecaneamide, N,
N-diethyl laurylamide, 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-tert-octylaniline); and hydrocarbons (eg, paraffin, dodecylbenzene, diisopropylnaphthalene). As the auxiliary solvent, for example, the boiling point is about 30 ° C. or more, preferably 50 ° C.
An organic solvent having a temperature of at least about 160 ° C. or less can be used. Typical examples include, for example, ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone,
2-ethoxyethyl acetate and dimethylformamide.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described, for example, in US Pat.
9,363, West German Patent Application (OLS) No. 2,541,
274 and 2,541,230.

In the color light-sensitive material of the present invention, phenethyl alcohol, JP-A-63-257747 and JP-A-63-257747, may be used.
272248 and JP-A-1-80941, for example, 1,2-benzisothiazolin-3-one, n-butyl-p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, −
It is preferable to add various preservatives or fungicides such as phenoxyethanol and 2- (4-thiazolyl) benzimidazole.

The present invention can be applied to various color light-sensitive materials. For example, color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers can be mentioned as typical examples. The present invention can be particularly preferably used for a color duplication film.

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

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, and 18 μm or less.
m or less, more preferably 16 μm or less.
Further, the film swelling speed T1 / 2 is preferably 30 seconds or less,
0 second or less is more preferable. Here, the film thickness means a film thickness measured under humidity control at 25 ° C. and 55% relative humidity (2 days).
Also, the film swelling rate T1 / 2 can be measured according to techniques known in the art, for example, by A. Green et al., Photographic Science and Engineering (Photo).
gr. Sci. Eng. ), Vol. 19, No. 2, 124-1
It can be measured by using a serometer (swelling meter) of the type described on page 29. T1 / 2 is defined as 90% of the maximum swollen film thickness reached when the film is processed at 30 ° C. for 3 minutes and 15 seconds with a color developing solution, and defined as the time required to reach 1/2 of the saturated film thickness. I do.

The film swelling speed T1 / 2 can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating.

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

The color photographic light-sensitive material according to the present invention is prepared by using the RD. No. No. 17643, pages 28 to 29;
No. 18716, page 651, left column to right column; 30
The development can be carried out by a usual method described on pages 880 to 881 of No. 7105.

The color developing solution used for developing the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as the color developing agent, but p-phenylenediamine compounds are preferably used, and a typical example thereof is 3-methyl-4-amino-
N, N diethylaniline, 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, and sulfates, hydrochlorides or p-toluenesulfonates thereof. Among these, in particular, 3-methyl-4-
Sulfates of amino-N-ethyl-N-β-hydroxyethylaniline are preferred. These compounds are used depending on the purpose.
More than one species may be used in combination.

The color developing solution may be, for example, a pH buffer such as an alkali metal carbonate, borate or phosphate,
It generally contains a development inhibitor or antifoggant such as chloride, bromide, iodide, benzimidazoles, benzothiazoles or mercapto compounds. If necessary, various preservatives such as hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazide, triethanolamine and catecholsulfonic acid; ethylene glycol; Organic solvents such as diethylene glycol; benzyl alcohol, polyethylene glycol, quaternary ammonium salts,
Development accelerators such as amines; dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone; viscosity-imparting agents; aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonos Various chelating agents such as carboxylic acids can be used. Examples of the chelating agent include ethylenediaminetetraacetic acid, nitriletriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-
Representative examples include diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof. be able to.

When the reversal processing is performed, color development is usually performed after black-and-white development. The black-and-white developer includes, for example, dihydroxybenzenes such as hydroquinone, for example, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or N-methyl-
Known black and white developing agents of aminophenols such as p-aminophenol can be used alone or in combination. The p of these color developing solutions and black-and-white developing solutions
H is generally 9 to 12. The replenishment 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. You can also When the replenishment amount is reduced, it is preferable to prevent the evaporation and air oxidation of the processing liquid by reducing the contact area of the processing liquid with air.

The contact area between the photographic processing solution and air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio = [contact area between processing solution and air (cm ² )] ÷ [capacity of processing solution (cm ³ )] The above-mentioned aperture ratio is preferably 0.1 or less, more preferably 0.1% or less. 001 to 0.05. As a method of reducing the aperture ratio in this way, in addition to a method of providing a shield such as a floating lid on the photographic processing liquid surface of the processing tank, a movable lid described in JP-A-1-82033 is used. And a slit developing method described in JP-A-63-216050. The reduction of the aperture ratio is preferably applied not only to both the color development and black-and-white development steps but also to the following various steps, for example, all the steps of bleaching, bleach-fixing, fixing, washing and stabilization. Further, by using means for suppressing the accumulation of bromide ions in the developer, the replenishing amount can be reduced.

The time for color development processing is usually set to 2 to 5 minutes, but the processing time can be further shortened by using a high temperature and high pH and using a high concentration of the color developing agent. .

The photographic emulsion layer after color development is usually subjected to bleaching. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Furthermore, processing in two continuous bleach-fix baths, fixing before bleach-fix processing,
Alternatively, bleaching after bleach-fixing can be arbitrarily performed according to the purpose. As the bleaching agent, for example, compounds of a polyvalent metal such as iron (III), peracids (particularly, sodium persulfate is suitable for a color negative film for movies), quinones, and nitro compounds are used. Representative bleaching agents include organic complex salts of iron (III), for example, ethylenediaminetetraacetic acid,
Complex salts with aminopolycarboxylic acids such as diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycoletherdiaminetetraacetic acid, or, for example, citric acid, tartaric acid, malic acid Can be used. Of these, iron (III) aminopolycarboxylate complexes, including iron (III) complex salts of ethylenediaminetetraacetate and 1,3-diaminopropanetetraacetate,
It is preferable from the viewpoint of rapid processing and prevention of environmental pollution. further,
The aminoboric acid iron (III) complex salt is particularly useful in a bleaching solution and a bleach-fixing solution. The pH of the bleaching solution or the bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually from 4.0 to 8, but the processing can be carried out at a lower pH in order to speed up the processing.

In the bleaching solution, the bleach-fixing solution and the prebath thereof, a bleaching accelerator can be used if necessary.
Specific examples of useful bleach accelerators are described in the following specification: for example, U.S. Pat. No. 3,893,858, West German Patent 1,290,812, and 2,059,988.
JP-A-53-32736 and JP-A-53-57831.
No. 53-37418, No. 53-72623, No. 53-95630, No. 53-95731, No. 53-
No. 104232, No. 53-124424, No. 53-1
No. 41623, No. 53-18426, Research Disclosure No. 17129 (July 1978)
Compounds having a mercapto group or a disulfide group described in JP-A-51-140129; thiazolidine derivatives described in JP-A-51-140129; Japanese Patent Publication No. 45-8506;
Nos. 832 and 53-32735, U.S. Pat.
No. 6,561, the thiourea derivative described in West German Patent 1,
127,715; JP-A-58-16235; West German Patent Nos. 966,410 and 2,741
8,430; polyamine compounds described in JP-B-45-8836; and JP-A-49-40943 and JP-A-49-59644.
Nos. 53-94927, 54-35727, 55
Compounds described in -26506 and 58-163940; bromide ions and the like can be used. Among them, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large accelerating effect, and in particular, US Pat.
No. 58, West German Patent No. 1,290,812,
Compounds described in -95630 are preferred. Further, the compounds described in U.S. Pat. No. 4,552,884 are also preferable. These bleaching accelerators may be added to the light-sensitive material. When bleach-fixing a color photographic material for photography, these bleaching accelerators are particularly effective.

The bleaching solution and the bleach-fixing solution preferably contain an organic acid in addition to the above compounds for the purpose of preventing bleaching stain. Particularly preferred organic acids are compounds having an acid dissociation constant (pKa) of 2 to 5, and specific examples include acetic acid, propionic acid, and hydroxyacetic acid.

Examples of the fixing agent used in the fixing solution or the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodides. Of these, use of thiosulfates is common, and in particular, ammonium thiosulfate can be used most widely. Also, thiosulfate and, for example, thiocyanate,
A combination use of a thioether compound and thiourea is also preferable. Examples of the preservatives of the fixing solution and the bleach-fixing solution include sulfites, bisulfites, carbonyl bisulfite adducts and European Patent No. 2
Sulfinic acid compounds described in No. 94,769A are preferred. Further, it is preferable to add various aminopolycarboxylic acids or organic phosphonic acids to the fixing solution or the bleach-fixing solution for the purpose of stabilizing the solution.

In the present invention, the fixing solution or the bleach-fixing solution contains a compound having a pKa of 6.0 to 9.0, preferably imidazole, 1-methylimidazole, 1-ethylimidazole, 2-methyl It is preferable to add imidazoles such as imidazole in an amount of 0.1 to 10 mol / l.

It is preferable that the total time of the desilvering step is shorter as long as the desilvering failure does not occur. Preferred time is 1 minute to 3
Minutes, more preferably 1 to 2 minutes. Further, the processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C.
In a preferable temperature range, the desilvering speed is improved, and generation of stain after processing is effectively prevented.

In the desilvering step, it is preferable that stirring is strengthened as much as possible. As a specific method for enhancing the stirring, a method described in JP-A-62-183460, in which a jet of a processing solution is made to impinge on the emulsion surface of a photosensitive material, or a method described in JP-A-62-183461, using a rotating means. There is a method to improve the effect. In addition, the photosensitive material is moved while the wiper blade provided in the solution is in contact with the emulsion surface, and the turbulence of the emulsion surface is used to improve the stirring effect, and the circulation flow rate of the entire processing solution is increased. There is a method to make it. Such an agitation improving means is effective for any of a bleaching solution, a bleach-fixing solution and a 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, thereby increasing the desilvering speed. The means for improving the stirring is more effective when a bleaching accelerator is used, and can significantly increase the accelerating effect or eliminate the fixing inhibition effect by the bleaching accelerator.

The automatic developing machine used for developing the light-sensitive material of the present invention is described in JP-A-60-191257 and JP-A-60-191257.
It is preferable to have the photosensitive material conveying means described in JP-A Nos. 1258 and 60-191259. Japanese Unexamined Patent Publication No. Sho 6
As described in Japanese Patent Application No. 0-191257, such a conveying means can significantly reduce the carry-in of the processing liquid from the pre-bath to the post-bath, and is highly effective in preventing the performance of the processing liquid from deteriorating. Such an effect is particularly effective in shortening the processing time in each step and reducing the replenishing amount of the processing solution.

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of water to be washed in the water washing step depends on the characteristics of the photosensitive material (for example, depending on the material used such as a coupler), the use,
Further, for example, the washing water temperature, the number of washing tanks (the number of stages),
It can be set in a wide range according to a replenishment method such as countercurrent or forward flow, and other various conditions. Among them, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is shown in Journal of
the Society of Motion Pi
cure and Television Engi
neers, vol. 64, p. 248-253 (1955)
May issue).

According to the multistage countercurrent method described in the above-mentioned document,
Although the amount of washing water can be greatly reduced, there is a problem that bacteria increase due to an increase in the residence time of water in the tank, and the generated suspended matter adheres to the photosensitive material.
In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ions and magnesium ions described in JP-A-62-288838 can be used very effectively. Also described in JP-A-57-8542, for example, isothiazolone compounds, thiabendazoles, chlorinated fungicides such as chlorinated sodium isocyanurate, and others, such as benzotriazole, by Horiguchi Hiroshi "The Chemistry of Bactericidal and Fungicides" (1986) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Techniques" (1982) Industrial Technology Association, Japan Bactericidal and Fungicide Society, Ed. A fungicide described in "A fungus encyclopedia" (1986) can also be used.

Washing water p during processing of the light-sensitive material of the present invention
H is 4-9, preferably 5-8. The washing water temperature and washing time can also be variously set depending on, for example, the characteristics and use of the photosensitive material, but are generally at 15 to 45 ° C. for 20 seconds to 1 hour.
A range of 0 minutes, preferably 30 seconds to 5 minutes at 25-40 ° C is selected. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned water washing. In such a stabilization process, Japanese Patent Application Laid-Open No. 57-8543
, 58-14834 and 60-220345 can all be used.

In some cases, a stabilization process may be performed after the water washing process. An example thereof is a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photography. Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine and aldehyde sulfite adducts. Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution accompanying the washing and / or replenishment of the stabilizing solution can be reused in another step such as a desilvering step.

For example, in processing using an automatic developing machine,
When each of the above-mentioned treatment liquids is concentrated by evaporation, it is preferable to add water to correct the concentration.

In the silver halide color photographic light-sensitive material of the present invention, a color developing agent may be incorporated for the purpose of simplifying and speeding up the processing. In order to incorporate them, it is preferable to use various precursors of a color developing agent. For example, indoaniline compounds described in U.S. Pat. No. 3,342,597, for example, U.S. Pat. No. 3,342,599, Research Disclosure No. 14, 850 and the same No.
Nos. 15, 15 and 159; 1
Aldol compounds described in U.S. Pat.
No. 719,492, a metal salt complex disclosed in JP-A-53-1
The urethane compounds described in JP-A-35628 can be exemplified.

The silver halide color light-sensitive material of the present invention comprises
If necessary, various 1-
Phenyl-3-pyrazolidones may be incorporated. Typical compounds are described, for example, in JP-A-56-64339, JP-A-57-144547 and JP-A-58-115438.

The various processing solutions in the present invention may be used at a temperature of 10 ° C. to 5
Used at 0 ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but a higher temperature promotes the processing and shortens the processing time, and a lower temperature achieves an improvement in the image quality and an improvement in the stability of the processing solution. be able to.

The silver halide light-sensitive material of the present invention comprises
U.S. Pat. No. 4,500,626, JP-A-60-133
No. 449, No. 59-218443, No. 61-2380
No. 56, EP 210,660 A2 and the like.

The silver halide color photographic light-sensitive material of the present invention is disclosed in JP-B-2-32615 and JP-B-3-397.
In the case where the invention is applied to a film unit with a lens described in No. 84 or the like, the effect is more easily exhibited and is effective.

The present invention can be preferably used for a diffusion transfer light-sensitive material. The most typical form of the diffusion transfer photosensitive material is a color diffusion transfer film unit, and the typical form is such that an image receiving element and a photosensitive element are laminated on one transparent support, and the transferred image is formed. After completion of the above, there is no need to peel the photosensitive element from the image receiving element. More specifically, the image-receiving element comprises at least one mordant layer, and in a preferred embodiment of the light-sensitive element, a combination of a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer, or a green-sensitive emulsion layer A combination of a red-sensitive emulsion layer and an infrared-sensitive emulsion layer, or a combination of a blue-sensitive emulsion layer, a red-sensitive emulsion layer and an infrared-sensitive emulsion layer, and a yellow dye image-forming compound in each of the above emulsion layers; The magenta dye image-forming compound and the cyan dye image-forming compound are respectively combined (here, the term “infrared-sensitive emulsion layer” means 700 nm or more, particularly 74 nm).
An emulsion layer having a spectral sensitivity maximum with respect to light of 0 nm or more). A white reflective layer containing a solid pigment such as titanium oxide is provided between the mordant layer and the photosensitive layer or the dye image forming compound-containing layer so that the transferred image can be viewed through the transparent support.

A light-shielding layer may be further provided between the white reflective layer and the photosensitive layer so that the developing process can be completed in a light place. If desired, a release layer may be provided at an appropriate position so that all or a part of the photosensitive element can be peeled from the image receiving element. Such an embodiment is disclosed in, for example,
67840 and Canadian Patent 674,082.

Further, as another embodiment of a laminate type, which is peeled off, at least (a) a layer having a neutralizing function, (b) a dye image-receiving layer, (b) a white support described in JP-A-63-226649. c) a release layer, (d) a photosensitive element sequentially having at least one silver halide emulsion layer in combination with a dye image-forming compound, an alkali treatment composition containing a light-blocking agent, and a transparent cover sheet. There is a color diffusion transfer photographic film unit having a layer having a light-shielding function on the side opposite to the side on which the processing composition is developed.

In another mode in which peeling is unnecessary, the above-described photosensitive element is coated on one transparent support, a white reflective layer is coated thereon, and an image receiving layer is further laminated thereon. .
An image receiving element, a white reflective layer, a release layer, and a photosensitive element are laminated on the same support, and an embodiment in which the photosensitive element is intentionally peeled from the image receiving element is described in US Pat. No. 3,730,71.
No. 8 is described.

On the other hand, there are roughly two typical forms in which a photosensitive element and an image receiving element are separately coated on two supports, respectively, one of which is a peelable type, and the other is a peelable type. is there. More specifically, in a preferred embodiment of the peelable film unit, at least one image receiving layer is coated on one support, and the photosensitive element is coated on a support having a light shielding layer. Before the end of the exposure, the coated surface of the photosensitive layer and the coated surface of the mordant layer do not face each other, but after the end of the exposure (for example, during the developing process), the coated surface of the photosensitive layer is inverted in the image forming apparatus and comes into contact with the coated surface of the image receiving layer. It is devised as follows. After the transfer image is completed in the mordant layer, the photosensitive element is immediately separated from the image receiving element.

In a preferred embodiment of the peeling-free film unit, at least one mordant layer is provided on a transparent support, and a photosensitive element is provided on a support having a transparent or light-shielding layer. The surface on which the photosensitive layer is applied and the surface on which the mordant layer is applied face each other.

A pressure-rupturable container (processing element) further containing an alkaline processing liquid may be combined with the above-described embodiment. In particular, in a peeling-free film unit in which an image receiving element and a photosensitive element are laminated on one support, the processing element is preferably arranged between the photosensitive element and a cover sheet overlaid thereon. In the case where the photosensitive element and the image receiving element are separately coated on the two supports, it is preferable that the processing element is arranged between the photosensitive element and the image receiving element at the latest at the time of development processing. The processing element preferably contains one or both of a light-shielding agent (such as carbon black or a dye whose color changes depending on pH) and a white pigment (such as titanium oxide) depending on the form of the film unit. Further, in the film unit of the color diffusion transfer system, it is preferable that a neutralization timing mechanism comprising a combination of a neutralization layer and a neutralization timing layer is incorporated in the cover sheet, the image receiving element, or the photosensitive element.

The dye image-forming substance used in the present invention is a non-diffusible compound which releases a diffusible dye (may be a dye precursor) in connection with silver development, or a substance which changes its own diffusivity. And "Theory of the Photographic Process"
It is stated in the edition. All of these compounds can be represented by the following general formula (XIII). Formula (XIII) (DYE-Y) n-ZＺDYE represents a dye group, a temporarily shortened dye group or a dye precursor group, Y represents a mere bond or a linking group,
Z is related to silver development (specifically, corresponding to or inversely corresponding to a photosensitive silver salt having an image-like latent image) (DYE-Y)
causing a difference in the diffusivity of the compound represented by n-Z,
Alternatively, DYE is released, and the released DYE and (DYE-
Y) represents a group having a property that causes a difference in diffusivity with n-Z, n represents 1 or 2, and n represents 2
At this time, the two DYE-Ys may be the same or different.機能 By the function of Z, the compound is roughly classified into a negative type compound which becomes diffusible in a silver developed portion and a positive type compound which becomes diffusible in an undeveloped portion. Specific examples of the negative type Z include those which oxidize as a result of development and are cleaved to release a diffusible dye.
Specific examples of Z are described in U.S. Pat. Nos. 3,928,312 and 3,9
Nos. 93,638, 4,076,529 and 4,15
No. 2,153, No. 4,055,428, No. 4,05
No. 3,312, No. 4,198,235, No. 4,17
9,291, 4,149,892 and 3,84
4,785, 3,443,943, 3,75
No. 1,406, No. 3,443,939, No. 3,44
No. 3,940, No. 3,628,952, No. 3,98
0,479, 4,183,753, 4,14
Nos. 2,891, 4,278,750, 4,13
9,379, 4,218,368, 3,42
1,964, 4,199,355, 4,19
9,354, 4,135,929, 4,33
6,322,4,139,389,
No. 50736, No. 51-104343, No. 54-13
No. 0122, No. 53-110827, No. 56-126
No. 42, No. 56-16131, No. 57-4043,
No. 57-650, No. 57-20735, No. 53-6
Nos. 9033, 54-130927, 56-164
342, 57-119345 and the like.
Among the Z of the negative dye-releasing redox compound, a particularly preferred group is an N-substituted sulfamoyl group (an N-substituent is a group derived from an aromatic hydrocarbon ring or a hetero ring). Representative groups of Z are exemplified below, but are not limited thereto.

[0289]

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Regarding the positive type compounds, see Angev. Chem. Int. Ed. Engl., 22, 191.
(1982). Specific examples include compounds (dye developing agents) which are initially diffusible under alkaline conditions, but are oxidized by development to become non-diffusible. Z useful in this type of compound is disclosed in US Pat.
No. 3606 is representative. Another type is a type which releases a diffusible dye by, for example, self-ring closure under alkaline conditions, but substantially does not release the dye when oxidized during development. For a specific example of Z having such a function, see US Pat.
980,479, JP-A-53-69033, 54
No. 130927, U.S. Pat. Nos. 3,421,964 and 4,199,355. Another type does not release the dye itself, but releases the dye when reduced. Compounds of this type can be used in combination with an electron donor to release the diffusible dye imagewise by reaction with the remaining electron donor imagewise oxidized by silver development. For atomic groups having such a function, see, for example, US Pat. No. 4,183,75.
No. 3, No. 4, 142, 891, No. 4, 278, 750
Nos. 4,139,379 and 4,218,368
JP-A-53-110827, U.S. Pat.
8,750, 4,356,249, 4,35
8,535, JP-A-53-110827, and 54-
130927, 56-164342, published technical report 8
No. 7-6199, European Patent Publication No. 220746A2, and the like. Specific examples of Z will be described below, but the present invention is not limited thereto.

[0291]

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When a compound of this type is used, it is preferably used in combination with a diffusion-resistant electron-donating compound (known as an ED compound) or a precursor thereof. Examples of ED compounds include, for example, US Pat.
Nos. 63,393 and 4,278,750;
No. 138736. Specific examples of other types of dye image-forming substances include the following.

[0293]

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The details are described in US Pat. Nos. 3,719,489 and 4,098,783. on the other hand,
Specific examples of the dye represented by DYE in the above general formula are described in the following documents. Examples of yellow dyes: U.S. Pat. Nos. 3,597,200, 3,309,199, 4,013,633, 4,245,028, 4,156,609 and 4,139. JP-A-51-114930, JP-A-56-71072, JP-A-51-114930 and JP-A-56-71072. Rese
arch Disclosure 17630 (1978), 164
75 (1977). Examples of magenta dyes: U.S. Pat. Nos. 3,453,107, 3,544,545, 3,932,380, 3,931,144, 3,932,308, and 3,954 No. 4,476, No. 4,233,237, No. 4,255,509, No. 4,250,246, No. 4,142,891, No. 4,207,104, No. 4,287,292 No .: JP-A-52-106,727
Nos. 53-23,628 and 55-36,804
No. 56-73,057, No. 56-71060,
No. 55-134. Examples of cyan dyes: U.S. Pat. Nos. 3,482,972, 3,929,760, 4,013,635, 4,268,625, 4,171,220 and 4,242 4,435,891,4,195,994,4,147,544,4,148,642; British Patent 1,551,138
Nos .: JP-A-54-99431 and JP-A-52-8827,
Nos. 53-47823, 53-143323, 5
4-99431 and 56-71061; European Patents (EP) 53,037 and 53,040; Rese
Arch Disclosure 17,630 (1978) and 16,475 (1977). These compounds are described in JP-A-62-215272, 14
It can be dispersed by the method described on pages 4-146. These dispersions are described in JP-A-62-215,272.
No. 137-144.

[0295]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

Example 1 (Preparation of seed emulsion a) 0.017 g of KBr, average molecular weight 2
Aqueous solution 11 containing 0.4 g of 0000 oxidized gelatin
64 ml was kept at 35 ° C. and stirred. AgNO ₃ (1.6
g) An aqueous solution, an aqueous KBr solution, and an aqueous solution of oxidized gelatin (2.1 g) having an average molecular weight of 20,000 were added over 48 seconds by a triple jet method. At this time, the silver potential was kept at 13 mV with respect to the saturated calomel electrode. After an aqueous KBr solution was added to adjust the silver potential to −66 mV, the temperature was raised to 60 ° C. 21 g of succinated gelatin having an average molecular weight of 100,000
Was added, and an aqueous solution of NaCl (5.1 g) was added. An aqueous solution of AgNO ₃ (206.3 g) and an aqueous solution of KBr were added over a period of 61 minutes while accelerating the flow rate by the double jet method. At this time, the silver potential was kept at -44 mV with respect to the saturated calomel electrode. After desalting, the average molecular weight is 100
000 succinated gelatin and pH 5 at 40 ° C.
The pAg was adjusted to 8, and a seed emulsion was prepared. This seed emulsion contains 1 mol of Ag and 8 gelatin per kg of emulsion.
0 g, tabular grains having an average equivalent circle diameter of 1.46 μm, a coefficient of variation of equivalent circle diameter of 28%, an average thickness of 0.046 μm, and an average aspect ratio of 32.

(Formation of core) 134 g of the above seed emulsion a was prepared.
Succinated KBr 1.9 g, average molecular weight 100000
Keep 1200 ml of aqueous solution containing 22 g of rat at 75 ° C
Stirred. AgNO _Three(43.9 g) aqueous solution and KBr water
Solution and an aqueous gelatin solution having a molecular weight of 20,000
-43570 Magnetic coupling induction type stirrer
25 minutes mixing just before addition in another chamber with
Added over time. At this time, the silver potential is changed to a saturated calomel electrode.
-40 mV.

(Formation of First Shell) After the formation of the core particles, an aqueous solution of AgNO ₃ (43.9 g), an aqueous solution of KBr, and an aqueous solution of gelatin having a molecular weight of 20,000 were mixed just before the addition in another chamber of the same type, and the mixture was added. Added over minutes. At this time, the silver potential was set to −40 with respect to the saturated calomel electrode.
mV.

(Formation of Second Shell) After the formation of the first shell, an aqueous solution of AgNO ₃ (42.6 g), an aqueous solution of KBr, and an aqueous solution of gelatin having a molecular weight of 20,000 were mixed immediately before addition in another chamber. Added over 17 minutes. At this time, the silver potential was set to -20 with respect to the saturated calomel electrode.
mV. Thereafter, the temperature was lowered to 55 ° C.

(Formation of Third Shell) After the formation of the second shell, the silver potential was adjusted to -55 mV, and AgNO ₃ (7.
1 g) aqueous solution, KI (6.9 g) aqueous solution and molecular weight 200
00 gelatin aqueous solution was mixed immediately before addition in another chamber as above and added over 5 minutes.

(Formation of Fourth Shell) After the formation of the third shell, an aqueous solution of AgNO ₃ (66.4 g) and an aqueous solution of KBr were added at a constant flow rate over 30 minutes by a double jet method. On the way, iridium potassium hexachloride and yellow blood salt were added. At this time, the silver potential is set at 30 with respect to the saturated calomel electrode.
mV. Perform normal water washing, add gelatin,
PH was adjusted to 5.8 and pAg to 8.8 at 40 ° C. This emulsion was designated as emulsion b. Emulsion b had an average equivalent circle diameter of 3.3 μm,
Coefficient of variation of equivalent circle diameter 21%, average thickness 0.090μm,
The tabular grains had an average aspect ratio of 37. Further, 70% or more of the total projected area has a circle equivalent diameter of 3.3 μ or more and a thickness of 0.3 μm.
Occupied by tabular grains of 090 μm or less. One layer saturation coverage of when the dye occupation area as 80 Å ² 1.4
It was 5 × 10 ⁻³ mol / mol Ag.

Comparative Example 1 Emulsion b was heated to 56 ° C., and D-7 was added to 1.2 × 10^-3mol
/ MolAg, potassium thiocyanate, chloride
Auric acid, sodium thiosulfate and N, N-dimethyl selenium
Nourea was added for optimal chemical sensitization. Further D-7
Is 2.5 × 10 ^-Four10 minutes after adding mol / mol Ag
Stirred. Comparative Examples 2, 3, 4 In Comparative Example 1, D-7 was changed to D-6, D-15, or D-4.
Furthermore, Comparative Examples 2, 3, and 4 were respectively obtained. Comparative Example 5 Emulsion b was heated to 56 ° C., and D-7 was 1.2 × 10^-3mol
/ MolAg, potassium thiocyanate, chloride
Auric acid, sodium thiosulfate and N, N-dimethyl selenium
Nourea was added for optimal chemical sensitization. Further D-7
Is 2.5 × 10 ^-Four10 minutes after adding mol / mol Ag
Stirred. Thereafter, D-15 and D-32 were each adjusted to 1.0
× 10^-3Addition of mol / molAg at a time for another 60 minutes
While stirring. Comparative Examples 6 and 7 In Comparative Example 5, D-7 was D-6, D-15 was D-1, and D-
32 to D-22, Comparative Example 6, D-7 to D-15, D-15
Comparative Example 7 was made by changing Compound 1 and D-32 to Compound 2.

[0303]

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[0304]

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Invention 1 Emulsion b was heated to 56 ° C., and D-15 was added in an amount of 1.2 × 10 ⁻³ mol.
After addition of / molAg, potassium thiocyanate, chloroauric acid, sodium thiosulfate and N, N-dimethylselenourea were added for optimal chemical sensitization. Further D-15
Was added at 2.5 × 10 ⁻⁴ mol / mol Ag, followed by stirring for 10 minutes. Thereafter, D-6 and D-27 were each added to 1.
0 × 10 ⁻³ mol / mol Ag was added in increments of 60 to
Stirred for minutes. However, the sensitizing dye is described in JP-A-11-5250.
This was used as a fine solid dispersion prepared by the method described in No. 7. That is, 0.8 parts by weight of sodium nitrate and 3.2 parts by weight of sodium sulfate are dissolved in 43 parts of ion-exchanged water, and 13 parts by weight of a sensitizing dye are added. By dispersing for 1 minute, a solid dispersion of the sensitizing dye was obtained. Inventions 2, 3, and 4 In Invention 1, D-6 was changed to D-1 and D-27 was changed to D-22 to provide Invention 2. In the present invention 1, D-15 is replaced with D-
7. The present invention 3 by changing D-6 to D-1 and D-27 to D-22.
And Further, in the present invention 1, D-15 was changed to D-4 to obtain the present invention 4. Inventions 5, 6, 7, 8 In the inventions 1, 2, 3, and 4, preferred examples of the general formula (VIII) include potassium thiocyanate, chloroauric acid, sodium thiosulfate and N, N-dimethylselenourea. The compound of the above (7) was added in an amount of 2 × 10 ^-4 mol per mol of silver halide, and the compounds of the invention 5, 6, 7, and 8 were added, respectively.
And The light absorption intensity per unit area of the grain surface contained in the emulsion obtained by adding the sensitizing dye as described above was measured.

The measurement of the light absorption intensity per unit area is as follows.
Apply the thin emulsion to a glass slide
Using Ice Microscope MSP65
The transmission spectrum and the reflection of each particle are
The emission spectrum was measured to determine the absorption spectrum. Transparent
The hyperspectral reference is the particle-free part
And the reflection spectrum is a silicon camera whose reflectance is known.
The carbide was measured and used as a reference. Measurement part is diameter
1μm circular aperture, with aperture on particle outline
Adjust the position so that the char section does not overlap and 14000
cm^-1(714 nm) to 28000 cm^-1(357n
Transmission spectrum and reflection spectrum in the wave number range up to m)
1-T (transmittance)-R (reflectance)
The absorption spectrum was determined as A. Silver halide absorption
Is subtracted to obtain an absorption rate A ′, and −Log (1-A ′) is
Wave number (cm^-1), Halving the integrated value
The light absorption intensity per surface area was used. Integration range is 1400
0cm^-1From 28000cm ^-1Up to. At this time,
The source is a tungsten lamp and the light source voltage is 8V
Was. Primary to minimize dye damage from light irradiation
Using the monochromator on the side, the wavelength interval is 2 nm,
The cut width was set to 2.5 nm. Absorb about 200 particles
The yield spectrum and light absorption intensity were determined.

Further, a gelatin hardener and a coating aid were added to the obtained emulsion, and a gelatin protective layer was formed on a cellulose acetate film support so that the coated silver amount was 3.0 g-Ag / m ^2. At the same time. The resulting film was exposed to a tungsten bulb (color temperature 2854K) for 1 second through a continuous wedge color filter.
Using a Fuji gelatin filter SC-50 (manufactured by FUJIFILM Corporation) for minus blue exposure which excites the dye side as a color filter, light of 500 nm or less was blocked and the sample was irradiated. The exposed sample was the following surface developer MAA
Developed at -20 ° C. for 10 minutes.

Surface developer MAA-1 formulation Metol 2.5 g L-ascorbic acid 10 g Navox (Fuji Film Co., Ltd.) 35 g Potassium bromide 1 g Water was added to add 1 liter pH 9.8

After development, fixing was performed at 20 ° C. with the following fixing solution. Fixer formulation Ammonium thiosulfate 170 g Sodium sulfite (anhydrous) 15 g Boric acid 7 g Glacial acetic acid 15 ml Potassium alum 20 g Ethylenediaminetetraacetic acid 0.1 g Tartaric acid 3.5 g Add water 1 liter Measure optical density with Fuji automatic densitometer. +0.
It is shown by the reciprocal of the amount of light required to give an optical density of 2.
Treated film at 40 ° C to evaluate raw storage
The change in sensitivity to Fresh sensitivity when sensitometry was performed after incubation at 60 ° C. and a relative humidity of 60% for 60 days was examined. The change in sensitivity was calculated according to the following equation. Sensitivity change = log10 (sensitivity after raw storage / Fresh sensitivity)

The results are shown in Table 1.

[0311]

[Table 1]

1) The light absorption intensities of Comparative Examples 5, 6, and 7 were 100% for Comparative Examples 1, 2, and 3, respectively.
2, 5, and 6 are Comparative Examples 3, Comparative Examples 4 and 4 are Comparative Examples 1 and 4, and Inventions 7 and 8 are Comparative Values when Comparative Examples 1 and 4 are 100. 2) The reduction potential of the dye in the second layer is the average of the two dyes. 3) Fresh sensitivity is represented by the reciprocal of the amount of light required to give an optical density of +0.2, and the sensitivities of Comparative Examples 5, 6, and 7 are the same as those of Comparative Examples 1, 2, and 3, respectively. 1, 2,
5 and 6 are Comparative Example 3, and the present inventions 3 and 4 are Comparative Example 1, respectively.
4. Comparative values of Comparative Examples 1 and 4 are 100 when the values of Comparative Examples 1 and 4 are 100, respectively. 4) log10 (sensitivity after raw storage / Fresh sensitivity). It has been clarified that the multilayer adsorption system using the dye having the combination of the reduction potentials of the present invention has improved raw preservability as compared with the multilayer adsorption system using the dye having any other combination.

Example 2 A tabular silver iodobromide emulsion was prepared in the same manner as in Emulsion D of Example 5 of JP-A-8-29904 to prepare Emulsion c. Comparative Examples 8, 9, 10, and 12 Multilayer color photographic materials were prepared in the same manner as in Sample 101 of Example 5 of JP-A-8-29904. Emulsion L of the twelfth layer in Sample 101 of Example 5 of JP-A-8-29904 was replaced with emulsion c, ExS-7 was changed to sensitizing dye D-20, and the dye was changed to 3 per mole of silver halide. Each of the samples to which × 10 ^-4 mol was added was designated as Comparative Example 8. The sensitizing dye D-20 of Comparative Example 8 was changed to D-16 or D-19 to obtain Comparative Examples 9 and 10, respectively. The sensitizing dye D-20 of Comparative Example 8 was changed to D-16, D-20, and D-37 to obtain Comparative Example 11. Further, sensitizing dye D-20 of Comparative Example 8 was used.
Comparative Example 12 was changed to D-16, Compound 3, and Compound 4.

[0314]

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[0315]

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Invention 9,10,11,12,13,14 The twelfth sample 101 of Example 5 of JP-A-8-29904 was used.
The emulsion L in the layer was replaced with the emulsion c, and ExS-7 was replaced with the sensitizing dye D-2.
A sample to which each of the dyes was added in an amount of 3 × 10 ^-4 mol per mol of silver halide, instead of D, D-18 and D-34, was designated as Invention 9. The sensitizing dye D-20 of the present invention 9 was changed to D-16 or D-19 to obtain the present inventions 10 and 11, respectively. In the present inventions 9, 10 and 11, the compounds of the formula (7) shown as preferred specific examples of the general formula (VIII) were added at the time of chemical sensitization to obtain the present inventions 12, 13 and 14, respectively. The light absorption intensity of the obtained coated film was measured in the same manner as in Example 1. The sensitivity was determined by measuring the yellow color density of the sample. Table 2 shows the results of the same evaluation as in Example 1 for evaluating the raw preservability.

[0317]

[Table 2]

1) The light absorption intensity of Comparative Examples 11 and 12 was
Is 100, inventions 9, 10, and 11 are comparative examples 8, 9, and 10, respectively, and inventions 12, 13, and 14 are comparative examples 8,
Relative value when 9 and 10 are set to 100. 2) The reduction potential of the dye in the second layer is the average of the two dyes. 3) Fresh sensitivity is indicated by the reciprocal of the amount of light required to give an optical density of +0.2, and the sensitivities of Comparative Examples 11 and 12 are the same as those of Comparative Example 9.
When 100, the present inventions 9, 10, and 11 are Comparative Examples 8, 9, and 10, and the present inventions 12, 13, and 14 are Comparative Example 8, respectively.
Relative value when 9 and 10 are set to 100. 4) log10 (sensitivity after raw storage / Fresh sensitivity). As in Example 1, it was revealed that the multilayer adsorption system using the dye having the combination of the reduction potentials of the present invention has improved raw preservability as compared with the multilayer adsorption system using the other combination of dyes.

[0319]

From the examples of the present invention, it is possible to obtain a silver halide photographic light-sensitive material excellent in raw preservability in an emulsion sensitized by multilayer adsorption of a sensitizing dye according to the present invention.

Claims (7)

[Claims] 1. A silver halide photographic material having at least one photosensitive silver halide emulsion layer on a support, wherein said emulsion layer contains silver halide grains having a sensitizing dye adsorbed in multiple layers. A silver halide photographic light-sensitive material characterized in that the reduction potential of the first-layer dye of the grains is more noble than the value obtained by subtracting 0.5 V from the reduction potential of the second-layer or higher dye. 2. A dye in which the reduction potential of the first-layer dye is more noble than a value obtained by subtracting 0.2 V from the value of the reduction potential of the second-layer or higher dye, and the reduction potential of the first-layer dye is higher than the second layer 2. The silver halide photographic light-sensitive material according to claim 1, wherein said material is lower than the value of said reduction potential. 3. The light having a maximum spectral absorption wavelength of less than 500 nm and a light absorption intensity of 60 or more, or a maximum spectral absorption wavelength of 500.
3. The silver halide photographic light-sensitive material according to claim 1, which contains silver halide grains having a light absorption intensity of 100 nm or more at nm or more. 4. The maximum value of the spectral absorption by the sensitizing dye is defined as Amax
4. The silver halide photographic light-sensitive material according to claim 1, wherein the wavelength interval between the shortest wavelength and the longest wavelength which indicates 50% of Amax is 120 nm or less. 5. A sensitizing dye having at least one aromatic group or a sensitizing dye having a basic nucleus condensed with three or more rings. The silver halide photographic light-sensitive material as described above. 6. The silver halide emulsion having an aspect ratio of 2
The above tabular grains account for 50% of all silver halide grains in the emulsion.
6. The silver halide photographic light-sensitive material according to claim 1, wherein the emulsion is present in an amount of at least% (area). 7. The method according to claim 1, wherein both the first-layer dye and the second-layer dye exhibit J-band absorption.
7. The silver halide photographic light-sensitive material according to 5 or 6.