JP2001343720A - Silver halide photographic emulsion and silver halide photographic sensitive material using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material having high sensitivity and high image quality. SOLUTION: The silver halide photographic sensitive material contains one or more methine compounds, each having a covalent bond with an inorganic material or is in a gel state.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[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, a sensitizing dye adsorbed on the surface of a silver halide grain absorbs light incident on a photographic material, and transmits light energy to the silver halide grain, thereby obtaining 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).
In Engineering, Vol. 20, No. 3, 97th Contribution (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, incorporated multiple dyes onto silver halide in multiple
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), 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.

A so-called linked dye having two chromophores that are not separately conjugated but linked by a covalent bond is described, for example, in US Pat. Nos. 2,393,351 and 2,42.
5,772, 2,518,732, 2,52
1,944, 2,592,196, European Patent 56
No. 5,083 and the like. However, these were not aimed at improving the light absorption rate. GB Bird (A.B.Bird) and A.L.Bolor (A.A.
L. Borrr et al., In U.S. Pat. Nos. 3,622,317 and 3,976,493, increase the light absorptivity by adsorbing linked sensitizing dye molecules having a plurality of cyanine chromophores and contribute to energy transfer. Sensitized. Ukai, Okazaki and Sugimoto disclose in JP-A-64-91134, at least one of a substantially non-adsorbing cyanine, merocyanine and hemicyanine dye containing at least two sulfo groups and / or carboxyl groups.
It has been proposed to couple to spectral sensitizing dyes that can be adsorbed on silver halide.

In addition, 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 linking dye of monomethine cyanine and pentamethine oxonol has red sensitivity. In this case, there is no overlap between the oxonol emission and the absorption of cyanine. -Spectral sensitization by migration does not occur, and high sensitivity cannot be expected due to the condensing action of the linked oxonol.

Also, Richard Parton et al., EP 0 885 964 A1, EP 0 885 965 A1,
European Patent 0985966A1, European Patent 0985867
In A1, a multilayer dye is adsorbed by a combination of a cationic dye and an anionic dye,
An attempt was made to increase the sensitivity by transferring energy to the layer dye.

However, in these methods, the degree to which the sensitizing dye is adsorbed in multiple layers on the surface of the silver halide grains is actually insufficient, and the light absorption per unit grain surface area of the silver halide grains must be sufficiently increased. At present, it is not possible to achieve high sensitivity. For this reason, it has been required to realize a substantially effective multilayer adsorption.

[0009]

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

[0010]

The object of the present invention has been found to be achieved by the following (1) to (20).

(1) A silver halide photographic emulsion comprising at least one methine compound having a covalent bond with an inorganic substance. (2) The silver halide photographic emulsion according to (1), wherein the methine compound is in a gel form. (3) The covalent bond with the inorganic substance according to (1), wherein the covalent bond is -O-Si-O-, -O-Al-O-, or -O-Ti-O-. The silver halide photographic emulsion according to (1). (4) In the covalent bond with the inorganic substance according to (1), the covalent bond is -O-Si-O-, -O-Al-O-, or -O-Ti-O-, and the methine compound Is a gel-like emulsion. (5) A silver halide photographic emulsion comprising at least one gel matrix in which at least one methine compound is present. (6) The silver halide photographic emulsion according to (5), wherein the gel matrix according to (5) is SiO ₂ or Al ₂ O ₃ . (7) The silver halide photographic emulsion according to any one of (1) to (6), wherein the sensitizing dye is adsorbed in multiple layers on the surface of the silver halide grain. The silver halide photographic emulsion according to any one of (1) to (6). (8) In the silver halide photographic emulsion according to (7),
The silver halide photographic emulsion has a spectral absorption maximum wavelength of 500 n.
The silver halide photographic emulsion according to (7), comprising silver halide grains having a light absorption intensity of less than m 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. (9) In the silver halide photographic emulsion according to (7) or (8), when the maximum value of the spectral absorption by the sensitizing dye of the emulsion is defined as Amax, the shortest wavelength and the longest wavelength exhibiting 50% of Amax. The silver halide photographic emulsion according to (7) or (8), wherein the wavelength interval of the wavelength is 120 nm or less. (10) In the silver halide photographic emulsion according to (7), (8) or (9), the longest wavelength having a spectral sensitivity of 50% of Smax is from 460 nm to 510 nm or 560.
nm to 610 nm, or 640 nm to 730 nm
The silver halide photographic emulsion according to (7), (8) or (9), wherein (11) In the silver halide grains of the silver halide photographic emulsion according to any one of (7) to (10), the excitation energy of the sensitizing dye in the second and subsequent layers is changed to the dye in the first layer, and the efficiency is 1
Characterized by energy transfer at 0% or more (7)
The silver halide photographic emulsion according to any one of (1) to (10). (12) In the silver halide grains of the silver halide photographic emulsion according to any one of (7) to (11), both the sensitizing dye in the first layer and the sensitizing dye in the second and subsequent layers exhibit J band absorption. The silver halide photographic emulsion according to any one of (7) to (11), wherein (13) The emulsion according to any one of (7) to (12), wherein the emulsion contains a methine compound having at least one aromatic group. 2. The silver halide photographic emulsion described in 1. above. (14) The silver halide photographic emulsion according to any one of (1) to (13), wherein tabular grains having an aspect ratio of 2 or more are present in 50% or more (area) of all silver halide grains in the emulsion. The silver halide photographic emulsion according to any one of (1) to (13), wherein (15) The silver halide photographic emulsion according to any one of (1) to (14), wherein the photographic emulsion according to any one of (1) to (14) is selenium-sensitized. Photographic emulsion. (16) The silver halide photographic emulsion according to any one of (1) to (15), further comprising a silver halide-adsorbing compound other than the methine compound.
A photographic silver halide emulsion according to any one of the above. (17) A silver halide photographic light-sensitive material comprising at least one layer of the silver halide photographic emulsion according to any one of (1) to (16).

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The present invention is characterized by containing at least one methine compound having a covalent bond with an inorganic substance. The term “inorganic” refers to all remaining elements except hydrogen, carbon, oxygen, nitrogen, sulfur, phosphorus, chlorine, bromine, and iodine from all elements described in the periodic table of elements. Preferred are silicon, aluminum and titanium, and particularly preferred are silicon and titanium. The covalent bond with the inorganic substance is -O
It is preferably -Si-O-, -O-Al-O-, or -O-Ti-O-. More preferably, it is -O-Si-O- or -O-Ti-O-, and particularly preferably -O-Si-O-. In the present invention,
The methine compound is in a gel state. Gel means a colloidal system consisting of two phases, solid and liquid. For details on organic gels, see Quarterly Review of Chemistry, Organic Polymer Gels, edited by The Chemical Society of Japan, Kagaku Shuppan Center, 1990, by Shio Sakuhana, application of the sol-gel method (optical, electronic, chemical, biofunctional materials) Agne Shofusha, 1997, Chemi
cal Reviews, 95, 399-438 (19)
95) (especially at page 433), Li Dequan, M .;
A. Ratner, T .; J. Marks, J.M. Am. C
hem. Soc. , 112, 7389 (1990), Ken Matsuoka, "Chemistry and Application of Dyes", Dainippon Books Co., Ltd., (1)
994). As a method of synthesizing a methine compound in a gel state, a method of bonding organic molecules to inorganic silica or silicate glass, a method of using alkyl or arylalkoxysilane as a raw material, and a method of using polydimethylsiloxane (PDMS) as a raw material Method, a method using an alkoxysilane or a similar compound containing Si and an alkoxyl group as a raw material,
A method of reacting an organic polymer or oligomer with an inorganic substance, a method of polymerizing an organic monomer during a gelation reaction and bonding the same to an inorganic substance, an inorganic portion using a complex-forming ligand (such as -Ti-O-Ti-O-) And a method of introducing an organic substance into an inorganic gel to form a bond between the two. As a specific method of each,
The following documents and reports are listed. ... Sakuo Sakuhana, Application of Ceramics to Immobilized Enzyme Carrier, Chemical Apparatus, Vol. 25, pp. 52-58, 1983, R.
D. Mason et al., Biotech. Bioeng., 14, 637
645 pages, 1972… P. Innocenzi, SPIE, vol.2288, Sol-Gel Optics I
II, pp. 87-95, 1994… JD Mackenzie et al., J. Sol-Gel Sci. Tec
h., 7, 151-161, 1996… L. Hou et al., J. Sol-Gel Sci. Tech., 2, 6
35-639, 1994… A. Morikawa et al., J. Mater. Chem.
9 pages, 1992… ABWojcik et al., J. Sol-Gel Sci. Tech., 5
Vol. 77-82, 1995… M. In et al., J. Sol-Gel Sci. Tech.
01-114, 1997… LC Klein et al., Polym. Prep .., 32,
519, 1991, preferably. Particularly preferred is the following method. In the present invention, the methine compound does not become a gel, and the methine compound may be contained in the gel matrix. As a gel matrix, for example,
Saio Sakuhana, Application of the sol-gel method (light, electron, chemistry, low-temperature synthesis of biofunctional materials), Agne Shofusha, 1997, quarterly chemistry review, organic polymer gel, edited by The Chemical Society of Japan, Society Publishing Center, 1990. Preferably, it is a gel matrix composed of silica (SiO ₂ ) gel or alumina (Al ₂ O ₃ ) gel. As a method of filling a methine compound in the pores of silica gel, for example, J.
N. Nogue et al J. Amer. Ceram. Soc. 71, 1159-1163
1988. At the same time, a method of forming a gel matrix in a solution containing a methine compound can also be applied. As a specific method, for example, the method of Reisfeld in which rhodamine 6G is introduced into silica (J. Non-Cryst. Solids, Vol. 121, 254-26)
6, p. 6, 1990), method of Suratwala in which coumarin dye was introduced into SiO ₂ -PDMS (J. Sol-Gel Sci. Tech., 7).
Vol. 151-161 (1996)) and the method of Shibata in which rhodamine 6G is introduced into a gel composed of aryl siloxane (Industrial Materials, Vol. 46, p. 37, 1998).

In the silver halide emulsion of the present invention, it is preferable that the sensitizing dye is adsorbed on the silver halide grains in multiple layers. Further, the adsorption energy of the sensitizing dye in the second and subsequent layers is preferably 10 kJ / mol or more. Also,
It is preferable that the second-layer dye exists in a layered state. It is particularly preferable to form a J-aggregate described below.

The presence state of the sensitizing dye in the second and subsequent layers may be observed by any method, but preferably, microspectroscopy, STM, AFM, near-field optical microscopy, cathodoluminescence, Fluorescence microscopy, imaging SIMS
, SEM and TEM methods.

Whether or not the dye adsorbed in multiple layers is layered adsorption is judged by the number of adsorbed dye layers formed on the surface of the silver halide grains or by the presence or absence of a change in the amount of dye depending on the location (site). it can. In the present invention, if the variation of the number of adsorbed dye layers or the amount of the dye due to the place (site) is within 5 times the variation of monolayer adsorption, it is regarded as laminar adsorption. Naturally, the smaller the fluctuation, the more preferable the laminar adsorption. The variation can be represented by the number of adsorbed dye layers for each location (site) on the surface of the silver halide grains, or the standard deviation or variation coefficient (standard deviation / average) of the dye amount. Using the measurement method for observing the presence state of the sensitizing dye described above, the number of adsorbed dye layers for each location (site) on the particle surface,
Alternatively, since the amount of the dye can be quantified, the layered adsorption can be determined by examining the variation.

The sensitizing dye in the first layer is preferably present in a layered state. In general, the interaction between the silver halide grains and the sensitizing dye in the first layer is strong, so that the first layer often grows in a layer form and exists in a layer state.

Any interaction may be used as a basis for the adsorption energy (ΔG) of the sensitizing dye. For example, van der Waa may be used.
ls) force (more specifically, it is divided into an orientation force acting between a permanent dipole and a permanent dipole, an induction force acting between a permanent dipole and an induced dipole, and a dispersion force acting between a temporary dipole and an induced dipole. ), Charge transfer force (CT), Coulomb force (electrostatic force), hydrophobic bonding force, hydrogen bonding force, covalent bonding force (chemical bonding force), coordination bonding force, and the like. One of these bonding forces can be used, or a plurality of arbitrary bonding forces can be used. (One of the requirements of the present invention, the adsorption energy of the sensitizing dye of the second and subsequent layers is 10
When a description of kJ / mol or more is made, the common bonding force is not considered as described above. )

Preferably, van der Waals force,
Charge transfer force, Coulomb force, hydrophobic bond force, hydrogen bond force, coordination bond force, more preferably van der Waals force, charge transfer force (CT), Coulomb force, hydrophobic bond force, hydrogen bond force And more preferably van der Waals force, charge transfer force (CT) and Coulomb force, particularly preferably van der Waals force and Coulomb force, and most preferably van der Waals force. is there.

Next, it will be described how the interaction based on the adsorption energy (ΔG) of the sensitizing dyes of the second and subsequent layers works with which dye and at what level of stabilizing energy it is preferable. .

The case of adsorption of two or more R layers will be described. In this case, the stabilization energy of the interaction based on the adsorption energy (ΔG) of the i-th layer dye is the stabilization energy of the interaction between the i-th layer dye and the (i-1) -th layer dye (ΔGi ( i-1)), the stabilization energy (ΔGii) of the interaction between the i-th dye and the i-th dye, and the stabilization energy (ΔGi) of the interaction between the i-th dye and the (i + 1) th dye.
Gi (i + 1)). (I is 2 or more) At this time, the following 1, 2, and 3 are preferable. Note that i
If = R (ie, the top layer), there is no interaction of ΔGi (i + 1).

1, ΔGi (i−1)> (Xi (i−
1)) kJ / mol and / or ΔGii> (Xi
i) kJ / mol and / or ΔGi (i + 1)>
(Xi (i + 1)) kJ / mol2, ΔGi (i-1)
> (Xi (i-1)) kJ / mol and ΔGii>
(Xii) kJ / mol and ΔGi (i + 1)>
(Xi (i + 1)) kJ / mol At 3, 1, and 2, ΔGi (i−1)> ΔGi
i, ΔGi (i + 1)> ΔGii

Xi (i-1), Xii, and Xi (i +
The value of 1) is 5, 10, 15, 20, 25, 30, 3
5,40,45,50,55,60,65,70,7
5, 80 are preferred.

The i-th layer dye and the (i-2) -th layer dye,
There are interactions between the i-th layer dye and the (i + 2) -th layer dye, and the i-th layer dye and silver halide grains, but they can be neglected because they are long-range interactions.

As described above, the dye adsorption energy (Δ
G) and the stabilization energy of the underlying interaction may be measured by any method.

For example, dye adsorption energy (ΔG)
Is determined thermodynamically by a method using a pigment desorbing agent described below (the method using a pigment desorbing agent is described in a report by Asanuma et al. (Journal of Physical Chemistry B (Jo)
urnal of Physical Chemist
ry B) Vol. 101, pp. 2149 to 2153 (19
1997)). ), A method of determining from the adsorption isotherm by a method of determining the amount of dye adsorption described later (for example, Journal of Physical Chemistry (Jou, W. West, et al.)
rnal of Physical Chemistr
y) Volume 56, p. 1054 (1952); G
unther, E .; Moisar, J .; Photog
r. Sci. , 13, 280 (1965); Tan
i, S. Kikuchi, Bull. Soc. Sci.
Photogr. Japan, No. 17, 1 (196
7), ibid. , 18, 1 (1968); Pho
togr. Sci. , 17, 22 (1969), etc., but it is useful to dissolve the precipitated silver halide grains and measure the amount of dye adsorption as described later. ), A method using a calorimeter (for example,
W. Gardner, A .; Herz, 49th Nat
ionical Colloid Symposium, A
m. Chem. Soc. , June, 1975. Sub
Mitted to Photogr. Sci. En
g. , Asanuma et al., Journal of Physical Chemistry B (Journal of Physical)
Chemistry B), Vol. 101, pages 2149 to 2153 (1997)). It is also possible to use computational chemistry such as molecular orbital calculation and molecular force field calculation.

The interaction stabilizing energy based on the dye adsorption energy (ΔG) can also be determined by using the above method. For example, in the case of two-layer adsorption, the adsorption energy (ΔG) of the second-layer dye is determined by the above method. Further, the stabilization energy of the interaction between the dyes in the second layer is determined. As the method, experimentally, for example, the method of Matsubara and Tanaka et al.
5 1989). For example, in a gelatin solution in which only silver halide grains are removed from the emulsion to be used, the absorption change due to the association between the dyes in the second layer when the dye in the second layer is changed to various concentrations at various temperatures. Stabilization energy can be determined. It is also possible to use computational chemistry such as molecular orbital calculation and molecular force field calculation.

At this time, (adsorption energy (ΔG) of second-layer dye) = (stabilization energy of interaction between first-layer dye and second-layer dye) + (stabilization of interaction between second-layer dye) From the equation (energy), (the stabilization energy of the interaction between the first-layer dye and the second-layer dye) can be determined.

In the case of three-layer adsorption, the adsorption energy (ΔG) of the dye in the third layer and the stabilization energy of the underlying interaction can be determined in the same manner as in the second layer. At this time, (the adsorption energy (Δ
G)) = (Stabilization energy of interaction between first-layer dye and second-layer dye) + (stabilization energy of interaction between second-layer dye) + (interaction between second-layer dye and third-layer dye) (Stabilizing energy of action), (stabilizing energy of interaction between second-layer dye and third-layer dye) is the same as (stabilizing energy of interaction between third-layer dye and second-layer dye). Because there is, you can find all.

In the case of four-layer adsorption or more, all can be obtained in the same manner.

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 grains having a particle diameter of less than nm, it is preferable that the silver halide grains having a light absorption intensity of 60 or more include at least 1/2 of the total projected area of the silver halide grains. 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, Yamashita et al.
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 x A x 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.

As a method of increasing the light absorption intensity, a method of adsorbing more than one layer of the dye chromophore on the particle surface, a method of increasing the molecular extinction coefficient of the dye, or a method of reducing the dye occupied area are available. Yes, any method may be used, but a method is preferred in which more than one layer of the dye chromophore is adsorbed on the particle surface. Here, the state where more than one layer of the dye chromophore is adsorbed on the grain surface means that more than one layer of the dye bound in the vicinity of the silver halide grain exists, and the dye existing in the dispersion medium Not included. Also, even when the dye chromophore is covalently linked to the substance adsorbed on the particle surface, the linking group is very long and increases the light absorption intensity when the dye chromophore is present in the dispersion medium. The effect is small and is not considered as more than one layer of adsorption. In so-called multilayer adsorption, in which more than one layer of a dye chromophore is adsorbed on the 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 dye not directly adsorbed to the particles to the dye directly adsorbed to 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 Products".
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 the general formulas described in 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 to 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 where more than one layer of the chromophore is adsorbed on the surface of the silver halide grain means that the dye occupying the smallest area on the surface of the silver halide grain among the sensitizing dyes added to the emulsion. The saturated adsorption amount per unit surface area reached by the above is defined as a one-layer saturated coating amount, and the amount of adsorption per unit area of the dye chromophore is larger than the one-layer saturated coating amount. The number of adsorbed layers means the amount of adsorption based on the one-layer saturated coverage. 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 showing 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. Hertz.
z) et al.'s Adsorption from Aqua Aquas solution
eous Solution) Advances Inn
Chemistry Series (Advances in C
hemistry Series) No. 17,173
Page (1968) and the like.

The amount of the sensitizing dye adsorbed on the emulsion particles was determined by separating the emulsion adsorbed with the dye into a centrifugal separator to separate the emulsion particles and the supernatant gelatin aqueous 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 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) can be referred to. 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. As a method for taking a transmission electron microscope photograph, for example, “Electron Microscope Sample Techniques” edited by Kanto Chapter of the Electron Microscope Society of Japan, Seibodo 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. Sauvenie
r) Editing, E. Klein et al. International Colloquium (International)
al Coloquium), Liege (Lieg)
e), 1959, "Scientific Photograph.
hy)). 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 in multiple layers on the silver halide grains, the so-called first-layer dye chromophore directly adsorbed on the silver halide grains and the dye in the second or more layers The reduction potential and oxidation potential of the chromophore may be any, but the reduction potential of the dye chromophore of the first layer is 2 or less.
It is preferable that the noble metal is nobler than the value obtained by subtracting 0.2 v from the value of the reduction potential of the dye chromophore of the layer or higher.

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).

The dye chromophore of the second or higher layer 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 described, for example, in Mitsuo Maeda, Laser Research, Vol. 8, pp. 694, 803, 958 (1980) and Vol. 9, 85 (1981), and F. Sehaefer.
Author, "Dye Lasers", Springer (1973).

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 chromophore of the second layer or more also forms a J-aggregate. 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. Here, the excitation energy of the second-layer dye refers to the energy of the dye in the excited state generated by absorbing the light energy of the second-layer dye. When the excitation energy of a certain molecule is transferred to another molecule, an excited electron transfer mechanism, a Forster type energy transfer mechanism (Fo)
It is considered that the excitation energy is transferred via an Rster Model), a Dexter energy transfer mechanism (Dextor Model), or the like. Therefore, even in the multilayer adsorption system of this study, it is necessary to cause efficient excitation energy transfer considered from these mechanisms. Preferably, the condition is satisfied. Furthermore, it is particularly preferable to satisfy the conditions for causing a Forster type energy transfer mechanism. In order to increase the energy transfer efficiency of the Forster type, it is also effective to lower the refractive index near the emulsion grain surface. 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 to which a dye chromophore is linked by a covalent bond, the dye occupied area of each dye in an unlinked state is used as a reference. 80 for simplicity
Å ² . Single layer saturated coating amount: Dye adsorption amount 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.

The shortest showing 50% each of the maximum value Amax of the spectral absorption by the sensitizing dye and the maximum value Smax of the spectral sensitivity of an emulsion containing silver halide photographic emulsion grains having a light absorption intensity of 60 or 100 or more. 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.

The spectral absorption maximum wavelength is less than 500 nm and the light absorption intensity is 60 or more, or 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 and a light absorption intensity of 100 or more is a method using the following specific dye.

For example, JP-A-10-239789, JP-A-8
-269,092 and 10-123650, JP-A-8-
Dyes having an aromatic group described in 328189;
A method using a combination of a cationic dye having an aromatic group and an anionic dye; a method using a dye having a multivalent charge described in JP-A-10-171588;
A method using a dye having a pyridinium group described in No. 4774, a method using a dye having a hydrophobic group described in JP-A-10-186559,
197980, a method using a dye having a coordination bonding group, and Japanese Patent Application Nos. 11-63588 and 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 a group having a polycyclic fused ring in which a hydrocarbon aromatic ring and a heteroaromatic ring are fused together, or a polycyclic fused ring structure in which an aromatic hydrocarbon ring and an aromatic heterocycle 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 described 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, and nonionic methine compounds represented by the following general formula (I). (2) A method of simultaneously using at least one of the cationic methine compounds (methine dyes) represented by the following general formula (I) and at least one of the anionic methine compounds represented by the following general formula (II) . General formula (I)

[0057]

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In the formula, Z ₁ represents an atomic 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 the general formula (I) to form a methine compound. 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 have a substituent in which the methine compound represented by the general formula (I) as a whole becomes a cationic dye, a betaine dye, or a nonionic dye.
However, when the general formula (I) is a cyanine dye or rhodacyanine dye, it preferably has a substituent serving as 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)

[0059]

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In the formula, Z ₂ represents an atom 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 compound. L ₃ and L ₄
Represents 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 compound represented by the general formula (II) as a whole becomes an anionic dye. M ₂ represents a counter ion for charge balancing, and m ₂ represents a number of 0 or more necessary to neutralize the 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.

In the case of the methine compound capable of forming a gel according to the present invention, the methine compound preferably has a reactive group capable of reacting with an inorganic substance as a substituent. Examples of such a reactive group include a hydroxy group, an amino group, a carboxy group, a carbonyl group, a thiol group, and a phosphate group. Preferably, they are a hydroxy group, an amino group, and a carboxy group.
The number of reactive groups may be any, but is preferably 1 or more and 10 or less, and particularly preferably 2 or more and 5 or less.
It is as follows.

The cationic dye referred to in the present invention may be any dye having a cationic charge except for a counter ion, but is preferably a dye having no anionic substituent. The anionic dye of the present invention may be any dye as long as the dye has an anionic charge excluding the counter ion.
It is a dye that has more than one. The betaine dye of the present invention is a dye that has an electric charge in a molecule but forms an intramolecular salt, and the molecule as a whole has no electric charge. The nonionic dye of the present invention is a dye having no charge in the molecule.

The term “anionic substituent” as used herein refers to a substituent having a negative charge, and includes, 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., these pka And a group at which the proton is dissociated depending on the surrounding pH. More preferably a sulfo group, a carboxyl group, -CONHSO ₂ - group, -CON
HCO- group, -SO ₂ NHSO ₂ - a group. Note that-
CONHSO ₂ — group, —CONHCO— group, —SO ₂ N
The HSO ₂ — group, due to these pka and surrounding pH,
In some cases, the proton does not dissociate, and in this case, it is not included in the anionic substituent described herein. That is, when the proton does not dissociate, for example, the general formula (I-1)
Even if two of these groups are substituted for the dye represented by the formula (2), it can be regarded as a cationic dye.

[0066] In the present invention, -CONHSO ₂ protons undissociated - group, -CONHCO- group, or -SO ₂ NHSO ₂ - If group, a contains at least one having a sensitizing dye is particularly preferred. More preferably, the aromatic group is substituted with these groups via a single bond or a linking group having 1 to 4 carbon atoms. These dyes are described in Japanese Patent Application No. 11-331571.

Examples of the cationic substituent include a substituted or unsubstituted ammonium group and a pyridinium group.

Examples of the methine compound capable of forming a gel include:
As the substituent, 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)

[0069]

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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 represent 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 are 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 , L _{5 to} L ₁₁ are
When (I-1) is a cationic dye, it has no anionic substituent, and when (I-1) is a betaine dye, it has one anionic substituent. General formula (I-2)

[0071]

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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 to form a heterocyclic or acyclic acidic terminal group together with (NR ₆ ) q ₁ . However, a ring may be condensed with Z ₅ , and Z ₆ and Z ₆ ′. R ₅ and R ₆ are 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, Z 6 ', L 12 ~
L ₁₅ has a cationic substituent when (I-2) is a cationic dye, and has one cationic substituent and one anionic substituent when (I-2) is a betaine dye; When I-2) is a nonionic dye, it has neither a cationic substituent nor an anionic substituent. General formula (I-3)

[0073]

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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 represent 0, 1, 2, 3 or 4. Z ₇ and Z ₉ represent an atomic group necessary for forming a nitrogen-containing heterocyclic ring. Z ₈ and Z ₈ ′ represent a group of atoms necessary for forming a heterocyclic ring together with (N—R ₈ ) q ₂ . Where Z
₇ , Z ₈ , Z ₈ ′, and Z ₉ may have a condensed ring. R ₇ , R ₈ and R ₉ are 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 ₈ ′, Z
₉ , L _{16 to} L ₂₄ have no anionic substituent when (I-3) is a cationic dye, and have one anionic substituent when (I-3) is a betaine dye.

Further, as the anionic dye represented by the general formula (II), more preferably, the following general formula (II-1):
This is the time represented by (II-2) and (II-3). General formula (II-1)

[0076]

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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 are 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 ₁₁ have an anionic substituent.

Formula (II-2)

[0079]

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In the formula (II-2), L ₃₂ , L ₃₃ , L ₃₄ and L
₃₅ represents a methine group. p ₉ represents 0 or 1. q ₃ 0
Or represents 1. n ₆ represents 0, 1, 2, 3, or 4. Z
₁₂ represents an atomic group necessary for forming a nitrogen-containing heterocyclic ring. Z ₁₃ and Z ₁₃ ′ represent atoms necessary for forming a heterocyclic or acyclic acidic terminal group together with (N—R ₁₃ ) q ₃ . However, a ring may be condensed to Z ₁₂ and Z ₁₃ and Z ₁₃ ′. R ₁₂ and R ₁₃ represent an alkyl group, an aryl group, or a heterocyclic group. M ₂ and m ₂ are represented by the general formula (I
Synonymous with I). However, at least one of R ₁₂ and R ₁₃ has an anionic substituent. General formula (II-3)

[0081]

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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 represent 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 atomic group necessary for forming a nitrogen-containing heterocyclic ring. Z ₁₅ and Z ₁₅ ′ represent an atom 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) Represents R _{3 to} R ₉ , and R ₁₀ to
At least one of R ₁₆ is a group having an aromatic ring, preferably two are groups having an aromatic ring, more preferably three are groups having an aromatic ring, and particularly preferably four The above is the 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 on the long wavelength side of the dye adsorbed on the second layer or more has It is defined as not more than twice the absorption width on 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 exhibits an absorption of 1/2 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 of the second layer or more 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. The method using a pigment desorbing agent
Report of Asanuma et al. (Journal of Physical Chemistry B)
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 dyes of the general formula (I) or (I)
The dye represented by I), more preferably the dye represented by the general formula (I). As the second layer dye, it is preferable to use a cationic dye, a betaine dye, or a nonionic dye of the general formula (I) alone. When 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 them 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.

Here, 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, Naft [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 fused ring heterocycle, 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 fused 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, Indro [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 and 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 preferred method of realizing an adsorption state in which a dye chromophore covers the surface of a silver halide grain in a multi-layer 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 (referred to as a linked dye in the present invention). 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 preferably, cyanine dyes, merocyanine dyes, rhodacyanine dyes, oxonol dyes, particularly preferably cyanine dyes, rhodacyanine dyes,
Merocyanine dyes, most preferably cyanine dyes.

However, in the present invention, 1
It is more preferable to use the other sensitizing dyes described above than to use a sensitizing dye in which the sensitizing dye of the layer and the sensitizing dyes of the second and subsequent layers are connected by a covalent bond.

Preferable examples include, 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 JP-A-10-30735.
8, Nos. 10-307359 and 10-310715, the method using a linking dye having a specific structure, and the specific linking groups 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.

Preferred linking dyes are those represented by the following formula (III). General formula (III)

[0097]

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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 required 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. Specifically, those described above for the dye chromophore can be used. Preferably, it is the polymethine dye chromophore represented by the aforementioned dye chromophore. More 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. The general formula of a preferred dye is described in US Pat. No. 5,994,051.
Nos. 32 to 36, and U.S. Pat.
47, 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 to 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, Maeda Mitsuo,
8, 694, 803, 958 (1980) and 9, 85 (1981), and by F. Sehaefer, "Dye Lasers", Springer (197).
3 years).

Further, it is preferable that the maximum absorption wavelength of D _{1 in} the silver halide photographic material is longer than the maximum absorption wavelength of D ₂ . Further, the emission of D ₂ is D ₁
Preferably overlap with the absorption of. 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 value of 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, sulfonamide group, sulfonic acid ester 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. In addition, these linking groups may contain a ring (aromatic or non-aromatic hydrocarbon ring or heterocycle).

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 (eg, phenylene, naphthylene), an alkenylene group having 2 to 10 carbon atoms (eg, for example, ethenylene, propenylene), an alkynylene group having 2 to 10 carbon atoms (eg, 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 interaction include Shammai Spacer (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 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):
It is a time when the methine dye is represented by (V), (VI), or (VII). General formula (IV)

[0113]

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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)

[0115]

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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)

[0117]

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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 atomic 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 fused to 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. General formula (VII)

[0119]

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In the formula (VII), L₆₅, L₆₆, And L₆₇Is meth
Represents a group. q₇ And q₈ Represents 0 or 1. n₁₃Is
Represents 0, 1, 2, 3 or 4. Z_{twenty four}And Z_{twenty four}’Is (N-R
_{twenty four}) Q ₇ Together with and Z_{twenty five}And Z_{twenty five}’Is (N−
R_{twenty five}) Q₈ Together 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 general formulas (IV), (V) and (VI), and 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 D ₂ in the general formula (I)
V) and methine dyes represented by (V), particularly preferably methine dyes 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.

Hereinafter, the general formula (I) (including (I-1,2,3)),
The methine compounds represented by (II) (including (II-1,2,3)), (IV), (V), (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 compound. Although any methine compound can be formed by Q ₁ and Q ₂ , the methine dyes exemplified as the aforementioned dye chromophores can be mentioned.

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, 482-515. 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.
(XI), (XII), and (XIII) in column 2 (however, the number of n12, n15, n17, and n18 is not limited;
Or more integers (preferably 4 or less). In the general formulas (I) and (II), when a cyanine dye or rhodacyanine dye is formed by Q ₁ and Q _2, it can be expressed by the following resonance formula. General formula (I)

[0126]

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Formula (II)

[0128]

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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 10, Z 11,} Z 12, Z 14, Z 16, Z 17, Z 18,
Z ₁₉ , Z ₂₁ , and Z ₂₃ each 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. The ring 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 heterocycle include a thiazoline nucleus, a thiazole nucleus, a benzothiazole nucleus, an oxazoline nucleus, an oxazole nucleus, a benzoxazole nucleus, a 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 (eg, 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, amino group ( Anilino group), an acylamino group, an aminocarbonylamino group,
An alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfamoylamino group, an alkyl and arylsulfonylamino group, a mercapto group, an alkylthio group, an arylthio group, a heterocyclic thio group, a sulfamoyl group, a sulfo group, an alkyl and arylsulfinyl group, Alkyl and arylsulfonyl groups, acyl groups, aryloxycarbonyl groups, alkoxycarbonyl groups,
Examples include carbamoyl, aryl and heterocyclic azo groups, imide groups, phosphino groups, phosphinyl groups, phosphinyloxy groups, phosphinylamino groups, and silyl groups. More specifically, V is a halogen atom (eg,
A fluorine atom, a chlorine atom, a bromine atom, an iodine atom) and an alkyl group [representing a linear, branched, or cyclic substituted or unsubstituted alkyl group; They include an alkyl group (preferably an alkyl group 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 monovalent obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms) For example, bicyclo [1,2,2] heptane-
2-yl, bicyclo [2,2,2] octan-3-yl), and a tricyclo structure having many ring structures. An alkyl group (for example, an alkyl group of an alkylthio group) in the substituents described below represents an alkyl group having such a concept, and further includes an alkenyl group and an alkynyl group. ], An alkenyl group [which represents a linear, branched, or cyclic substituted or unsubstituted alkenyl group.
They are alkenyl groups (preferably having 2 to 30 carbon atoms).
A substituted or unsubstituted alkenyl group such as vinyl,
Allyl, prenyl, geranyl, oleyl), a cycloalkenyl group (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, that is, a monovalent obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms) For example, 2-cyclopenten-1-yl,
2-cyclohexen-1-yl), bicycloalkenyl group (substituted or unsubstituted bicycloalkenyl group, preferably substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, bicycloalkene having one double bond) It is a monovalent group with one hydrogen atom removed.
For example, bicyclo [2,2,1] hept-2-ene-1
-Yl, bicyclo [2,2,2] oct-2-ene-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 having 6 to 30 carbon atoms) Groups such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), heterocyclic groups (preferably 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocycles) A monovalent group obtained by removing one hydrogen atom from a compound, and more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, for example, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group (preferably Alternatively, 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 having 6
To 30 substituted or unsubstituted aryloxy groups, for example, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy), silyloxy group (preferably carbon number A silyloxy group having 3 to 20, for example, trimethylsilyloxy, t-butyldimethylsilyloxy), a heterocyclic oxy group (preferably having 2 to 3 carbon atoms);
0 substituted or unsubstituted heterocyclic oxy group, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), acyloxy group (preferably formyloxy group, substituted or unsubstituted alkyl having 2 to 30 carbon atoms) A carbonyloxy group, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, for example, formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), a carbamoyloxy group (preferably A substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, for example, N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy,
Morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy), alkoxycarbonyloxy group (preferably substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, for example, Methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy), an aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, for example, phenoxy Carbonyloxy, p-
Methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy), amino group (preferably amino group, substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, substituted or unsubstituted having 6 to 30 carbon atoms) Substituted anilino groups, for example, amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino), acylamino group (preferably formylamino group, substituted or unsubstituted alkylcarbonyl having 1 to 30 carbon atoms) An amino group, a 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 substituted or unsubstituted aminocarbonylamino having 1 to 30 carbon atoms, for example, carbamoylamino, N, N
-Dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino), alkoxycarbonylamino group (preferably substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, for example, methoxycarbonylamino, ethoxycarbonylamino , T-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino), an aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, for example, Phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino), a sulfamoylamino group (preferably having 0 to 30 substituted or unsubstituted sulfamoylamino groups, for example, sulfamoylamino, N, N-dimethylaminosulfonylamino, N-
n-octylaminosulfonylamino), alkyl and arylsulfonylamino groups (preferably substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms, for example, methyl Sulfonylamino,
Butylsulfonylamino, phenylsulfonylamino,
2,3,5-trichlorophenylsulfonylamino, p
-Methylphenylsulfonylamino), a mercapto group,
An alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms such as methylthio,
Ethylthio, n-hexadecylthio), an arylthio group (preferably substituted or unsubstituted arylthio having 6 to 30 carbon atoms, for example, phenylthio, p-chlorophenylthio, m-methoxyphenylthio), a heterocyclic thio group (preferably carbon number 2 to 30 substituted or unsubstituted heterocyclic thio groups, 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 substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfinyl having 6 to 30 carbon atoms) Groups such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p
-Methylphenylsulfinyl), alkyl and arylsulfonyl groups (preferably substituted or unsubstituted alkylsulfonyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonyl groups having 6 to 30 carbon atoms, for example, methylsulfonyl, ethylsulfonyl) Phenylsulfonyl, p-methylphenylsulfonyl), an acyl group (preferably a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, A heterocyclic carbonyl group having a substituted or unsubstituted carbon atom having 4 to 30 carbon atoms bonded to a carbonyl group, for example, acetyl, pivaloyl, 2-chloroacetyl, stearoyl,
Benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl), aryloxycarbonyl group (preferably substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, for example, phenoxycarbonyl , O-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl), an alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl , T-butoxycarbonyl, n-octadecyloxycarbonyl), carbamoyl group (preferably 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 having 6 to 30 carbon atoms) A substituted arylazo group, 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 substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, for example, dimethylphosphino, diphenyl Phosphino, methylphenoxyphosphino), phosphinyl group (preferably having 2 to 30 carbon atoms)
A substituted or unsubstituted phosphinyl group such as phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl), a phosphinyloxy group (preferably
A substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, for example, diphenoxyphosphinyloxy,
Dioctyloxyphosphinyloxy), a phosphinylamino group (preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, for example, dimethoxyphosphinylamino, dimethylaminophosphinylamino), Represents a silyl group (preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms, for example, trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl). 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 , 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,
A quinoxaline ring, a quinoxazoline ring, a quinoline ring, a carbazole ring, a phenanthridine ring, an acridine ring, a phenanthroline ring, a thianthrene ring, a chromene ring, a xanthene ring, a phenoxatiin ring, a phenothiazine ring, and a phenazine ring. ) May have a condensed structure.

Among the above functional groups, those having a hydrogen atom may be removed and further substituted with the above group. Examples of such functional groups include alkylcarbonylaminosulfonyl, arylcarbonylaminosulfonyl, alkylsulfonylaminocarbonyl,
An arylsulfonylaminocarbonyl group is exemplified.
Examples include methylsulfonylaminocarbonyl,
p-Methylphenylsulfonylaminocarbonyl, acetylaminosulfonyl and benzoylaminosulfonyl groups.

Preferred examples of the substituent include the above-mentioned alkyl group, aryl group, alkoxy group, halogen atom, aromatic ring condensation, 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 _{(N-R 24) q 7} , and Z ₂₅ and Z
₂₅ ′ and (N—R ₂₅ ) q ₈ together represent an atomic group necessary to form a heterocyclic or acyclic acidic terminal 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 1 3'} ,
Z ₂₀ ′, Z ₂₄ ′, and Z ₂₅ ′ represent the remaining atomic group necessary for forming an acidic nucleus and an acyclic acidic terminal group. When forming an acyclic acidic terminal group, it is preferably a thiocarbonyl group, a carbonyl group, an ester group, an acyl group, a carbamoyl group, a cyano group, a sulfonyl group, or the like.

Q ₁ , q ₃ , q ₅ , q ₇ , and q ₈ are 0 or 1, but preferably 1.

The acidic nucleus and the acyclic acidic terminal group referred to herein are described, for example, in “Theory of the Photographic Process” edited by James (The Theory).
Theory of the Photograph
ic Process) 4th edition, Macmillan Publishing Company, 1
977, 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) composed of carbon, nitrogen and / or chalcogen (typically oxygen, sulfur, selenium and tellurium) atoms. It is more preferable to form 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-1,1dioxide, 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 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₎
q _5, Z ₂₄ and Z ₂₄ 'and _{(N-R 24) q 7} , and Z ₂₅ and Z
Preferably, ₂₅ ′ and (NR ₂₅ ) q ₈ are hydantoin, 2 or 4-thiohydantoin, 2-oxazoline-5-one, 2-thiooxazoline-2,4dione,
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, 2-thiobarbituric acid. Particularly preferred are 2- or 4-thiohydantoin, 2-oxazolin-5-one, rhodanine and barbituric acid.

Z₈ And Z₈’And (N-R₈) q_Two , Z_FifteenAnd 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
₆ And Z ₆’And (N-R₆) q₁ , Z₁₃And Z₁₃’And (N-R
₁₃) 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 Z₆ And Z₆’And (N-R₆) q₁
 , Z₁₃And Z₁₃’And (N-R₁₃) Q_Three , Z₂₀And Z_{Two 0}'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}) Q₈ In the description of the heterocycle
An oxo group or a thioxo group is removed from the acidic nucleus described above.
It is.

More preferably, Z ₆ and Z ₆ ′ and (NR ₆ ) q ₁ , Z ₁₃ and Z ₁₃ ′ and (NR ₁₃ ) q ₃ , Z
₂₀ and Z ₂₀ 'and _{(N-R 20) q 5} , Z 24 and Z _24' and (N-
R ₂₄ ) q ₇ , and an acidic nucleus of Z ₂₅ , Z ₂₅ ′, and (NR ₂₅ ) q ₈ , which is obtained by removing an oxo group or a thioxo group from the acidic nucleus;

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, and 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, but preferably 1.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R
_{7, R 8, R 9,} R 10, R 11, R 12, R 13, R 14,
R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ , R
₂₃ , R ₂₄ and R ₂₅ are an alkyl group, an aryl group and a heterocyclic group, specifically, for example, a carbon atom having 1 to 18, preferably 1 to 7, and particularly preferably 1 to 4 carbon atoms. Substituted alkyl groups (eg, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl), carbon atoms 1 to 1
8, preferably 1 to 7, particularly preferably 1 to 4, substituted alkyl groups, for example, the above-mentioned V-substituted alkyl groups as substituents. Preferably, an aralkyl group (eg, benzyl, 2-phenylethyl), an unsaturated hydrocarbon group (eg, an allyl group), a hydroxyalkyl group (eg, 2-hydroxyethyl, 3-hydroxypropyl), a carboxyalkyl group (eg, 2- Carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, carboxymethyl), alkoxyalkyl group (for example, 2-methoxyethyl, 2- (2-methoxyethoxy) ethyl), aryloxyalkyl group (for example, 2-phenoxyethyl, 2- (1-naphthoxy) ethyl), an alkoxycarbonylalkyl group (eg, ethoxycarbonylmethyl, 2-benzyloxycarbonylethyl),
Aryloxycarbonylalkyl group (eg, 3-phenoxycarbonylpropyl), acyloxyalkyl group (eg, 2-acetyloxyethyl), acylalkyl group (eg, 2-acetylethyl), carbamoylalkyl group (eg, 2-morpholinocarbonylethyl), sulfamoyl Alkyl group (for example, N, N-dimethylsulfamoylmethyl), sulfoalkyl group (for example, 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl,
4-sulfobutyl, 2- [3-sulfopropoxy] ethyl, 2-hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl), sulfoalkenyl group, sulfatoalkyl group (for example, 2-sulfatoethyl group, 3 -Sulfatopropyl, 4-sulfatobutyl), heterocyclic-substituted alkyl groups (eg, 2- (pyrrolidin-2-one-1-yl) ethyl, tetrahydrofurfuryl), alkylsulfonylcarbamoylalkyl groups (eg, methanesulfonylcarbamoylmethyl) Group), an acylcarbamoylalkyl group (for example, acetylcarbamoylmethyl group), a carbamoylalkyl group substituted with -alkylene-Si (OEt) ₃ or the like (an example of alkylene is ethylene or the like);
An acylsulfamoylalkyl group (for example, acetylsulfamoylmethyl group), an alkylsulfonylsulfamoylalkyl group (for example, methanesulfonylsulfamoylmethyl group)}, having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, Preferably, it is an unsubstituted aryl group having 6 to 8 carbon atoms (eg, phenyl group, 1 naphthyl group), 6 to 20 carbon atoms, preferably 6 to 1 carbon atoms.
0, more preferably a substituted aryl group having 6 to 8 carbon atoms (for example, an aryl group substituted by V described above as an example of the substituent. Specifically, a p-methoxyphenyl group, a p-methylphenyl group , A p-chlorophenyl group, etc.), an unsubstituted heterocyclic group having 1 to 20 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 4 to 8 carbon atoms (for example, 2-furyl group, 2-thienyl group,
2-pyridyl group, 3-pyrazolyl, 3-isoxazolyl, 3-isothiazolyl, 2-imidazolyl, 2-oxazolyl, 2-thiazolyl, 2-pyridazyl, 2-pyrimidyl, 3-pyrazyl, 2- (1,3,5-triazolyl),
3- (1,2,4-triazolyl), 5-tetrazolyl), a substituted heterocyclic group having 1 to 20 carbon atoms, preferably 3 to 10 carbon atoms, and more preferably 4 to 8 carbon atoms (for example, as a substituent, And the above-mentioned heterocyclic group substituted by V. Specific examples include a 5-methyl-2-thienyl group and a 4-methoxy-2-pyridyl group.

R ₁ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R
Preferred as ₈ and R ₉ are groups having an aromatic ring. Examples of the aromatic ring include a hydrocarbon aromatic ring and a heteroaromatic ring, and these further include a hydrocarbon aromatic ring,
And a polycyclic fused ring in which heteroaromatic rings are fused with each other, or a polycyclic fused ring in which an aromatic hydrocarbon ring and an aromatic heterocyclic ring are combined, and may be substituted with the aforementioned substituent V or the like. Is also good. As the aromatic ring, those described as examples of the aromatic ring in the above description of the aromatic group are preferred.

The group having an aromatic ring is represented by -Lb-A
It can be represented by ₁ . Here, Lb represents a single bond or a linking group. A ₁ represents an aromatic group. As the linking group for Lb, preferably, the linking group described for La or the like is mentioned. As the aromatic group for A ₁ , those described above as examples of the aromatic group are preferred.

Preferably, the alkyl group having a hydrocarbon aromatic ring is 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 preferably, the above-mentioned alkyl group 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 two 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 preferred.

The group having an aromatic ring is represented by -Lc-A
_Two Can be represented by Here, Lc represents a single bond.
Or a linking group. A_Two Represents 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 preferable that the substituent is substituted.

Preferably, the alkyl group having a hydrocarbon aromatic ring is an aralkyl group substituted with 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 phosphoric acid 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, and particularly preferred are the above-mentioned sulfo group and phosphorus 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 (VI
When the methine dye represented by I) represents the chromophore represented by D ₁ in the general formula (III), R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ , R
_{21, R 22, 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,
Aralkyl groups and aryloxyalkyl groups).

Formula (IV), (V), (VI) or (VI
When the methine dye represented by I) represents the chromophore represented by D ₂ in the general formula (III), R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ , R
_{21, R 22, R 23,} R 24, and examples of preferable substituents represented by R _25, an unsubstituted alkyl group, a substituted alkyl group, more preferably an alkyl group (such as carboxy with an anionic substituent Alkyl group and sulfoalkyl group), and more preferably a sulfoalkyl group.

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 groups 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 Numbers 6 to 20,
Preferably it has 6 to 15 carbon atoms, more preferably 6 carbon atoms.
To 10 aryl groups (e.g., phenyl, o-carboxyphenyl), substituted or unsubstituted 3 to 20 carbon atoms,
Preferably it has 4 to 15 carbon atoms, more preferably 6 carbon atoms.
To 10 heterocyclic groups (eg, N, N-dimethylbarbituric acid group), halogen atoms (eg, chlorine, bromine, iodine, fluorine), having 1 to 15 carbon atoms, preferably 1 carbon atom
To 10, more preferably an alkoxy group having 1 to 5 carbon atoms (eg, methoxy, ethoxy);
Preferably it has 2 to 10 carbon atoms, more preferably 4 carbon atoms.
To 10 amino groups (eg, methylamino, N, N-dimethylamino, N-methyl-N-phenylamino, N-
Methylpiperazino), an alkylthio group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms (eg, methylthio, ethylthio), 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms, and Preferably, an arylthio group having 6 to 10 carbon atoms (eg, phenylthio, p-methylphenylthio) and the like are mentioned.
It may form a ring 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 , N
₇ , N₈ , N₉ , N_Ten, N₁₁, N ₁₂, And n₁₃Each
And independently represents 0, 1, 2, 3 or 4. Preferably
0, 1, 2, 3 and more preferably 0, 1, 2.
And particularly preferably 0 and 1. n₁ , N_Two , N_Three ,
n_Four , N_Five , N₆ , N₇ , N₈ , N₉ , N_Ten, N₁₁, N
₁₂, And n₁₃Is greater than 2, the methine group is repeated
It need not be the same.

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 represent 0 or 1. Preferably it is 0.

M ₁ , M ₂ , M ₃ , M ₄ , M ₅ , M ₆ , and M ₇ indicate the presence of a cation or an anion when necessary to neutralize the ionic charge of the dye. Because it is included in the formula. Typical cations include inorganic cations such as hydrogen ion (H ⁺ ), 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] -7-undecenium ion). The anion may be either an inorganic anion or an organic anion, such as 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-toluene ion). 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, trifluoromethanesulfonate ion. 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 described as CO ₂ H and SO ₃ H.

M ₁ , m ₂ , m ₃ , m ₄ , m ₅ , m ₆ , and m ₇ represent a number of 0 or more necessary to balance the electric charge, preferably a number of 0 to 4, More preferably, 0
It is a number of １1 and is 0 when a salt is formed in the molecule.

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

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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 above-mentioned sensitizing dyes but also other sensitizing dyes may be further 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.S.
turmer), Heterocyclic Compounds-Special topics in Heterocyclic Compounds-Special topics in Heterocyclic Compounds-Special topics in
heterocyclic chemistry ", Chapter 18, Section 14, 482-515. Preferred dyes include U.S. Patent No. 5,994,051 32-
No. 44, and U.S. Pat. No. 5,747,236, No. 3,
The sensitizing dyes are shown by the general formulas described on pages 0 to 39 and the specific examples. The general formulas of preferred cyanine dyes, merocyanine dyes and rhodacyanine dyes are described in U.S. Pat. No. 5,340,694, columns 21 to 22, (XI) and (X).
II) and (XIII) (where n12, n1
The number of 5, 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 sensitizing dyes may be used, and a combination of sensitizing dyes is often used particularly for supersensitization. Representative examples are U.S. Pat. Nos. 2,688,545 and 2,977,229.
No. 3,397,060 and 3,522,052
No. 3,527,641, No.3,617,293
No. 3,628,964 and 3,666,480
Nos. 3,672,898 and 3,679,428
Nos. 3,303,377 and 3,769,301
No. 3,814,609 and 3,837,862
No. 4,026,707, British Patent 1,344,2
No. 81, No. 1, 507, 803, JP-B-43-493
No. 36, No. 53-12375, JP-A-52-1106
No. 18, No. 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 spectral sensitization in 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 patents is preferred for the use thereof.

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, U.S. 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, any time during or immediately before chemical ripening, during a process, or after chemical ripening and before coating, the emulsion may be added at any time before the coating. 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.

The sensitizing dye of the present invention (the same applies to other sensitizing dyes and supersensitizers) can be directly dispersed in an emulsion. These can be first dissolved in an appropriate solvent, for example, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine or a mixed solvent thereof, and added to the emulsion in the form of a solution. At this time, additives such as a base, an acid and a surfactant can be coexisted. Also, ultrasonic waves can be used for dissolution. As a method for adding this compound, as described in US Pat. No. 3,469,987, the compound is dissolved in a volatile organic solvent, and the solution is dispersed in a hydrophilic colloid. As described in JP-B-46-24185, and a method of dispersing in a water-soluble solvent and adding this dispersion to the emulsion, described in U.S. Pat. No. 3,822,135. A method of dissolving the compound in a surfactant and adding the solution to the emulsion, and dissolving using a compound that causes a red shift as described in JP-A-51-74624, and then adding the solution to the emulsion. For example, as described in JP-A-50-80826, a method of dissolving a compound in an acid substantially free of water and adding the solution to an emulsion is used. In addition, US Pat.
No. 2,343, No. 3,342,605, No. 2,99
Nos. 6,287, 3,429,835 and the like can also be used.

In the present invention, examples of the silver halide-adsorbing compound other than the sensitizing dye (a photographically useful compound adsorbed on silver halide grains) include an anti-fogging agent, a stabilizer, and a nucleating agent. Antifoggants and stabilizers are described in, for example, Research Disclosure Magazine (Research)
Disclosure) Volume 176 Item 17643
(RD17643), Volume 187 of the same Item 18716 (RD18716)
And the compounds described in Item 308119 (RD308119) of Vol. 308 can be used. Examples of the nucleating agent include, for example, U.S. Pat. Nos. 2,563,785 and 2,582.
Hydrazines described in US Pat.
27,552, hydrazides, hydrazones, British Patent 1,283,835, JP-A-52-696.
13, No. 55-138742, No. 60-11837
No. 62-210451, No. 62-291637
No. 3,615,515 and 3,719,49.
4, 3,734, 738, 4,094,683, 4,115,122, 4306016, 44710
Heterocyclic quaternary salt compounds described in US Pat.
Sensitizing dyes having a substituent having a nucleating effect in a dye molecule described in US Pat. No. 4,030,9;
25, 4,031,127, 4,245,037,
4,255,511, 4,266,013, 4,
276, 364, thiourea-linked acylhydrazine-based compounds described in British Patent 2,012,443 and the like, and US Pat. Nos. 4,080,270 and 4,278,748.
Sialhydrazine-based compounds having a thioamide ring or a heterocyclic group such as triazole or tetrazole and the like as described in British Patent 2,011,391B or the like as an adsorptive group are used.

In the present invention, preferred photographically useful compounds include nitrogen-containing heterocyclic compounds such as thiazole and benzotriazole, mercapto compounds, thioether compounds, sulfinic acid compounds, thiosulfonic acid compounds, thioamide compounds, urea compounds, selenourea compounds and the like. It is a thiourea compound, particularly preferably a nitrogen-containing heterocyclic compound, a mercapto compound, a thioether compound and a thiourea compound, and particularly preferably a nitrogen-containing heterocyclic compound. The nitrogen-containing heterocyclic compound has a general formula (C-I)
The nitrogen-containing heterocyclic compound represented by (C-IV) is preferred.

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The compound of the general formula (C-I) is a nitrogen-containing heterocyclic compound containing an imino group (which can be interchangeably isomer) in a heterocyclic ring, and the compound of the general formula (C-II) is A) a nitrogen-containing heterocyclic compound containing a mercapto group, the compound of the general formula (C-III) is a nitrogen-containing heterocyclic compound containing a thione group (which is not interchangeable isomerism), and a compound of the general formula (C-IV) Is a nitrogen-containing heterocyclic compound containing a quaternary ammonium group. They may also be in the form of suitable salts. In the formula, Q ₁ , Q ₂ , Q ₃ , and Q ₄ represent a nitrogen-containing heterocyclic ring, for example, an imidazole ring, a benzoimidazole ring, a naphthimidazole ring, a thiazole ring, a benzothiazole ring, a naphthothiazole ring, an oxazole ring, and a benzoxazole. Ring, naphthoxazole ring, benzoselenazole ring,
Triazole ring, benzotriazole ring, tetrazole ring, azaindene ring (for example, diazaindene ring, triazaindene ring, tetrazaindene ring, pentazaindene ring), purine ring, thiadiazole ring, oxadiazole ring, selenadiazole ring, Examples include an indazole ring, a triazine ring, a pyrazole ring, a pyrimidine ring, a pyridazine ring, a quinoline ring, a rhodanine ring, a thiohydantoin ring, an oxazolidinedione ring, and a phthalazine ring. Among them, preferred are an azaindene ring, a (benzo) triazole ring, an indazole ring, a triazine ring, a purine ring and a tetrazole ring in the general formula (C-I). In the general formula (C-II), Tetrazole ring,
A triazole ring, a (benzo) imidazole ring, a (benzo) thiazole ring, a (benzo) oxazole ring, a thiadiazole ring, an azaindene ring and a pyrimidine ring. In the general formula (C-III), a (benzo) thiazole ring,
A (benzo) imidazole ring, a (benzo) oxazole ring, a triazole ring, a tetrazole ring, and the like. In the general formula (C-IV), a (benzo, naphtho) thiazole ring,
(Benzo, naphtho) imidazole ring and (benzo, naphtho) oxazole ring. The “(benzo, naphtho) thiazole ring” in the above display shall mean “thiazole ring, benzothiazole ring or naphthothiazole ring” (the same applies to other cases). These heterocycles may have a suitable substituent, for example, a hydroxyl group, an alkyl group (such as a methyl group, an ethyl group, or a pentyl group), an alkenyl group (such as an allyl group), and an alkylene group (such as an ethynyl group). ), Aryl groups (phenyl group, naphthyl group, etc.),
Aralkyl groups (such as benzyl groups), amino groups, hydroxyamino groups, alkylamino groups (such as ethylamino groups), dialkylamino groups (such as dimethylamino groups),
Arylamino group (phenylamino group, etc.), acylamino group (acetylamino group, etc.), acyl group (acetyl group, etc.), alkylthio group (methylthio group, etc.), carboxy group, sulfo group, alkoxyl group (ethoxy group, etc.), aryloxy Group (such as a phenoxy group), an alkoxycarbonyl group (such as a methoxycarbonyl group), an optionally substituted carbamoyl group, an optionally substituted sulfamoyl group, an optionally substituted ureido group, a cyano group, and a halogen atom (such as a chlorine atom or a bromine atom) ), A nitro group, a mercapto group, a heterocyclic ring (such as a pyridyl group), and the like. In the formula, R is an alkyl group (eg, methyl group, ethyl group, hexyl group), an alkenyl group (eg, allyl group, 2-butenyl group), an alkylene group (eg, ethynyl group), an aryl group (eg, phenyl group), Aralkyl group (benzyl group, etc.)
And these may further have a suitable substituent. X ^- represents an anion (e.g., an organic anion, such as an inorganic anion or paratoluene sulphonate such as a halogen ion). Preferred among the above compounds are the compounds of the general formulas (CI), (C-II) and (C-IV). Particularly preferred in the general formula (C-I) are tetrazaindenes substituted with a hydroxyl group (which may have an imino group in tautomeric isomerism). In general formula (C-II), it is a mercaptotetrazole having an acidic group (carboxy group, sulfo group). In general formula (C-IV), they are benzothiazoles. Among the above compounds, compounds of the general formulas (CI) and (C-II) combine with silver ions to form a silver salt, and the solubility product of the silver salt in water around room temperature is 10 ^-9 to 10 ^-20 , especially 5 × 10 ^-10 to 1
0 nitrogen-containing heterocyclic compound is ^-18 is preferred.

The photographic useful compound may be added before the sensitizing dye is added, after the end of the addition, or during the period from the start of the addition to the end of the addition. This is the period before the addition of the dye and from the start to the end of the addition, and more preferably the period from the start to the end of the addition of the sensitizing dye. The addition amount of the photographically useful compound varies depending on the function of the additive and the type of emulsion, but typically,
It is 5 × 10 ^{−5 to} 5 × 10 ⁻³ mol / mol Ag.

Next, specific examples of the photographically useful compound which is adsorbable to particles will be shown. Of course, the present invention is not limited to these.

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In the present invention, the photographic emulsion controlling the photosensitive mechanism includes any of silver bromide, silver iodobromide, silver chlorobromide, silver iodide, silver iodochloride, silver iodobromochloride and silver chloride. 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, and rhombohedral, and irregular such as spherical, tabular, etc. It may be one having an (irregular) crystal form, one having a higher-order plane ((hkl) plane), or a mixture of grains of these crystal forms. The particles are described in detail below. See Journal of Imagi for particles with higher planes.
ng Science, Vol. 30 (1986), pages 247 to 254. 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 the case of 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 silver chloride or the (111) flat plate having a high silver chloride content used in the present invention is disclosed in the following patents. 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 silver halide grains having an aspect ratio of 2 or more (preferably 100 or less), preferably 5 or more and 80 or less, more preferably 8 or more and 80 or less are all silver halide grains. 50% (area)
The above emulsion is present, and the tabular grains have a thickness of 0.2
μm, preferably less than 0.1 μm,
More preferably, it is less than 0.07 μm. The following technique 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. In the emulsion of the present invention, silver halide grains containing 10 or more dislocation lines per grain preferably account for 100 to 50% (number) of all grains, more preferably 100 to 70%, and particularly preferably 100 to 100%. Or 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, and various synthetic hydrophilic polymer materials such as polyvinylpyrazole 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 preferably washed with water for desalting and dispersed in a newly prepared protective colloid.
The temperature of water washing can be selected according to the purpose, but is preferably selected in the range of 5 ° C to 50 ° 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. Noodle washing method, dialysis method using semi-permeable membrane,
It can be selected from centrifugation, 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,
Deionization step, chemical sensitization, metal ion salt before coating
It is preferable to perform the above depending on the purpose. Dope particles
In the case of grain formation, modification or chemical sensitization of the grain surface
When used as an agent, add after grain formation and before completion of chemical sensitization
Is preferred. Doping the whole grain and the grain
Dope only the core part or only the shell part
You can also choose the law. 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 are
Ammonium, acetate, nitrate, sulfate, phosphate, hydroxide, etc.
Or a 6-coordinate complex, a 4-coordinate complex, etc.
Any form of salt that can be added can be added. For example,
CdBr_Two , CdCl_Two , Cd (NO_Three)_Two , Pb (NO
_Three)_Two , Pb (CH_Three COO)_Two , K_Three [Fe (CN)
₆ ], (NH_Four)_Four [Fe (CN) ₆ ], K_Three IrCl
₆ , (NH_Four)_Three RhCl₆ , K_Four Ru (CN)₆ Is raised
Can be Halo, aquo, shea as ligands for coordination compounds
, Cyanate, thiocyanate, nitrosyl, thioni
You can choose from trosyl, oxo, and carbonyl
Wear. These may use only one kind of metal compound,
Two or more kinds may be used in combination.

The metal compound is preferably added after being dissolved in water or a suitable organic solvent such as methanol or acetone. In order 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.

In some cases, a method of adding a chalcogen compound during preparation of an emulsion as described in US Pat. No. 3,772,031 is also 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, Macmilllan, 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. Pat. 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 a plurality 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 R ₂ PdX ₆ or R ₂ PdX ₄ . 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_Two PdCl_Four , (NH_Four)_Two 
PdCl₆ , Na_Two PdCl_Four , (NH_Four)_Two PdCl
_Four , Li_Two PdCl_Four , Na_Two PdCl₆ Or K_Two P
dBr _Four Is preferred. Gold and palladium compounds
Is used in combination with thiocyanate or selenocyanate
Is preferred. Hypo and thiourea as sulfur sensitizers
Compound, rhodanine compound and US Patent No. 3,853
No. 7,711, No. 4,266,018 and No.
Sulfur-containing compounds described in 4,054,457
Can be used. In the presence of so-called chemical sensitization aids
Can also be chemically sensitized. Useful chemical sensitizer
For azaindene, azapyridazine and azapyrimidine
Fog in the process of chemical sensitization
Compounds known to be augmented are used. Chemistry
Examples of sensitizing aid modifiers are described in US Pat. No. 2,131,038.
No. 3,411,914, No. 3,554,75
No. 7, JP-A-58-126526 and the aforementioned duffin
"Photographic Emulsion Chemistry", pages 138-143.
You. The emulsion of the present invention is preferably used in combination with gold sensitization.
The preferred amount of the gold sensitizer is 1 per mole of silver halide.
× 10^-Four~ 1 × 10^-7Mole, more preferably
1 × 10^-Five~ 5 × 10^-7Is a mole. Palladium compound
Is preferably 1 × 10^-3From 5 × 10^-7It is. H
Preferred of ocyan compound or selenocyan compound
The range is 5 × 10^-2From 1 × 10^-6It is. Halo of the present invention
The preferred amount of sulfur sensitizer to be used for silver gemide grains is
1 × 10 per mole of silver halide^-Four~ 1 × 10^-7In mole
Yes, more preferably 1 × 10^-Five~ 5 × 10^-7Mole
It is. A preferred sensitizing method for the emulsion of the present invention is
There is Len sensitization. Known instability in selenium sensitization
Using a selenium compound, specifically, a colloidal metal
, Selenoureas (eg, N, N-dimethylselene)
Nourea, N, N-diethylselenourea), selenoketone
Use of selenium compounds such as selenium and selenoamides
Can be. Selenium sensitization is sulfur sensitization or precious metal sensitization
Or it is better to use in combination with both.
is there.

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 an atmosphere of a low pAg of pAg 1 to 7 called silver ripening, and a method of pH 8 to ripening 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 since 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 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. Further, 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 several times as the grains grow, or to add them continuously for a long time.

It is preferable to use an oxidizing agent for silver during the production process of the emulsion of the present invention. The oxidizing agent for silver is
A compound that acts on metallic silver to convert it into silver ions. In particular, a compound that converts extremely fine silver grains by-produced during the formation process of silver halide grains and the chemical sensitization process into silver ions is effective. The silver ion generated here may form a water-insoluble silver salt such as silver halide, silver sulfide or silver selenide, or a water-soluble silver salt such as silver nitrate. May be formed. The oxidizing agent for silver may be inorganic or organic. As the inorganic oxidizing agent, for example, ozone, hydrogen peroxide and its adduct (eg, NaBO ₂
・ H ₂ O ₂ .3H ₂ O, 2NaCO ₃ .3H ₂ O ₂ , N
_{a 4 P 2 O 7 · 2H} 2 O 2, 2Na 2 SO 4 · H 2 O 2
2H ₂ O), peroxy acid salt (for example, K ₂ S ₂ O)
₈ , K ₂ C ₂ O ₆ , K ₂ P ₂ O ₈ ), peroxy complex compounds (for example, K ₂ [Ti (O ₂ ) C ₂ O ₄ ] · 3H ₂
O, 4K ₂ SO ₄ .Ti (O ₂ ) OH.SO ₄ .2H ₂
O, Na ₃ [VO (O ₂ ) (C ₂ H ₄ ) ₂ ] · 6H ₂ O),
Oxygenates such as permanganate (eg, KMnO ₄ ), chromate (eg, K ₂ Cr ₂ O ₇ ), halogen elements such as iodine and bromine, perhalates (eg, periodate) Potassium), salts of higher valent metals (eg, potassium hexacyanoferrate) 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 both methods. 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 may contain a compound other than the above-mentioned silver halide-adsorbing compound for the purpose of preventing fog during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. Can also be included. 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 comprises a support, a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer. 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 photosensitive layer is a unit photosensitive 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 photosensitive 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 silver halide light-sensitive layers and as the uppermost layer and the lowermost layer.

[0215] 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 structure 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 can 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 Japanese Patent No. 6, the 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 the silver halide emulsion layer having the highest sensitivity, the middle layer is the silver halide emulsion layer having a lower sensitivity, and the lower layer is the middle layer. Further, there is an arrangement in which a silver halide emulsion layer having a low sensitivity is arranged 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, the medium-sensitive emulsion layer / The layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer.

In addition, a high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or a low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer may be arranged in this order.

Also, 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).
December 18), 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 page 25 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 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.

Various color couplers can be used in the present invention, 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-based and naphthol-based couplers.
No. 52,212, No. 4,146,396, No. 4,
No. 228,233, No. 4,296,200, No. 2,369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826,
No. 3,772,002 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-
Patents 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 an image-like manner 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 recolor 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 and 24241;
55,477 and the like; 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 (eg, 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 (for example, 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, JP-A-63-257747, and US Pat.
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, for example, in 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).
In addition, the film swelling rate T1 / 2 can be measured according to a method known in the art, for example, Photographic Science and Engineering (Photo) by A. Green et al.
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 color developing solution is processed at 30 ° C. for 3 minutes and 15 seconds, and is 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 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 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-described 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 according to 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 in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution mainly containing an aromatic primary amine-based color developing agent. 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, 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, and 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 process 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 replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per square meter of the photographic material, and is 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also When the replenishment amount is reduced, it is preferable to prevent the 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 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 subsequent 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 of the color development processing is usually set between 2 and 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. Among these, iron (III) aminopolycarboxylate complex salts such as iron (III) complex salt of ethylenediaminetetraacetate and 1,3-diaminopropanetetraacetate complex salt are:
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. 53-95763, 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 for adjusting pH. 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 defective desilvering 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 of strengthening 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 a stirring improving means is effective in any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, 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 disclosed in JP-A-60-191257 and JP-A-60-19.
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 transporting means can significantly reduce the carry-in of the processing solution from the pre-bath to the post-bath, and is highly effective in preventing the performance of the processing solution 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 system 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, for example, benzotriazole, written by Hiroshi Horiguchi "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 temperature and washing time can also be variously set depending on, for example, the characteristics of the photosensitive material and the intended use.
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 treatment may be further performed after the water washing treatment. 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 resulting from 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 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 color developing agents. 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. 15, 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 photographic 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, especially 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, and (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 of 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 (VIII). Formula (VIII) (DYE-Y) n -Z ｛DYE represents a dye group, a temporarily shortened dye group or a dye precursor group, Y represents a simple 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.
Of the Z of the negative dye-releasing redox compound, a particularly preferred group is an N-substituted sulfamoyl group (an example of the N-substituent is a group derived from an aromatic hydrocarbon ring or a hetero ring). The representative groups of Z are exemplified below, but are not limited thereto.

[0277]

Embedded image

For 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.

[0279]

Embedded image

When a compound of this type is used, it is preferable to use it 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.

[0281]

Embedded image

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. , 383, 4,195,992, 4,148,641, 4,148,643 and 4,336,322: JP-A-51-114930,
No. 56-71072: Research Disclosure 1763
No. 0 (1978) and No. 16475 (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 disclosed in JP-A-62-215272, 1
It can be dispersed by the method described on pages 44 to 146. These dispersions are described in JP-A-62-215,272.
No. 137-144.

[0283]

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 Gel 1 Containing Methine Compound No. 3)
14 g of tetraethyl orthosilicate and 10 ml of N, N-dimethylformamide were added to 6 ml of ethanol, and then 1.1 g of the methine compound No. 3 of the present invention was added. Then, 6ml
Of ethanol and 0.7 g of 35% hydrochloric acid, and 7 ml of pure water. The mixture was stirred at 25 degrees for 1 hour to obtain a gel 1 comprising the methine compound No. 3 of the present invention. (Preparation of Gel 2 Containing Methine Compound No. 6)
20 g of polydimethylsiloxane (PDMS) and 10 g of titanium ethoxide (Ti (Oet) 4) were added to 40 ml of ethanol, and then 5 g of the methine compound No. 6 of the present invention was added. Next, 2
0 ml of pure water was added. The mixture was stirred at 60 degrees for 1 hour to obtain a gel 2 comprising the methine compound No. 6 of the present invention. (Preparation of Gel 3 Formed from Methine Compound No. 18) At room temperature, 1.0 g of the methine compound of the present invention (No. 18) and 2 ml of N, N-dimethylformamide were added to 5 ml of methanol.
Next, 0.5 g of 35% hydrochloric acid and 5 ml of pure water were added. The mixture was stirred at 50 degrees for 1 hour to obtain a gel 3 formed from the methine compound No. 18 of the present invention. (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. (AgNO ₃ 206.3 g) aqueous solution and KBr aqueous solution were added over 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 1000
Succinated gelatin at pH 5.8 at 40 ° C.
The pAg was adjusted to 8.8 to prepare a seed emulsion. This seed emulsion contains 1 mol of Ag and 80 g of gelatin per kg of emulsion.
It contained 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(43.9g) aqueous solution and KBr aqueous solution
Solution and an aqueous gelatin solution having a molecular weight of 20,000
No. 43570, a magnetic coupling induction type stirrer.
Mixing just before addition in another chamber with 25 minutes
Was added. At this time, the silver potential is applied to the saturated calomel electrode.
On the other hand, it was kept at -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 in the same manner as described above. Added over minutes.
At this time, the silver potential was set to -40 mV with respect to the saturated calomel electrode.
Kept.

(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 of the same type. 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 2000
The gelatin aqueous solution was mixed immediately before the 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 was set to 30 m with respect to the saturated calomel electrode.
Kept at V. Perform normal water washing, add gelatin,
The pH was adjusted to 5.8 and the pAg to 8.8 at 0 ° C. This emulsion was designated as emulsion b. Emulsion B was tabular grains having an average equivalent circle diameter of 3.3 μm, a coefficient of variation of the equivalent circle diameter of 21%, an average thickness of 0.090 μm, and 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 0.0 μm.
It was occupied by tabular grains of 90 μ or less. One layer saturation coverage of when the dye occupation area as 80 Å ² 1.45
× 10 ⁻³ mol / mol Ag.

Invention 1 Emulsion b was heated to 56 ° C., and Gel 1 of the invention was added to give a methine compound content of 2.4 × 10 ⁻⁴ mol / mol Ag, and then C-5 and thiocyanic acid were added. Potassium, chloroauric acid, sodium thiosulfate and N, N-dimethylselenourea were added for optimal chemical sensitization. Invention 2 Emulsion b was heated to 56 ° C., and Dye 1 was changed to 2.4 × 10 ⁻⁴ mo.
After the addition of 1 / molAg, C-5, potassium thiocyanate, chloroauric acid, sodium thiosulfate and N, N-dimethylselenourea were added for optimal chemical sensitization. Furthermore, the gel 1 of the present invention was prepared by using a methine compound having a content of 2.5 × 1
It was added so as to have a concentration of 0 ^-4 mol / mol Ag and stirred for 10 minutes. Comparative Example 1 Emulsion b was heated to 56 ° C., and 2.4 × 10 ⁻⁴ mol / mol Ag of methine compound No. 3 was added without gelling, and then C-5, potassium thiocyanate, and chloroauric acid were added. , Sodium thiosulfate and N, N-dimethylselenourea were added for optimal chemical sensitization. Comparative Example 2 Emulsion b was heated to 56 ° C., and Dye 1 was changed to 2.4 × 10 ⁻⁴ mo.
After the addition of 1 / molAg, C-5, potassium thiocyanate, chloroauric acid, sodium thiosulfate and N, N-dimethylselenourea were added for optimal chemical sensitization. In addition, methine compound No.
10 ^-4 mol / mol Ag was added and stirred for 10 minutes. Invention 3 Emulsion b was heated to 56 ° C., and Dye 1 was changed to 2.4 × 10 ⁻⁴ mo.
After the addition of 1 / molAg, C-5, potassium thiocyanate, chloroauric acid, sodium thiosulfate and N, N-dimethylselenourea were added for optimal chemical sensitization. Furthermore, the gel 2 of the present invention was prepared by using a methine compound having a content of 2.5 × 1
It was added so as to have a concentration of 0 ^-4 mol / mol Ag and stirred for 10 minutes.

Comparative Example 3 Emulsion b was heated to 56 ° C. and Dye 1 was changed to 2.4 × 10 ^-4 mo
After the addition of 1 / molAg, C-5, potassium thiocyanate, chloroauric acid, sodium thiosulfate and N, N-dimethylselenourea were added for optimal chemical sensitization. Further, the methine compound No. 6 was converted to a 2.5
× 10 ^-4 mol / mol Ag was added and stirred for 10 minutes. Invention 4 Emulsion b was heated to 56 ° C., and Dye 1 was changed to 2.4 × 10 ⁻⁴ mo.
After the addition of 1 / molAg, C-5, potassium thiocyanate, chloroauric acid, sodium thiosulfate and N, N-dimethylselenourea were added for optimal chemical sensitization. Further, the gel 3 of the present invention was prepared by using a methine compound having a content of 2.5 × 1
It was added so as to have a concentration of 0 ^-4 mol / mol Ag and stirred for 10 minutes. Comparative Example 4 Emulsion b was heated to 56 ° C., and Dye 1 was changed to 2.4 × 10 ⁻⁴ mo.
After the addition of 1 / molAg, C-5, potassium thiocyanate, chloroauric acid, sodium thiosulfate and N, N-dimethylselenourea were added for optimal chemical sensitization. Comparative Example 5 Emulsion b was heated to 56 ° C., and Dye 1 was changed to 2.4 × 10 ⁻⁴ mo.
After the addition of 1 / molAg, C-5, potassium thiocyanate, chloroauric acid, sodium thiosulfate and N, N-dimethylselenourea were added for optimal chemical sensitization. Further, 2.5 × 10 ⁻⁴ mol / mol Ag of the methine compound No. 18 of the present invention was added without forming a gel, and the mixture was stirred for 10 minutes.

The measurement of the light absorption intensity per unit area is
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
Obtain the absorption spectrum and light absorption intensity,
The coefficient of variation of the child distribution was determined.

The amount of dye adsorbed was determined as follows.
After centrifugation at 000 rpm for 10 minutes, the precipitate was freeze-dried, and 0.05 g of the precipitate was made up to 50 ml by adding 25 ml of a 25% aqueous sodium thiosulfate solution and methanol. This solution was analyzed by high performance liquid chromatography, and the dye concentration was quantified and determined. The number of dye adsorption layers was determined from the dye adsorption amount and the one-layer saturated coating amount thus obtained.

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 Nabox (Fuji Film Co., Ltd.) 35 g Potassium bromide 1 g Water is added to 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 Water added 1 liter Film was processed and optical density was measured with Fuji automatic densitometer The sensitivity was represented by the reciprocal of the amount of light required to give an optical density of +0.2. Inventive Examples 1 and 2 and Comparative Example 2 were represented by relative values when the sensitivity of Comparative Example 1 was set to 100. Invention 3 was represented by a relative value when the sensitivity of Comparative Example 3 was set to 100. Inventive 4 and Comparative Example 4 had a sensitivity of Comparative Example 5 of 100.
And expressed as a relative value. Therefore, Comparative Example 1,
2, Inventions 1 and 2, Comparative Example 3 and Invention 3, Comparative Example 4,
The absolute values of the sensitivities of the group No. 5 and the group of the present invention 4 are different.

Table 1 shows the results. Comparative Examples 1, 2, 3,
4 and 5 are single-layer adsorption. On the other hand, in the present invention, all the layers are adsorbed in a multilayer, and the light absorption intensity and the sensitivity corresponding to the number of the adsorbed layers are obtained.

Further, at the absorption maximum wavelength of the dyes in the second and subsequent layers (for example, 565 nm in the present invention 2), the ratio of the relative quantum yield of the spectral sensitization to the relative quantum yield of the dye in the first layer alone indicates the excitation. When the ratio of energy transfer to the first-layer dye among the excitation energies of the dyes in the second and subsequent layers was estimated, the ratio of the present invention 2 was 90% or more.

Further, the half value width of the absorption spectrum of the emulsion of the present invention 3 was measured to be 105 nm, and it was found that the second-layer dye formed a J-aggregate similarly to the first-layer dye.

The adsorption energy of the sensitizing dye in the second and subsequent layers was measured using the report by Asanuma et al. Using a dye desorbing agent described in the detailed description of the present invention. While no desorption was observed, desorption of the dye was observed in the comparative example, and it was confirmed that the present invention was stable multilayer adsorption.

As described above, the present inventors have found that, in the present invention, when the adsorption energy of the sensitizing dye in the second and subsequent layers or the state of the sensitizing dye in the second and subsequent layers satisfies the requirements of the present invention, It has been found that light absorption intensity and sensitivity commensurate with the number of adsorption layers can be obtained.

[0301]

[Table 1]

[0302]

Embedded image

Example 2 A comparison similar to that of Example 1 was conducted by comparing the color negative sensitive material system of Example 5 of JP-A-8-29904 with that of JP-A-7-92601.
No. 11-160828, the color reversal sensitive material of Example 1 of JP-A-6-347944, the color paper system of Example 1 of JP-A-6-347944, and the X-ray sensitive material of Example 1 of JP-A-8-122954. The system of the instant photosensitive material of Example 1 of Japanese Patent Application No. 11-89801, the system of the heat-developable photosensitive material of Example 1 of Japanese Patent Application No. 2000-89436, and the system of Example 1 of Japanese Patent Application Laid-Open No. 8-292512. The evaluation was performed in the system of the printing photosensitive material. As a result, the same effects as in Example 1 were obtained, and it was found that they were similarly useful.

[0304]

According to the present invention, it has become possible to provide a silver halide photographic emulsion and a silver halide photographic light-sensitive material which are highly sensitive due to the multilayer adsorption of the sensitizing dye.

Claims (17)

[Claims] 1. A silver halide photographic emulsion comprising at least one methine compound having a covalent bond with an inorganic substance. 2. The methine compound according to claim 1, wherein
2. The silver halide photographic emulsion according to claim 1, wherein said methine compound is in a gel form. 3. The covalent bond with an inorganic substance according to claim 1, wherein the covalent bond is -O-Si-O-, -O-Al-O-, or -O-Ti.
2. The silver halide photographic emulsion according to claim 1, wherein the emulsion is -O-. 4. The covalent bond with the inorganic substance according to claim 1, wherein the covalent bond is -O-Si-O-, -O-Al-O-, or -O-Ti
2. The silver halide photographic emulsion according to claim 1, wherein the methine compound is a gel. 5. A silver halide photographic emulsion comprising at least one gel-like matrix in which at least one methine compound is present. 6. The silver halide photographic emulsion according to claim 4, wherein the gel matrix according to claim 5 is SiO ₂ or Al ₂ O ₃ . 7. The silver halide photographic emulsion according to claim 1, wherein a sensitizing dye is adsorbed in multiple layers on the surface of the silver halide grain. A silver halide photographic emulsion according to any one of claims 1 to 6. 8. The silver halide photographic emulsion according to claim 7, wherein said silver halide photographic emulsion has a spectral absorption maximum wavelength of less than 500 nm and a light absorption intensity of 60 or more, or a light absorption maximum of 500 nm or more. 8. The silver halide photographic emulsion according to claim 7, comprising silver halide grains having an intensity of 100 or more. 9. The silver halide photographic emulsion according to claim 7 or 8, wherein the maximum value of the spectral absorption by the sensitizing dye of the emulsion is Amax, the shortest wavelength and the longest wavelength exhibiting 50% of Amax. 9. The silver halide photographic emulsion according to claim 7, wherein the wavelength interval is 120 nm or less. 10. The silver halide photographic emulsion according to claim 7, wherein the longest wavelength showing a spectral sensitivity of 50% of Smax is from 460 nm to 510 nm, or 560 nm.
10. The silver halide photographic emulsion according to claim 7, 8 or 9, wherein the range is from m to 610 nm, or from 640 nm to 730 nm. 11. In the silver halide grains of the silver halide photographic emulsion according to any one of claims 7 to 10, the excitation energy of the sensitizing dye of the second and subsequent layers is changed to the dye of the first layer by an efficiency of 10% or more. The silver halide photographic emulsion according to any one of claims 7 to 10, wherein the energy is transferred by: 12. The silver halide grains of the silver halide photographic emulsion according to claim 7, wherein both the sensitizing dye in the first layer and the sensitizing dye in the second and subsequent layers have J band absorption. The silver halide photographic emulsion according to any one of claims 7 to 11, wherein 13. The emulsion according to claim 7, wherein the emulsion contains a methine compound having at least one aromatic group.
A photographic silver halide emulsion according to any one of the above. 14. The silver halide photographic emulsion according to claim 1, wherein tabular grains having an aspect ratio of 2 or more are present in an amount of 50% or more (area) of all silver halide grains in the emulsion. The silver halide photographic emulsion according to any one of claims 1 to 13, wherein 15. The silver halide photographic emulsion according to any one of claims 1 to 14, wherein the silver halide photographic emulsion according to any one of claims 1 to 14 is selenium-sensitized. . 16. The silver halide photographic emulsion according to claim 1, further comprising a silver halide adsorbing compound other than a methine compound.
5. The silver halide photographic emulsion according to any one of 5. 17. A silver halide photographic light-sensitive material comprising at least one layer of the silver halide photographic emulsion according to claim 1.