JP2001075221A - 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 emulsion high in sensitivity and a silver halide photographic sensitive material using it. SOLUTION: The silver halide photographic emulsion contains silver halide grains having a spectral absorption maximum wavelength of <500 nm and a light absorptivity of >=30 or a spectral absorption maximum wavelength of >=500 nm and a light absorptivity of >=50, and at least one of sensitizing dyes except cyanine dyes.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel compound, a silver halide photographic emulsion containing the novel compound, 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, the sensitizing dye adsorbed on the surface of the silver halide grains absorbs light incident on the photographic material and transmits the light energy to the silver halide grains to obtain photosensitivity. Therefore, in the spectral sensitization of silver halide, the light energy transmitted to the silver halide can be increased by increasing the light absorptivity per unit grain surface area of the silver halide grains, thereby increasing the spectral sensitivity. It is believed that sensitivity is achieved. In order to improve the light absorptance on the surface of the silver halide grains, the amount of the spectral sensitizing dye adsorbed per unit grain surface area may be increased. However, the amount of sensitizing dye adsorbed on the surface of silver halide grains is limited, and it is difficult to adsorb more dye chromophores than monolayer saturated adsorption (that is, single-layer adsorption). Therefore,
At present, the absorptance of the incident light quantum of each silver halide grain in the spectral sensitization region is still low.

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

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 which 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. For the purpose of positively aiming at the improvement of the light absorption rate, GB Bird (A.B.
L. Borrr et al., In U.S. Pat. Nos. 3,622,317 and 3,976,493, incorporated a linked sensitizing dye molecule having a plurality of cyanine chromophores to increase light absorptivity 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.

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

[0007] Also, R. L. Parton (RL
(Parton et al.) In EP 887,700 A1 proposed a linking dye having a specific linking group.

Further, M. Roberts (MR.
Roberts et al. In US Pat. No. 4,950,587 proposed spectral sensitization with cyanine dye polymers.

As described above, many studies have been made to improve the light absorptivity, but none of them has been effective in improving the light absorptivity and high sensitivity.

In particular, in the case of a color photographic material, it is necessary to keep the spectral sensitivity within a target wavelength range. Normally, in spectral sensitization of a silver halide light-sensitive material, the J band formed when adsorbed on the surface of silver halide grains is used instead of using the absorption of the sensitizing dye in a monomer state.
The J band has a sharp absorption shifted to a longer wavelength side than the monomer state, and thus is very useful for keeping light absorption and spectral sensitivity in a desired wavelength range. Therefore, even if the light absorption rate can be increased by multilayer adsorption of the sensitizing dye on the grain surface, when the second and subsequent dyes that do not directly adsorb to the silver halide grains are adsorbed in a monomer state. Causes a very wide absorption, which is not appropriate as the spectral sensitivity of the actual photosensitive material. On the other hand, each color gamut has a width of about 100 nm, and it is not preferable that an unnecessarily large sensitivity difference occurs for light in that range. From the above, the sensitizing dye is multilayer-adsorbed on the surface of the silver halide grains, and while increasing the light absorption area intensity per unit grain surface area, the absorption and spectral sensitivity are limited to the width of a desired color gamut, and There has been a demand for a technique for minimizing changes in spectral absorptance and sensitivity for light in that range.

[0011]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide photographic emulsion having high sensitivity by efficiently capturing light incident on the silver halide photographic material and a silver halide photographic material using the same. Is to provide.

[0012]

Means for Solving the Problems The object of the present invention is to carry out the following studies (1), (2), (3),
(4), (5), (6), (7), (8), (9),
(10), (11), (12), (13), and (14) have been found to be achieved.

(1) Includes silver halide grains having a spectral absorption maximum wavelength of less than 500 nm and a light absorption intensity of 30 or more, or a spectral absorption maximum wavelength of 500 nm or more and a light absorption intensity of 50 or more. A silver halide photographic emulsion comprising at least one sensitizing dye. (2) A sensitizing dye other than a cyanine dye containing silver halide grains having a spectral absorption maximum wavelength of less than 500 nm and a light absorption intensity of 60 or more, or a spectral absorption maximum wavelength of 500 nm or more and a light absorption intensity of 100 or more. A silver halide photographic emulsion comprising at least one. (3) The silver halide photographic emulsion according to (1) or (2), wherein the sensitizing dye other than the cyanine dye is a merocyanine dye or rhodacyanine dye. The photographic silver halide emulsion described in 1 above. (4) The silver halide photographic emulsion according to (1), (2) or (3), wherein the sensitizing dye other than the cyanine dye is a merocyanine dye.
Or the silver halide photographic emulsion according to (3). (5) In the silver halide photographic emulsion described in (1), (2), (3) or (4), when the maximum value of the spectral absorption of the emulsion by the sensitizing dye is defined as Amax, 50%
The silver halide photographic emulsion according to (1), (2), (3) or (4), wherein the wavelength interval between the shortest wavelength and the longest wavelength is 120 nm or less. (6) In the silver halide photographic emulsion described in (1), (2), (3) or (4), when the maximum value of the spectral absorption of the emulsion by the sensitizing dye is defined as Amax, 80%
(1), wherein the wavelength interval between the shortest wavelength and the longest wavelength indicating 20% or more is 20 nm or more, and the wavelength interval between the shortest wavelength and the longest wavelength indicating 50% of Amax is 120 nm or less. The silver halide photographic emulsion according to 2), (3) or (4). (7) In the silver halide photographic emulsion described in (1), (2), (3) or (4), when the maximum value of the spectral sensitivity of the emulsion by the sensitizing dye is Smax, 50% of Smax. %. The silver halide photographic emulsion according to (1), (2), (3) or (4), wherein the wavelength interval between the shortest wavelength and the longest wavelength indicating% is 120 nm or less. (8) In the silver halide photographic emulsion described in (1), (2), (3) or (4), when the maximum value of the spectral sensitivity of the emulsion by the sensitizing dye is Smax, the Smax is 80. %, The wavelength interval between the shortest wavelength and the longest wavelength is 20 nm or more, and the wavelength interval between the shortest wavelength and the longest wavelength showing 50% of Smax is 120 nm or less (1). The silver halide photographic emulsion according to (2), (3) or (4). (9) In the silver halide photographic emulsion according to (5) or (6), the longest wavelength showing a spectral absorption of 50% of Amax is in the range of 460 nm to 510 nm, or 560 nm to 610 nm, or 640 nm to 730 nm. The silver halide photographic emulsion according to (5) or (6), wherein (10) In the silver halide photographic emulsion according to (7) or (8), the longest wavelength showing a spectral sensitivity of 50% of Smax is in the range of 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) or (8), wherein (11) The sensitizing dye is adsorbed in multiple layers on the surface of the silver halide grains, and the structure of the sensitizing dye other than cyanine in the second layer is different from the sensitizing dye other than cyanine in the first layer, and (1), (2), (3), (4), (5), (6), wherein the sensitizing dye other than cyanine in the second layer contains both a cationic dye and an anionic dye. ),
(7) The silver halide photographic emulsion according to (8), (9) or (10). (12) (1), (2), (3), (4), (5),
(6), (7), (8), (9), (10) or (1)
(1), (2), (3), (4), and (5), wherein the silver halide grains of the silver halide photographic emulsion described in 1) are tabular grains having an aspect ratio of 2 or more. ),
(6), (7), (8), (9), (10) or (1)
The silver halide photographic emulsion according to 1). (13) (1), (2), (3), (4), (5),
(6), (7), (8), (9), (10), (11)
Or (1), (2), (3), (4), (5), wherein the silver halide grains of the silver halide photographic emulsion according to (12) are selenium-sensitized. (6),
(7), (8), (9), (10), (11) or (1)
The silver halide photographic emulsion according to 2). (14) A silver halide photographic light-sensitive material containing at least one silver halide photographic emulsion layer, wherein (1)
(2), (3), (4), (5), (6), (7),
(8) A silver halide photographic light-sensitive material comprising the silver halide photographic emulsion described in (9), (10), (11), (12) or (13).

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The present invention is a silver halide photographic material using silver halide grains spectrally sensitized by a sensitizing dye other than a cyanine dye, wherein at least one of the sensitizing dyes has a large light absorption intensity, and is preferably The present invention relates to a silver halide photographic material having an appropriate spectral absorption waveform and sensitivity distribution. Here, the “cyanine dye” refers to, for example, two basic nuclei (hereinafter, referred to as a “nitrogen-containing heterocyclic ring”) as represented by general formulas (I-1), (II-1), and (IV). (Corresponding to "nucleus") and a methine group (which can be substituted) and a dye bonded at a position other than the N-position of the basic nucleus.

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 50 or more and a spectral absorption maximum wavelength of 500 n in the case of grains having a spectral absorption maximum wavelength of 500 nm or more.
In the case of a grain having a particle diameter of less than m, it is preferred that the silver halide grain having a light absorption intensity of 30 or more contains at least 1/2 of the total projected area of the silver halide grain. Further, the spectral absorption maximum wavelength is 500
In the case of particles of nm or more, the light absorption intensity is preferably 1
00 or more, more preferably 150 or more, particularly preferably 170 or more, and most preferably 200 or more. In the case of particles having a spectral absorption maximum wavelength of less than 500 nm, the light absorption intensity is preferably 60 or more, more preferably 90
Or more, particularly preferably 100 or more, and most preferably 12 or more.
0 or more. There is no particular upper limit, but preferably 2000
Below, more preferably 1000 or less, particularly preferably 500 or less. The spectral absorption maximum wavelength is 500 nm.
For particles less than 350 nm, the spectral absorption maximum wavelength is 350 nm
It is preferable that it is above.

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

The method of increasing the light absorption intensity includes a method of adsorbing more dye chromophore on the particle surface, a method of increasing the molecular extinction coefficient of the dye, and a method of reducing the area occupied by the dye. Any of these methods may be used, but is preferably a method in which the dye chromophore is further adsorbed on the particle surface. Here, the state in which the dye chromophore is more adsorbed on the grain surface means that more bound dye is present in the vicinity of the silver halide grains, and includes the dye present in the dispersion medium. Absent. Even when the dye chromophore is covalently linked to the substance adsorbed on the particle surface, the effect of increasing the light absorption intensity is long when the linking group is long and the dye chromophore is present in the dispersion medium. It is not considered small and more adsorption. Further, in the so-called multilayer adsorption, in which the dye chromophore is adsorbed on the particle surface more than one layer, it is necessary that spectral sensitization is caused by the dye not directly adsorbed on the particle surface,
For that purpose, it is necessary to transfer excitation energy or electrons from a dye not directly adsorbed to silver halide to a dye directly adsorbed to grains. Therefore, the excitation energy,
Alternatively, when the electron transfer needs to occur in more than 10 steps, the final excitation energy or the electron transfer efficiency is undesirably low. An example of this is disclosed in
Most of the dye chromophores, such as polymer dyes such as 13239, are present in the dispersion medium and transfer of excitation energy is
There are cases where more than one stage is required. In the present invention,
It is preferable to transmit the excitation energy among the excitation energy and the electrons. In the present invention, the number of dye chromophores per molecule is preferably from 1 to 3.

The chromophore described herein means an atomic group that is the main cause of the absorption band of a molecule 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. However, in the present invention, at least one contains a dye other than the cyanine dye. Preferably, styryl dye, hemicyanine dye, merocyanine dye, trinuclear merocyanine dye, tetranuclear merocyanine dye, rhodacyanine dye, complex cyanine dye, complex merocyanine dye, allopolar dye, oxonol dye,
And polymethine chromophores such as hemioxonol dyes, squarium dyes, croconium dyes, and azamethine dyes. More preferred are merocyanine dyes, trinuclear merocyanine dyes, tetranuclear merocyanine dyes, and rhodacyanine dyes, particularly preferred are merocyanine dyes and rhodacyanine dyes, and most preferred are merocyanine 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, Inc.- 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. The general formula of a cyanine dye, a merocyanine dye, and rhodacyanine dye is
U.S. Pat. No. 5,340,694 at columns 21-22 (X
Those shown in (I), (XII) and (XIII) are preferred. However, the number of n12, n15, n17, n18 is not limited,
It is an integer of 0 or more.

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 more than two layers. Although there is no particular upper limit, the number is preferably 10 or less, more preferably 5 or less.

In the present invention, the state in which the chromophore is further adsorbed on the surface of the silver halide grain is defined as the sensitizing dye added to the emulsion, the dye having the smallest area occupied by the dye on the surface of the silver halide grain. The reached saturated adsorption amount per unit surface area is defined as the more saturated coating amount, and the state in which the amount of adsorption of the dye chromophore per unit area is larger than this more saturated coating amount. The number of adsorbed layers means the amount of adsorption based on the amount of one-layer saturated coating. Here, in the case of a dye in which a dye chromophore is 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
Chemistry 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. Method to determine the amount of adsorbed dye by subtracting it from the amount of dye added, and drying the precipitated emulsion particles, dissolving a fixed weight of the precipitate in a 1: 1 mixture of aqueous sodium thiosulfate and methanol, and measuring the spectral absorption 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). 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 can be easily separated from the sedimented dye, and the dye adsorbed on the particles can be easily separated. Only the quantity can be measured accurately. This method is the most reliable as a method for obtaining the dye adsorption amount. As an example of a method for measuring the surface area of silver halide grains, a transmission electron micrograph is taken by a replica method,
There is a method of calculating and calculating the shape and size of each particle.
In this case, the thickness of the tabular grains is calculated from the length of the shadow of the replica. Examples of a method for taking a transmission electron micrograph include, for example, “Electron Microscope Sample Techniques”, edited by Kanto Chapter of the Japan Electron Microscope Society, published by Seikado Shinkosha in 1970, Butterworths, London, 1965, P.B. Hirsch (P.B.
Hirsch et al. Electron microscope
Of Chin Crystal (Electron Micr)
oscopy of ThinCrystals). Other methods include, for example, AM Kragin et al., Journal of Photographic Science (T.
he Journal of Photographi
c Science) Vol. 14, p. 185 (196
6 years), JF Paddy (JF Paddy)
Transactions of the Faraday-Society
Faraday Society, Vol. 60, p. 1325 (1964), S. Boyer
Journal de Chimi et al.
e Physique et de Physicoc
himie biologique) Vol. 63, 112
Page 3 (1963), W. West (W.C.
West et al., Journal of Physical Chemistry (Journal of Physical C)
hemistry) Vol. 56, page 1054 (195
2 years), H. Sauveni
er) editor, E. Klein et al. International Colloquium
nal Coloquium), Liege (Lieg)
e), 1959, "Scientific Photograph.
hy)) can be referred to. The dye occupation area can be determined experimentally for each case by the above method, but the molecular occupation area of a commonly used sensitizing dye is approximately 80%.
Since in the vicinity of A ^2, simply all of the dye can also be estimated roughly the number of adsorption layers a dye occupation area as 80A ² for.

In the present invention, when the dye chromophore is adsorbed on the silver halide grains in multiple layers, the so-called first-layer dye chromophore directly adsorbed on the silver halide grains and the second or higher dye chromophore The reduction potential and oxidation potential of the chromophore may be any values, but the reduction potential of the first dye chromophore is no less than the value obtained by subtracting 0.2 v from the reduction potential of the second or higher dye chromophore. It is preferred that

Various methods can be used for measuring the reduction potential and the oxidation potential. Preferably, the measurement is carried out 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, 8, 694, 803, 958 (1980) and 9, 85, (1981), and F. Sehaefer.
Author, "Dye Lasers", Springer (1973).

Further, it is preferable that the maximum absorption wavelength of the first-layer dye chromophore in the silver halide photographic light-sensitive material is longer than the maximum absorption wavelength of the second or higher-layer dye chromophore. 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 first-layer dye chromophore 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 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. The simple 80Å ^2. Saturated coating amount: The amount of dye adsorbed per unit particle surface area at the time of one-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 even larger than the saturated coating amount. Number of adsorbed layers: The amount of dye chromophore adsorbed per unit particle surface area based on the amount of one-layer saturated coating.

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 100 or more are 5 respectively.
The interval between the shortest wavelength and the longest wavelength indicating 0% is preferably 120 nm or less, more preferably 100 nm.
It is as follows. Further, the interval between the shortest wavelength and the longest wavelength indicating 80% of Amax and Smax is preferably 20 nm or more, preferably 100 nm or less, more preferably 80 nm or less.
nm or less, particularly preferably 50 nm or less. Also Am
The interval between the shortest wavelength and the longest wavelength indicating 20% of ax and Smax is preferably 180 nm or less, more preferably 150 nm or less, particularly preferably 120 nm or less, and most preferably 100 nm or less. Amax or Smax 5
The longest wavelength showing a spectral absorption of 0% is preferably 460
nm to 510 nm, or 560 nm to 610 n
m, or 640 nm to 730 nm.

The spectral absorption maximum wavelength is less than 500 nm and the light absorption intensity is 30 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 50 or more and a light absorption intensity of 50 or more is a method using the following specific dye.

For example, JP-A-10-239789, JP-A-8
269,092, 10-123650, Japanese Patent Application No. 7-
No. 75349, a method using a dye having an aromatic group, or a combination of a cation dye having an aromatic group and an anion dye, and a method using a dye having a multivalent charge described in JP-A-10-171588 JP-A-10-104
774, a method using a dye having a pyridinium group, a method using a dye having a hydrophobic group described in JP-A-10-186559, and a method using a dye having a hydrophobic group described in JP-A-10-186559.
A method using a dye having a coordination bonding group described in JP-A-197980 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 a positive and negative charge In this method, at least one of the charged dyes has 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.

More preferably, they are the above-mentioned hydrocarbon aromatic rings, particularly preferably benzene and naphthalene, and most preferably benzene.

The dye includes at least one dye other than the cyanine dye, and examples thereof include the dyes described above as examples of the dye chromophore. Preferably, a polymethine dye other than the cyanine dye shown as an example of the aforementioned polymethine dye chromophore is used.

More preferably, 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 dyes and azamethine dyes, more preferably merocyanine dyes, trinuclear merocyanine dyes, tetranuclear merocyanine dyes and rhodacyanine dyes, particularly preferably merocyanine dyes and rhodacyanine dyes, and most preferably merocyanine 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.
However, in (1) and (2), at least one contains a dye other than the cyanine dye. (1) A method using at least one of cationic, betaine, and nonionic methine dyes represented by the following general formula (I). (2) A method in which at least one of the cationic methine dyes represented by the following general formula (I) and at least one of the anionic methine dyes represented by the following general formula (II) are simultaneously used. General formula (I)

[0040]

Embedded image

In the formula, Z ₁ represents an atom group necessary for forming a nitrogen-containing heterocyclic ring. However, the rings may be condensed with these. R ₁ is an alkyl group, an aryl group, or a heterocyclic group. Q ₁ represents a group necessary for the compound represented by the general formula (I) to form a methine dye. L ₁ and L ₂ represent a methine group. p ₁ represents 0 or 1. However, Z ₁ , R ₁ , Q ₁ , L ₁ , and L ₂ have a substituent in which the methine dye 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 rhodocyanine 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)

[0042]

Embedded image

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 dye. L ₃ and L ₄ represent a methine group. p ₂ represents 0 or 1. However, Z ₂ , R ₂ , Q ₂ , L ₃ and L ₄ have a substituent in which the methine dye represented by the general formula (II) as a whole becomes an anion dye. M ₂ represents a counter ion for charge balancing, and m ₂ represents a number of 0 or more necessary to neutralize the charge of the molecule.

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

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

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

The term "anionic substituent" as used herein refers to a substituent having a negative charge, for example, a proton dissociable acidic group dissociated by 90% or more between pH 5 and 8. Specifically, for example, a sulfo group, a carboxyl group, a sulfato group,
Phosphoric acid group, boric acid group, alkylsulfonylcarbamoylalkyl group (for example, methanesulfonylcarbamoylmethyl group), acylcarbamoylalkyl group (for example, acetylcarbamoylmethyl group), acylsulfamoylalkyl group (for example, acetylsulfamoylmethyl group), alkyl And a sulfonylsulfamoylalkyl group (eg, a methanesulfonylsulfamoylmethyl group). More preferred are a sulfo group and a carboxyl group. Particularly preferred is a sulfo group. Examples of the cationic substituent include a substituted or unsubstituted ammonium group and a pyridinium group.

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

[0049]

Embedded image

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

Formula (I-2)

[0052]

Embedded image

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

[0054]

Embedded image

In the formula (I-3), L₁₆, L₁₇, L₁₈, L₁₉, L
₂₀, L_{twenty one}, L_{twenty two}, L_{twenty three}, And L_{twenty four}Represents a methine group. p
₆And p₇Represents 0 or 1. n_ThreeAnd n_FourIs 0, 1,
Represents 2, 3 or 4. Z₇, Z₈And Z₉Is the nitrogen-containing complex
Represents an atomic group necessary for forming a ring. However,
Z₇, And Z₉In, the ring may be condensed. R₇,
R ₈And R₉Is an alkyl group, an aryl group, or a heterocyclic group
Represents M₁, M₁Has the same meaning as in formula (I). However,
R₇, R₈, R₉, Z₇, Z₈, Z₉, L₁₆~ L_{twenty four}Is
When (I-3) is a cationic dye, it has an anionic substituent
When (I-3) is a betaine dye,
Have one.

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)

[0057]

Embedded image

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 atom 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)

[0060]

Embedded image

In the formula (II-2), L ₃₂ , L ₃₃ , L ₃₄ and L
₃₅ represents a methine group. p ₉ represents 0 or 1. n ₆ represents 0, 1, 2, 3, or 4. Z ₁₂ and Z ₁₃ represent an atom group necessary for forming a nitrogen-containing heterocyclic ring. However, the rings may be condensed with these. R ₁₂ and R ₁₃ 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 one of R ₁₂ and R ₁₃ has an anionic substituent. General formula (II-3)

[0062]

Embedded image

In the formula (II-3), L ₃₆ , L ₃₇ , L ₃₈ , L ₃₉ ,
_{L 40, L 41, L 42} , L 43, and L ₄₄ each represents a methine group.
p ₁₀ and p ₁₁ each represents 0 or 1. n ₇ and n ₈ are 0,
Represents 1, 2, 3 or 4. Z ₁₄ , Z ₁₅ and Z ₁₆ represent an atom group necessary for forming a nitrogen-containing heterocyclic ring. However,
Z ₁₄ and Z ₁₅ may have a condensed ring. 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, (I-1), (I-2), (I-3), (II-1), (II-
When 2) and (II-3) are used, at least one of them has the general formula (I-
1), Includes other than (II-1).

However, when the compounds of the general formulas (I-2) and (I-3) are used alone, at least one of R ₅ and R ₆
Preferably, both groups have an aromatic ring, and R ₇ , R
_And at least one, preferably two, of R ₉ ,
More preferably, all three groups have an aromatic ring.

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) (However, except for the combination of (I-1) and (II-1))
Is at least one of R _{3 to} R ₉ and R _{10 to} R ₁₆ of the combined dyes is a group having an aromatic ring, preferably two are groups having an aromatic ring, and more preferably 3 One is a group having an aromatic ring, and particularly preferably is a group having four or more aromatic rings.

In the present invention, the dyes in the second and higher layers may be adsorbed in any state, but it is more preferable to adsorb by forming a J-aggregate. In the present invention, the dyes in the second or higher layer are dyes that are adsorbed on silver halide grains but are not directly adsorbed on silver halide.
In the present invention, the J-aggregate of the dye in the second layer or more, the absorption width on the long wavelength side of the absorption indicated by the dye adsorbed in the second or more layers, the monomer state of no interaction between the dye chromophore It is defined as not more than twice the absorption width of the long wavelength side of the absorption exhibited by the dye solution. Here, the absorption width on the long wavelength side indicates an energy width between an absorption maximum wavelength and a wavelength that is longer than the absorption maximum wavelength and 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 the second layer is adsorbed in the monomer state, the adsorption position and the state are non-uniform, so that the absorption width on the long wavelength side of the monomer state of the dye solution is twice or more. 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 and higher layers is
It can be determined by subtracting the spectral absorption of the first-order dye from the total spectral absorption of the emulsion. Spectral absorption by the first-layer dye can be determined by measuring the absorption spectrum when only the first-layer dye is added. In addition, 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 first-layer dye can be measured. In experiments 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 are desorbed. Can be requested. This makes it possible to determine the spectral absorption of the dyes in the second and higher layers. The method using a pigment desorbent is
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) Preferably, the dye to be adsorbed as the first layer and the dye to be adsorbed to the second and subsequent layers are separately added, and it is more preferable to use dyes having different structures for the first-layer dye and the second-layer and higher dyes. 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 and subsequent dyes.

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

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

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

Another preferable method for realizing an adsorption state in which a dye chromophore is coated in multiple layers on the surface of a silver halide grain is to form two or more dye chromophores linked by a covalent bond by a linking group. This is a method using a dye compound having a group moiety. The dye chromophore that can be used is not particularly limited, and examples thereof include those described above for the dye chromophore. Preferably, it is the polymethine dye chromophore represented by the aforementioned dye chromophore. More preferred are cyanine dyes, merocyanine dyes, rhodacyanine dyes and oxonol dyes, particularly preferred are rhodacyanine dyes and merocyanine dyes, and most preferred are merocyanine dyes. However, among the chromophores of the linked dye compound, at least one chromophore other than the cyanine dye chromophore is included. Preferably, no cyanine dye chromophore is contained.

As a preferable example, see, for example,
No. 265144, a method using a dye linked by a methine chain, a method described in 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 a specific linking group described in Japanese Patent Application Nos. 8-31212 and 10-204306. And a method of forming a linked dye in an emulsion using a dye having a reactive group described in Japanese Patent Application No. 10-249971.

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

[0077]

Embedded image

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 chromophores represented by D ₁ and D ₂ may be any, but at least one has a dye chromophore other than the cyanine dye. 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 preferably, a cyanine dye, a merocyanine dye,
Rhodocyanine dyes and oxonol dyes, particularly preferably merocyanine dyes and rhodocyanine dyes, and most preferably merocyanine dyes.

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

La is a linking group (preferably a divalent linking group)
Or, represents a single bond. The linking group preferably comprises an atom or an atomic group containing at least one of a carbon atom, a nitrogen atom, a sulfur atom and an oxygen atom. Preferably, an alkylene group (eg, methylene, ethylene, propylene, butylene, pentylene), an arylene group (eg, phenylene, naphthylene), an alkenylene group (eg, ethenylene, propenylene), an alkynylene group (eg, ethinylene, propynylene), an amide group, an ester Group, sulfoamide group, sulfonic 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-
A diyl group) in combination with one or more 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 sulfoamide group, and a sulfonic 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 general formula (III) preferably has a charge of -1 as a whole.

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

[0093]

Embedded image

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. R ₁₇ and R ₁₈ represent an alkyl group, an aryl group, or a heterocyclic group. General formula (V)

[0095]

Embedded image

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

[0097]

Embedded image

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. n ₁₁ and n ₁₂ are 0, 1,
Represents 2, 3 or 4. Z ₂₁ , Z ₂₂ and Z ₂₃ represent an atomic group necessary for forming a nitrogen-containing heterocyclic ring. However,
A ring may be condensed on Z ₂₁ 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 _{2 1,} R ₂₂ and R ₂₃ represents an alkyl group, an aryl group, or a heterocyclic group.

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, general formula (I) (including (I-1,2,3)),
(II) (including (II-1,2,3)), (IV), (V), and (V
The methine compound represented by I) will be described in detail.

In the general formulas (I) and (II), Q ₁ and Q ₂ represent groups necessary for forming a methine dye. Q ₁ and Q
_{According to 2} , any methine dye can be formed, and examples thereof include the methine dyes shown as examples of the dye chromophores described above.

However, at least one of Q ₁ and Q ₂ in formulas (I) and (II) represents a group necessary for forming a dye other than a cyanine dye.

In addition to the cyanine dye, preferably, a merocyanine dye, rhodacyanine dye, trinuclear merocyanine dye, tetranuclear merocyanine dye, allopolar dye, hemicyanine dye, styryl dye and the like are exemplified. More preferably merocyanine dyes, rhodocyanine dyes,
Particularly preferred are merocyanine dyes. For more information on these dyes, see FM Harmer
Heterocyclic Compounds-Heterocycli
c Compounds-Cyanine Dyes and Related Compound
s) ", John Wiley and Sons
&amp; Sons), New York, London, 1964, DMSturmer, Heterocyclic Compound Special Topics in Heterocyclic Chemistry (Heterocyc)
lic Compounds-Special topics in heterocyclic chemi
stry) ", Chapter 18, Section 14, 482-515. The general formula of cyanine dye, merocyanine dye and rhodacyanine dye is described in US Pat.
(XI), (XII), columns 0 to 694, columns 21 to 22;
Those shown in (XIII) are preferred. Where n12
, N15, n17, and n18 are not limited and are integers of 0 or more (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 , the following resonance formula can be used. General formula (I)

[0104]

Embedded image

Formula (II)

[0106]

Embedded image

The general formulas (I), (II), (IV), (V) and
And (VI), Z₁, Z_Two, Z_Three, Z _Four, Z_Five, Z₇, Z
₉, Z_Ten, Z₁₁, Z₁₂, Z₁₄, Z₁₆, Z₁₇, Z₁₈,
Z₁₉, Z _{twenty one}, And Z_{twenty three}Is a nitrogen-containing heterocyclic ring, preferably 5 or
Represents the atoms required to form a 6-membered nitrogen-containing heterocyclic ring.
You. However, the rings may be condensed with these. As a ring
May be an aromatic ring or a non-aromatic ring. Like
Or an aromatic ring such as a benzene ring or naphthalene
Aromatic ring such as ring, pyrazine ring, thiophene
And a heteroaromatic ring such as a ring.

Examples of the nitrogen-containing heterocyclic ring include a thiazoline nucleus, a thiazole nucleus, a benzothiazole nucleus, an oxazoline nucleus, an oxazole nucleus, a benzooxazole 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
-A quinoline nucleus, a 4-quinoline nucleus, a 1-isoquinoline nucleus,
Examples thereof include a 3-isoquinoline nucleus, an imidazo [4,5-b] quinoxaline nucleus, an oxadiazole nucleus, a thiadiazole nucleus, a tetrazole nucleus, and a pyrimidine nucleus, and preferably a benzothiazole nucleus, a benzoxazole nucleus, and 3,3 nucleus. A dialkylindolenine nucleus (e.g. 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), or a benzimidazole nucleus. Yes, particularly preferred are benzoxazole nuclei, benzothiazole nuclei and benzimidazole nuclei, most preferred are benzoxazole nuclei and benzothiazole nuclei.

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 (for example, chlorine, bromine, iodine, fluorine), a mercapto group, a cyano group, a carboxy group, a phosphoric acid group, a sulfo group, a hydroxy group, having 1 to 10 carbon atoms, preferably 2 to 8 carbon atoms, more preferably Is from 2 to 5 carbon atoms
A carbamoyl group (eg, methylcarbamoyl, ethylcarbamoyl, morpholinocarbonyl), a sulfamoyl group having 0 to 10, preferably 2 to 8, more preferably 2 to 5 carbon atoms (eg, methylsulfamoyl, ethylsulfa Moyl, piperidinosulfonyl), a nitro group, an alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms (eg, methoxy, ethoxy, 2-methoxyethoxy, 2-phenyl) Ethoxy), an aryloxy group having 6 to 20, preferably 6 to 12, and more preferably 6 to 10 carbon atoms (for example, phenoxy, p-methylphenoxy, p-chlorophenoxy, naphthoxy),

An acyl group having 1 to 20 carbon atoms, preferably 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms (eg, acetyl, benzoyl, trichloroacetyl), 1 to 20 carbon atoms, preferably 2 to 20 carbon atoms 12, more preferably an acyloxy group having 2 to 8 carbon atoms (eg, acetyloxy, benzoyloxy);
It preferably has 2 to 12 carbon atoms, and more preferably 2 carbon atoms.
To 8 acylamino groups (eg, acetylamino), 1 to 20, preferably 1 to 10, more preferably 1 to 8 carbon atoms, sulfonyl groups (eg, methanesulfonyl, ethanesulfonyl, benzenesulfonyl), 1 to 20, preferably 1 to 1 carbon atoms
0, more preferably a sulfinyl group having 1 to 8 carbon atoms (for example, methanesulfinyl, ethanesulfinyl, benzenesulfinyl), a sulfonylamino group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 8 carbon atoms. Groups (eg, methanesulfonylamino, ethanesulfonylamino, benzenesulfonylamino),

An amino group, a substituted amino group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms (eg, methylamino, dimethylamino, benzylamino, anilino, diphenylamino); An ammonium group having a number of 0 to 15, preferably 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms (eg, trimethylammonium, triethylammonium);
To 15, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, such as a trimethylhydrazino group, 1 to 15 carbon atoms, preferably 1 carbon atoms.
To 10, more preferably a ureido group having 1 to 6 carbon atoms (e.g., a ureido group, an N, N-dimethylureido group);
C1 to C15, preferably C1 to C10, more preferably C1 to C6 imide group (for example, succinimide group), C1 to C20, preferably C1 to C12, more preferably C1 to C12 1 to 8 alkylthio groups (eg methylthio, ethylthio, propylthio),
An arylthio group having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms (eg, phenylthio, p-methylphenylthio, p-chlorophenylthio, 2-pyridylthio, naphthylthio), 2 carbon atoms To 20, preferably 2 to 12, more preferably 2 to 8 alkoxycarbonyl groups (eg methoxycarbonyl, ethoxycarbonyl, 2-benzyloxycarbonyl), 6 to 20 carbon atoms, preferably 6 to 20 carbon atoms 12, more preferably 6 to 10 carbon atoms
Aryloxycarbonyl group (for example, phenoxycarbonyl),

An unsubstituted alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms (eg, methyl, ethyl, propyl, butyl), and 1 to 18 carbon atoms, preferably A substituted alkyl group having 1 to 10, more preferably 1 to 5 carbon atoms {eg, hydroxymethyl, trifluoromethyl, benzyl, carboxyethyl, ethoxycarbonylmethyl, acetylaminomethyl, and here having 2 to 18 carbon atoms, preferably Unsaturated hydrocarbon groups having 3 to 10 carbon atoms, more preferably 3 to 5 carbon atoms (for example, vinyl group, ethynyl group 1-cyclohexenyl group, benzylidine group, benzylidene group) are also included in the substituted alkyl group. Having 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms, and more preferably 6 to 10 carbon atoms.換又 unsubstituted aryl group (e.g., phenyl, naphthyl, p- carboxyphenyl, p- nitrophenyl, 3,5-dichlorophenyl, p- cyanophenyl, m- fluorophenyl, p- tolyl)

A substituted or unsubstituted heterocyclic group having 1 to 20, preferably 2 to 10, more preferably 4 to 6 carbon atoms (eg, pyridyl, 5-methylpyridyl, thienyl, furyl, morpholino, tetrahydro Furfuryl). Further, a structure in which rings (aromatic or non-aromatic hydrocarbon rings or hetero rings, for example, a benzene ring, a naphthalene ring, an anthracene ring, and a quinoline ring) can be used. These substituents represented by V may be further substituted by V.

Preferred examples of the substituent are 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 , Z ₁₃ , and Z ₂₀ represent the atoms necessary to form an acidic nucleus, but can take the form of an acidic nucleus of any general merocyanine dye. The acidic nucleus referred to here is, for example, “The ・ ed.” Edited by James.
Theory of the Photographic Process "
(The Theory of the Photog
Raffic Process) 4th edition, defined by Macmillan Publishing Co., 1977, 198 Tribute. Specifically, U.S. Patent Nos. 3,567,719, 3,57
No. 5,869, No. 3, 804, 634, No. 3, 83
No. 7,862, No. 4, 002, 480, No. 4, 92
5,777, and JP-A-3-167546. The acidic nucleus is preferred when it forms a 5- or 6-membered nitrogen-containing heterocycle consisting of carbon, nitrogen and chalcogen (typically oxygen, sulfur, selenium and tellurium) atoms, and includes the following nuclei. 2-pyrazolin-5-one, pyrazolidine-3,5-dione, imidazoline-5-one, hydantoin, 2 or 4-thiohydantoin, 2-iminooxazolidine-4-one,
-Oxazoline-5-one, 2-thiooxazoline-2,4 dione, isoxazoline-5-one, 2-thiazolin-4-one, thiazolidine-4-one, thiazolidine-2,4 dione, rhodanine, thiazolidine-2,4 dithione, isorhodanine, indan-1,3
Dione, thiophen-3-one, thiophen-3-one-1,1, dioxide, indoline-2-one, indoline-3-one, 2-oxoindazolinium, 3-oxoindazolinium, 5,7-dioxo6,7 dihydrothiazolo [3, 2-a] pyrimidine, cyclohexane-1,3 dione, 3,4 dihydroisoquinoline-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] thiophen-1,1,1-dioxide, 3- Dicyanometin-2,3-dihydrobenzo [d] thiophen-1,1-dioxide nucleus.

As Z ₆ , Z ₁₃ , and Z ₂₀ , hydantoin, 2- or 4-thiohydantoin, 2-oxazoline-5-one, 2-thiooxazoline-2,4 dione, thiazolidine-2,4 dione, rhodanine,
Thiazolidine-2,4-dithione, barbituric acid, 2
-Thiobarbituric acid, more preferably hydantoin, 2 or 4-thiohydantoin, 2-oxazoline-5-one, rhodanine, barbituric acid, 2-thiobarbituric acid. Particularly preferably 2 or 4
-Thiohydantoin, 2-oxazoline-5-one, rhodanine, barbituric acid.

Z₈, Z_Fifteen, And Z_{twenty two}Formed by
The 5- or 6-membered nitrogen-containing heterocycle is represented by Z ₆, Z₁₃, And Z₂₀
An oxo or thioxo group from the heterocyclic ring represented by
Is excluded. Preferably hydantoin, 2 or
Is 4-thiohydantoin, 2-oxazoline-5-o
2-thiooxazoline-2,4-dione, thiazolyl
Gin-2, 4-dione, rhodanine, thiazolidine
2,4 dithione, barbituric acid, 2-thiobarbit
Oleic acid without oxo or thioxo groups
And more preferably hydantoin, 2 or 4-h
Ohidantoin, 2-oxazoline-5-one, loader
From nin, barbituric acid and 2-thiobarbituric acid
It excludes a xo group or a thioxo group, and is particularly preferable.
Or 2- or 4-thiohydantoin, 2-oxazoly
N-5-one, rhodanine to oxo group, or thioxo
Without the group.

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 , and R ₂₃ are an alkyl group, an aryl group, and a heterocyclic group. 1 to 18, preferably 1 to 7, particularly preferably 1 to 4 unsubstituted alkyl groups (eg methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl), carbon atoms 1 to 18, preferably 1 to 7, particularly preferably 1 to 4, substituted alkyl groups, such as the aforementioned 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, carboxymethyl) , 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl), an alkoxyalkyl group (eg, 2-methoxyethyl, 2- (2-methoxyethoxy) ethyl), an aryloxyalkyl group (eg, 2-phenoxyethyl, 2
-(1-naphthoxy) ethyl), alkoxycarbonylalkyl group (for example, ethoxycarbonylmethyl, 2-benzyloxycarbonylethyl), aryloxycarbonylalkyl group (for example, 3-phenoxycarbonylpropyl), acyloxyalkyl group (for example, 2-acetyloxyethyl) ), Acylalkyl groups (eg, 2-acetylethyl), carbamoylalkyl groups (eg, 2-morpholinocarbonylethyl), sulfamoylalkyl groups (eg, N, N-dimethylsulfamoylmethyl), sulfoalkyl groups (eg, 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 group ( For example, 2- (pyrrolidin-2-one-1-yl) ethyl, tetrahydrofurfuryl), alkylsulfonylcarbamoylalkyl group (for example, methanesulfonylcarbamoylmethyl group), acylcarbamoylalkyl group (for example, acetylcarbamoylmethyl group), acylsulfa Moylalkyl group (for example, acetylsulfamoylmethyl group), alkylsulfonylsulfamoylalkyl group (for example, methanesulfonylsulfamoylmethyl group)}, having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, and more preferably Unsubstituted aryl group having 6 to 8 carbon atoms (e.g., phenyl, 1-naphthyl group), a carbon number 6
To 20, preferably 6 to 10, more preferably 6 to 8 substituted aryl groups (for example, the above-mentioned V-substituted aryl groups exemplified as substituents. Specific examples include p- A methoxyphenyl group, a p-methylphenyl group, a p-chlorophenyl group, etc.), having 1 to 20 carbon atoms, preferably 3 to 1 carbon atoms.
0, and more preferably an unsubstituted heterocyclic group having 4 to 8 carbon atoms (eg, 2-furyl, 2-thienyl, 2-pyridyl, 3-pyrazolyl, 3-isoxazolyl, 3-isothiazolyl, 2-imidazolyl, 2-oxazolyl,
-Thiazolyl, 2-pyridazyl, 2-pyrimidyl, 3-pyrazyl, 2- (1,3,5-triazolyl), 3- (1,2,4-
Triazolyl), 5-tetrazolyl), having 1-2 carbon atoms
0, preferably a substituted heterocyclic group having 3 to 10 carbon atoms, and more preferably a substituted heterocyclic group having 4 to 8 carbon atoms (for example, a heterocyclic group substituted by V described above as an example of the substituent. Specifically, 5 -Methyl-2-thienyl group, 4-methoxy-2
-Pyridyl group and the like. ).

R ₁ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R
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 together, or a polycyclic fused ring in which an aromatic hydrocarbon ring and an aromatic heterocycle 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.

Further, 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 as examples of the aforementioned 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 preferred are the above-mentioned alkyl groups having a substituted or unsubstituted hydrocarbon aromatic ring or heteroaromatic ring. Particularly preferred are the above-mentioned alkyl groups having a substituted or unsubstituted hydrocarbon aromatic ring.

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

The group having an aromatic ring is represented by -Lc-A
It can be represented by ₂ . Here, Lc represents a single bond or a linking group. A ₂ represents an aromatic group. As the linking group for Lc, preferably, the linking group described for La or the like is mentioned. The aromatic group for A ₂ is preferably the same as the above-mentioned aromatic group. Lc or A ₂ is preferably substituted by at least one anionic substituent.

Preferably, as the alkyl group having a hydrocarbon aromatic ring, an aralkyl group substituted with a sulfo group, a phosphate group or a carboxyl group (for example, 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, phosphorus 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.

When the methine dye represented by formula (IV), (V) or (VI) represents the chromophore represented by D ₁ in formula (III), R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ ,
The substituent represented by R ₂₂ and R ₂₃ is preferably the above-mentioned unsubstituted alkyl group or substituted alkyl group (for example, carboxyalkyl group, sulfoalkyl group, aralkyl group, aryloxyalkyl group).

When the methine dye represented by formula (VI), (VII) or (VIII) represents the chromophore represented by D2 in formula (I), R ₁₇ , R ₁₈ , R _{18 19,} R _20, R _21,
The substituent represented by R ₂₂ and R ₂₃ is preferably an alkyl group having an anionic substituent (for example, a carboxyalkyl group or a 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 and L ₆₄ each independently represent a methine group. L ₁
Methine group represented by ~L ₆₄ may have a substituent, the aforementioned V is enumerated as the substituent. For example, a substituted or unsubstituted alkyl group having 1 to 15, preferably 1 to 10, and particularly preferably 1 to 5 carbon atoms (eg, methyl, ethyl, 2-carboxyethyl),
A substituted or unsubstituted aryl group having 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms, more preferably 6 to 10 carbon atoms (eg, phenyl, o-carboxyphenyl);
A substituted or unsubstituted heterocyclic group having 3 to 20, preferably 4 to 15, and more preferably 6 to 10 carbon atoms (eg, N, N-dimethylbarbituric acid group), a halogen atom, , Bromine, iodine, fluorine), an alkoxy group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms (for example, methoxy, ethoxy), and 0 to 15 carbon atoms, preferably An amino group having 2 to 10, more preferably 4 to 10 carbon atoms (for example, methylamino, N, N-dimethylamino, N
-Methyl-N-phenylamino, N-methylpiperazino), having 1 to 15 carbon atoms, preferably 1 to 1 carbon atoms
0, more preferably an alkylthio group having 1 to 5 carbon atoms (eg, methylthio, ethylthio);
An arylthio group having 0, preferably 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms (for example, phenylthio,
p-methylphenylthio) and the like. It may also form a ring with another methine group, or Z _{1 to} Z ₂₃ ,
A ring may be formed together with R _{1 to} R ₂₃ .

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, And n₁₂Are independent
Represents 0, 1, 2, 3 or 4. Preferably 0, 1,
2, 3, more preferably 0, 1, 2, and especially
It is preferably 0 or 1. n ₁, N_Two, N_Three, N_Four, N
_Five, N₆, N₇, N₈, N₉, N_Ten, N₁₁, And n₁₂But
When 2 or more, the methine group is repeated but must be the same
There is no.

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.

M₁, M_Two, M_Three, M_Four, M_Five, And M₆
Is necessary to neutralize the ionic charge of the dye.
In the formula to indicate the presence of a cation or anion
Is included. A typical cation is hydrogen ion
(H⁺), Alkali metal ions (for example, sodium ion
, Potassium ion, lithium ion), alkaline earth
Inorganic positive ions such as metal ions (for example, calcium ions)
ON, ammonium ion (for example, ammonium ion
, Tetraalkylammonium ion, pyridinium
Organic ions such as ion, ethylpyridinium ion)
Is mentioned. Anions can be inorganic or organic
Ion, any of which may be a halogen anion (eg,
For example, fluorine ion, chlorine ion, iodine ion), substitution
Arylsulfonate ion (for example, p-toluenesulfo
Acid ion, p-chlorobenzenesulfonic acid ion),
Aryl disulfonate ion (for example, 1,3-benzene
Sulfonate ion, 1,5-naphthalenedisulfonic acid
On, 2,6-naphthalenedisulfonic acid ion), al
Kill sulfate ion (eg methyl sulfate ion), sulfate ion
Thiocyanate ion, perchlorate ion, tetraflu
Oloborate ion, picrate ion, acetate ion,
And trifluoromethanesulfonate ion. Further
Other colors having an opposite charge to the ionic polymer or dye
Element may be used. Also, CO_Two ^-, SO_Three ^-Is
When hydrogen ion is on, CO _TwoH, SO_ThreeH
It is also possible to write.

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

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

Specific examples of the compounds (other than cyanine dyes) of the present invention represented by the general formula (I) (including the lower conceptual structure).

[0140]

Embedded image

[0141]

Embedded image

[0142]

Embedded image

[0143]

Embedded image

Specific examples (other than cyanine dyes) of the compounds represented by the general formula (II) (including the lower conceptual structure) of the present invention.

[0145]

Embedded image

[0146]

Embedded image

[0147]

Embedded image

[0148]

Embedded image

Specific examples of the compound represented by formula (III) (other than cyanine dye chromophore) of the present invention.

[0150]

Embedded image

[0151]

Embedded image

[0152]

Embedded image

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 &amp; Sons)-New York, London, 1
964, DMSturmer, Heterocyclic Compounds-Special Topics in Heterocyclic Chemistry (H
eterocyclic Compounds-Special topics in heterocycl
ic chemistry), Chapter 18, Section 14, 482-515, John Wiley and Sons (John Wi
ley & Sons)-New York, London, 197
7th year, "Rodd's Chemistry of Carbon Compounds"
2nd.Ed.vol.IV, partB, 1977, Chapter 15, Chapter 369
422, Elsevier Science Public
Company Inc. (Elsevier Science Publishing Com
pany Inc.), New York, and the above-mentioned patents and literatures (cited for describing specific examples) and the like.

In the present invention, not only the sensitizing dye of the present invention but also other spectral sensitizing dyes other than the present invention may be used in combination.

The time when the sensitizing dye of the present invention (and the same applies to other sensitizing dyes) is added to the silver halide emulsion of the present invention. It may be in any process. For example, U.S. Pat. Nos. 2,735,766 and 3,628,960,
As disclosed in JP-A-4,183,756, JP-A-4,225,666, JP-A-58-184142, JP-A-60-196,749, etc., a step of forming silver halide grains and / or desalting. Before, during and / or after desalination and before the start of chemical ripening.
As disclosed in No. 3920, etc., it may be added at any time before the chemical ripening or during the process, or at any time before the application of the emulsion after the chemical ripening and before coating. Further, as disclosed in U.S. Pat. No. 4,225,666, 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. It may be divided and added during the ripening step or after the completion of chemical ripening, or may be divided and added before or after the completion of the chemical ripening or during the step,
Compounds to be divided and added may be added by changing the kind of the combination of the compounds.

The addition amount of the compound of the present invention varies depending on the shape and size of silver halide grains, but it can be used in an amount of 1 × 10 ^-6 to 8 × 10 ^-3 mol per mol of silver halide. For example, when the silver halide grain size is 0.
In the case of 2 to 1.3 μm, the addition amount is preferably 2 × 10 ^{−6 to} 3.5 × 10 ⁻³ mol, and 7.5 × 10 ^{−6 to} 1.5 × 10 per mol of silver halide. An addition amount of ^-3 mol is more preferred. However, as described above, an amount necessary for multilayer adsorption of the sensitizing dye is added.

The compounds of the present invention can be dispersed directly 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 made to coexist. Also, ultrasonic waves can be used for dissolution. As a method for adding the 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 a compound in a surfactant and adding the solution to an emulsion, and dissolving using a compound that causes a red shift as described in JP-A-51-74624, and dissolving the solution in the emulsion. As described in JP-A-50-80826, a method in which a compound is dissolved in an acid substantially free of water and the solution is added 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, the photographic emulsion controlling the light-sensitive mechanism includes any of silver bromide, silver iodobromide, silver chlorobromide, silver iodide, silver iodochloride, silver iodobromochloride and silver chloride as silver halide. Although a halogen composition on the outermost surface of the emulsion may contain iodine of 0.1 mol% or more, more preferably 1 mol% or more, particularly preferably 5 mol% or more, a stronger multilayer adsorption structure can be constructed. The particle size distribution may be wide or narrow, but narrower is more preferable. The silver halide grains of a photographic emulsion have regular crystals such as cubic, octahedral, tetradecahedral, and rhombohedral, and irregular grains such as spheres and plates. (Irregular) crystal form,
It may have a higher-order plane ((hkl) plane) or a mixture of grains of these crystal forms, but is preferably a tabular grain, and the tabular grain will be described in detail below. For particles with higher planes, see Journal of I
See pages 247 to 254 of the Journal of Maging Science, Vol. 30, (1986). Further, the silver halide photographic emulsion used in the present invention may contain the above-mentioned silver halide grains singly or as a mixture of two or more.
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.

The silver halide emulsion used in the present invention has a higher surface area / absorbing sensitizing dye disclosed in the present invention.
Tabular silver halide grains having a high volume ratio are preferred, and the aspect ratio is 2 or more (preferably 100 or less), preferably 5 or more and 80 or less, more preferably 8 or more and 80 or less. Less than 0.2 μm is preferred,
More preferably less than 0.1 μm, even more preferably 0.0
It is less than 7 μm. The following technique is applied to prepare such thin tabular grains having a high aspect ratio.

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 (100) or (111) main surface. Tabular grains having a (111) major surface, hereinafter referred to as (111) tabular, usually have triangular or hexagonal faces. In general, the more uniform the distribution, the higher the proportion of tabular grains having more hexagonal faces. Hexagonal monodisperse flat plate
5.

Tabular grains having a (100) plane as a main surface,
Hereinafter, 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, which is described in JP-A-9-80660, JP-A-9-80656, and US Pat. No. 5,298,388. I have.

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
No. 4,443,426, US Pat. No. 4,395,395.
No. 20, U.S. Pat. No. 4,414,310, U.S. Pat.
No. 33048, U.S. Pat. No. 4,647,528, U.S. Pat. No. 4,650,012, U.S. Pat. No. 4,672,027, U.S. Pat. No. 4,678,745, U.S. Pat. No. 4,684,607.
No. 4,593,964, U.S. Pat.
No. 886, U.S. Pat. No. 4,722,886, U.S. Pat.
No. 755617, U.S. Pat. No. 4,755,456, U.S. Pat. No. 4,806,461, U.S. Pat. No. 4,801,522, U.S. Pat. No. 4,835,322, U.S. Pat. No. 4,839,268.
No. 4,940,014, U.S. Pat.
No. 015, U.S. Pat. No. 4,977,074, U.S. Pat.
No. 98350, 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. 8, US Pat. No. 5,334,469, US Pat.
No. 4495, US Pat. No. 5,358,840, US Pat. No. 5,372,927.

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 is generally used after chemical sensitization. Chemical sensitization includes chalcogen sensitization (sulfur sensitization, selenium sensitization, tellurium sensitization), noble metal sensitization (eg,
Gold sensitization) and reduction sensitization are performed alone or in combination. In the present invention, a silver halide emulsion sensitized at least with selenium is preferred. That is, selenium sensitization alone, in combination with selenium sensitization and other chalcogen sensitization and / or noble metal sensitization (particularly gold sensitization) is preferred,
Particularly preferred is a combination with selenium sensitization and noble metal sensitization.

In selenium sensitization, an unstable selenium compound is used as a sensitizer. Unstable selenium compounds are described in JP-B-43-13489 and JP-B-44-15748.
No., JP-A-4-25832, JP-A-4-109240,
It is described in JP-A-4-271341 and JP-A-5-40324. Examples of selenium sensitizers include colloidal metal selenium, selenoureas (eg, N, N-dimethylselenourea, trifluoromethylcarbonyl-trimethylselenourea, acetyl-trimethylselenourea), selenoamides (eg, selenourea) Acetamide, N, N-diethylphenylselenoamide), phosphine selenides (eg, triphenylphosphine selenide, pentafluorophenyl-triphenylphosphine selenide), selenophosphates (eg, tri-p-) Tolylselenophosphate, tri-n-butylselenophosphate, selenoketones (eg, selenobenzophenone),
Includes isoselenocyanates, selenocarboxylic acids, selenoesters and diacyl selenides. In addition, relatively stable selenium compounds such as selenous acid, potassium selenocyanide, selenazoles and selenides (described in JP-B-46-4553 and JP-B-52-34492) can also be used as selenium sensitizers.

In the sulfur sensitization, an unstable sulfur compound is used as a sensitizer. For unstable sulfur compounds, see P.
By Glafkides Chemie et Physique Photographique (Pa
ul Montel, 1987, 5th edition), Research Dis
It is described in closure magazine 307, 307105. Examples of sulfur sensitizers include thiosulfates (eg, hypo), thioureas (eg, diphenylthiourea, triethylthiourea, N
-Ethyl-N '-(4-methyl-2-thiazolyl) thiourea, carboxymethyltrimethylthiourea), thioamides (eg, thioacetamide), rhodanines (eg,
Diethyl rhodanine, 5-benzylidene-N-ethyl-
Rhodanine), phosphine sulfides (eg, trimethylphosphine sulfide), thiohydantoins,
4-oxooxazolidine-2-thiones, dipolysulfides (eg, dimorpholine disulfide, cystine, hexathiocan-thione), mercapto compounds (eg, cysteine), polythionates and elemental sulfur. Activated gelatin can also be used as a sulfur sensitizer.

In tellurium sensitization, an unstable tellurium compound is used as a sensitizer. Unstable tellurium compounds are described in Canadian Patent 800958, British Patent 12954
Nos. 62 and 1396696, JP-A No. 4-20
No. 4640, No. 4-271341, No. 4-33304
Nos. 3 and 5-303157.
Examples of tellurium sensitizers include telluroureas (eg, tetramethyltellurourea, N, N'-dimethylethylenetellurourea, N, N'-diphenylethylenetellurourea), phosphine tellurides (eg, butyl) -Diisopropylphosphine telluride, tributylphosphine telluride,
Tributoxyphosphine telluride, ethoxy-diphenylphosphine telluride), diacyl (di) tellurides (eg, bis (diphenylcarbamoyl) ditelluride,
Bis (N-phenyl-N-methylcarbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl)
Telluride, bis (ethoxycarbonyl) telluride), isotellurocyanates, telluramides, tellurohydrazides, telluroesters (eg, butylhexyl telluroester), telluroketones (eg, telluroacetophenone), colloidal tellurium, (di) Includes tellurides and other tellurium compounds (eg, potassium telluride, sodium telluropentathionate).

In the noble metal sensitization, a salt of a noble metal such as gold, platinum, palladium or iridium is used as a sensitizer. For precious metal salts, see P. Glafkides, Chemie et P
hysique Photographique (Paul Montel, 1987
Year, 5th edition), Research Disclosure Magazine, Volume 307
No. 105. Gold sensitization is particularly preferred. As described above, the present invention is particularly effective in the mode of performing gold sensitization. The ability to remove gold from sensitizing nuclei on emulsion grains with a solution containing potassium cyanide (KCN) has been demonstrated by Photographic Science and Engineering (Photo
graphic Science and Engineering) Vol 19322 (1
975) and Journal Imaging Science (Jou
rnal of Imaging Science) Vol 3228 (1988). According to these descriptions, cyan ions release gold atoms or gold ions adsorbed on silver halide grains as a cyan complex, thereby inhibiting gold sensitization. According to the present invention, if the generation of cyan is suppressed, the effect of gold sensitization can be sufficiently obtained.

Examples of gold sensitizers include chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide and gold selenide. Also, U.S. Pat.
Nos. 42361, 5049484 and 50494
No. 85, the gold compounds described in each specification can also be used. In reduction sensitization, a reducing compound is used as a sensitizer. For reducing compounds, see P. Glafkides's Che
mie et Physique Photographique (Paul Montel,
1987, 5th edition), Research Disclosure 307
No. 307105. Examples of reduction sensitizers include:
Aminoiminomethanesulfinic acid (thiourea dioxide),
Borane compounds (eg, dimethylamine borane), hydrazine compounds (eg, hydrazine, p-tolylhydrazine),
It includes polyamine compounds (eg, diethylenetriamine, triethylenetetramine), stannous chloride, silane compounds, reductones (eg, ascorbic acid), sulfites, aldehyde compounds, and hydrogen gas. Further, reduction sensitization can be carried out in an atmosphere having a high pH or an excess of silver ions (so-called silver ripening). The reduction sensitization is preferably performed at the time of forming silver halide grains.

The amount of the sensitizer used is determined depending on the type of silver halide grains generally used and the conditions of chemical sensitization. The amount of the chalcogen sensitizer used is generally 10 ^-8 to 10 ^-2 mol, preferably 10 ^{-7 to} 5 × 10 ^-3 mol, per mol of silver halide. The use amount of the noble metal sensitizer is preferably 10 ^-7 to 10 ^-2 mol per mol of silver halide. There are no particular restrictions on the conditions for chemical sensitization. The pAg is generally 6-11, preferably 7-10. p
H is preferably 4 to 10. Temperature is 40-95
° C, more preferably 45 to 85 ° C.

The preparation method of the photographic emulsion used in the present invention is described in JP-A-10-239789, column 63, 36.
Line to column 65, 2 lines, etc. can be applied. The type of the light-sensitive material to which the present invention is applied, the processing of the light-sensitive material, and the like, such as additives such as color couplers and additives to photographic light-sensitive materials, are described in JP-A-10-239789, col. Col. 73 1
Three lines can be applied.

[0173]

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 a silver bromide octahedral emulsion (emulsion A) and a silver bromide tabular emulsion (emulsion B and emulsion C). 1000 ml of water, 25 g of deionized bone gelatin, 15 ml of a 50% NH ₄ NO ₃ aqueous solution and 7.5 ml of a 25% NH ₃ aqueous solution are added to a reaction vessel, and the mixture is kept at 50 ° C., stirred well, and 750 ml of a 1N silver nitrate aqueous solution is added. And 1
A mol / l aqueous solution of potassium bromide was added in 50 minutes, and the silver potential during the reaction was kept at -40 mV. The obtained silver bromide particles are octahedral and have a sphere equivalent diameter of 0.846 ± 0.036 μm.
Met. The temperature of the emulsion was lowered, a copolymer of isobutene and monosodium maleate was added as a flocculant, and the emulsion was washed by settling and desalted. Then, 95 g of deionized bone gelatin and 430 ml of water were added, and the pH was adjusted at 50 ° C.
After adjusting to 6.5 and pAg 8.3, potassium thiocyanate, chloroauric acid and sodium thiosulfate were added and the mixture was aged at 55 ° C. for 50 minutes to obtain optimum sensitivity. This emulsion was designated as emulsion A.

Potassium bromide 6.4 in 1.2 liters of water
g and low molecular weight gelatin having an average molecular weight of 15,000 or less6.
While dissolving 2 g and keeping the temperature at 30 ° C., 8.1 ml of a 16.4% aqueous silver nitrate solution and 7.2 ml of a 23.5% aqueous potassium bromide solution were added by a double jet method over 10 seconds. Next, a 11.7% aqueous gelatin solution was further added, the temperature was raised to 75 ° C., and the mixture was aged for 40 minutes. Then, 370 ml of a 32.2% aqueous silver nitrate solution and a 20% aqueous potassium bromide solution were added to a silver potential of −20 mV. The temperature was lowered to 35 ° C. after physical ripening for 1 minute. Thus, the average projected area diameter is 2.32 μm, and the thickness is 0.0
A monodispersed pure silver bromide tabular emulsion (specific gravity: 1.15) having a diameter of 9 μm and a variation coefficient of diameter of 15.1% was obtained. Thereafter, soluble salts were removed by the coagulation sedimentation method. The temperature was again maintained at 40 ° C., and 45.6 g of gelatin, 10 ml of an aqueous solution of sodium hydroxide having a concentration of 1 mol / l, 167 ml of water and 1.66 ml of 35% phenoxyethanol were added, the pAg was 8.3, and the pH was 6.3. Adjusted to 20. This emulsion was ripened at 55 ° C. for 50 minutes by adding potassium thiocyanate, chloroauric acid and sodium thiosulfate to obtain the optimum sensitivity. This emulsion was designated as emulsion B. Also, instead of potassium thiocyanate, chloroauric acid and sodium thiosulfate,
The emulsion chemically sensitized with potassium thiocyanate, chloroauric acid, pentafluorophenyl-diphenylphosphine selenide and sodium thiosulfate was used as emulsion C. When the dye occupied area is 80 色素² , the saturated coating amounts of emulsions A and B are 5.4 × 10 ^-4 and 1.42 × 1 respectively.
It was 0 ^-3 mol / mol Ag.

The emulsion obtained as described above was added at a temperature of 50 ° C., and the first dye shown in Table 1 was added and stirred for 30 minutes. Then, the second dye and the third dye were added successively.
The mixture was further stirred at 50 ° C. for 30 minutes.

[0177]

[Table 1]

The amount of the 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.

Measurement of the light absorption intensity per unit area
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.

A gelatin hardener and a coating aid were added to the obtained emulsion, and a gelatin protective layer was coated 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 Metol 2.5 g L-ascorbic acid 10 g Nabox (Fuji Film Co., Ltd.) 35 g Potassium bromide 1 g 1 liter with water pH 9.8 Developed film is Fuji Automatic Densitometer And the sensitivity is the reciprocal of the amount of light required to give an optical density of +0.2, and is shown as a relative value when the sensitivity of Comparative Example 1 is 100. Table 2 shows the results.

[0182]

[Table 2]

[0183]

Embedded image

[0184]

Embedded image

The adsorption amount when only the first dye of Comparative Example 1 was added was 1.28 × 10 ⁻³ (mol / mol A).
g), the number of adsorption layers was 0.9, and the light absorption intensity was 45.
As shown in Table 2, according to the present invention, higher adsorption amount, higher number of adsorption layers, higher light absorption intensity and higher spectral sensitivity than the comparative dye were obtained. In addition, according to the present invention,
Thus, the sensitizing dyes of the first layer and the second or higher layers can be J-associated and adsorbed in multiple layers, and the light absorption intensity increases in a narrow wavelength range. In one of the present invention, the absorption width (80% of Amax, 50%) obtained from the spectrum obtained by converting the diffuse reflection spectrum of the emulsion by the Kubelka-Munk equation is used.
%) Are 27 nm and 105 nm, respectively, and the spectral sensitivity widths (80% and 50% of Smax) are 31 nm and 106 n, respectively.
m.

Example 2 A pure silver chloride tabular grain emulsion was prepared in the same manner as in Emulsion D of Example 2 of JP-A-8-227117. Particle surface area is 5.
In ^{15 × 10 2 m 2 / molAg} , more saturation coverage is 1.07 × 10 ^-3 mol / molAg of when the dye occupation area as 80 Å ²
Met. Instead of Sensitizing Dyes 2 and 3, SS-1 was added at 1.1 × 10 ⁻³ mol / mol Ag at 56 ° C. and stirred for 30 minutes. ^-3 mol /
molAg was added and stirred for another 20 minutes.
Emulsion 2A (comparative), sensitizing dyes 2 and 3 were chemically sensitized in the same manner as emulsion D of Example 2 of Example-227117.
Instead of (4), 1.1 × 10 ⁻³ mo at 56 ° C.
After adding l / molAg and stirring for 30 minutes, (4) and (2)
7) was stirred for an additional 20 minutes was added each 1.1 × 10 ^-3 mol / molAg, emulsion Emulsion 2B was then subjected to the same chemical sensitization of Emulsion D of Example 2 of JP-A-8-227117 (The present invention). Emulsion 2C (comparative) was prepared after adding SS-1 for the first time and then adding neither SS-1 nor SS-2. The coated sample is disclosed in JP-A-8-2
It was produced in the same manner as the coating sample F of Example 3 of No. 27117. Coated sample F of Example 3 of JP-A-8-227117
Emulsion F of Emulsion 2A was used as a feed 2B and a sample 2C.
The amount of dye adsorbed, the number of adsorbed layers, and the light absorption intensity were determined in the same manner as in Example 1. To examine the sensitivity of the coated sample, use a Fuji FW type photometer (Fuji Photo Film Co., Ltd.) to pass the optical wedge and blue filter on the coated sample.
/ 100 sec. Exposure, and subjected to Fuji Photo Film CN16 processing, and the photographic properties were compared. The sensitivity is represented by the reciprocal of the exposure amount required to give a density of fog + 0.2, and is represented by a relative value based on the sensitivity of Sample 2C.

[0187]

[Table 3]

By using the dye of the present invention, higher adsorption amount, number of adsorbed layers, light absorption intensity and higher spectral sensitivity than the comparative dye can be obtained.

Example 3 A pure odor having a projected area equivalent circular diameter of 0.56 μm was prepared according to the method of preparing an octahedral latent direct positive emulsion described in Example 1 of Japanese Patent Application No. 11-89,801. A silver halide octahedral latent direct positive emulsion was prepared. The specific gravity of this emulsion was 1.10, the silver content was 61.7 g / kg of the emulsion, and the gelatin content was 4.85%. While maintaining the emulsion at 60 ° C,
The first dye shown in Table 4 was added and stirred at 60 ° C. for 30 minutes. Thereafter, the temperature was lowered to 40 ° C, the second dye was added, and the mixture was further stirred at 40 ° C for 20 minutes.

[0190]

[Table 4]

This emulsion was prepared by measuring the amount of sensitizing dye adsorbed in exactly the same manner as described in Example 1 and coating a sample for photographic properties on a cellulose acetate film support. The prepared coated sample was exposed in exactly the same manner as described in Example 1, bleached at 20 ° C. for 3 minutes using the bleaching solution described below,
Development was performed at a temperature of 3 minutes for 30 minutes. The method of determining the sensitivity is represented by the reciprocal of the amount of light required to give an optical density of “coverage +0.1” according to the method described in Example 1, and the sensitivity of the first dye of Comparative Example 4-1 is set to 100. The values are shown as relative values. Table 5 summarizes the obtained results.

<Bleach liquid> Phenosafranine 0.0123 g Hot water 75 ml 後 に After dissolution, water 875 ml red blood salt 3.0 g ──────────────────────────── Add water, 1000 ml <Total developer> Methol 2.2 g Sodium sulfite 96. 0 g Hydroquinone 8.8 g Sodium carbonate monohydrate 56.0 g Potassium bromide 5.0 g Potassium iodide 0.5 g Add water, 1000ml

[0193]

[Table 5]

As shown in Table 5, according to the present invention,
A higher adsorption amount, a higher number of adsorbed layers, and a higher light absorption intensity than the comparative dye were obtained, and a higher spectral sensitivity was obtained.

Example 4 The average projected area of silver bromide grains was obtained according to the method for preparing a hexagonal tabular internal latent image type direct positive emulsion T described in Example 1 of Japanese Patent Application No. 11-89,801. Equivalent circle diameter 2.20μ
A hexagonal tabular internal latent image type silver bromide direct positive emulsion (6-0) having a thickness of 0.38 μm and a thickness of 0.38 μm was prepared. The emulsion was kept at 60 ° C., the first dye shown in Table 6 was added, and the mixture was stirred for 30 minutes, then cooled to 40 ° C., and the nucleating agent 2- {4- [3- (3-phenylthioureido) benzoylamino) was added. Phenyl} -1
0.061 mmol of formylhydrazine was added per mole of silver. Five minutes later, the second dye was added, and the mixture was stirred for 15 minutes to prepare emulsions 6-1 to 6-2. The amount of sensitizing dye adsorbed on these emulsions was measured in exactly the same manner as described in Example 1. Next, Japanese Patent Application No. 11-89,801
No change except that the thirteenth layer was deleted from the comparative photosensitive element 101 described in Example 1 and the emulsion A-1 in the fourteenth layer was replaced with the emulsions 6-1 and 6-2. And Comparative Sample 6-1 and Sample 6-2 of the present invention.

[0196]

[Table 6]

The prepared sample was prepared according to the method described in Japanese Patent Application No. 11-8 / 1999.
Exposure was carried out in exactly the same manner as described in Example 1 of Example 9,801, and after developing and developing at 25 ° C., the transfer magenta density was measured with a color densitometer to determine the sensitivity. The method for determining the sensitivity was performed in exactly the same manner as that described in Example 1 of Japanese Patent Application No. 11-89,801, and the results obtained as relative values with the sensitivity of Sample 6-1 being 100 are summarized in Table 7. Was.

[0198]

[Table 7]

Comparative sample 6-1 did not contain only the first dye. Therefore, the amount of the sensitizing dye added is less than the monolayer saturated adsorption amount, and the light absorption intensity and sensitivity are low. 6-2 of the present invention has higher light absorption intensity and sensitivity than Comparative Sample 6-1. As described above, according to the present invention, a large increase in light absorption intensity and a large increase in sensitivity were obtained even in a photosensitive material having a multilayer structure of a diffusion transfer color system.

Example 5 A similar sample was prepared in accordance with the preparation of the sample 101 of the multi-layer color photographic material described in Example 5 of JP-A-8-29,904. In preparing this sample, Japanese Patent Application Laid-Open No. 8-29,90
The ninth layer emulsion H in Sample 101 of Example 5 of Example 4 was replaced with the emulsion described in Example 1 of the present invention. That is, ExS-4, ExS-5 and Es added in the patent examples.
Sample 8-1 was prepared in the same manner as in Comparative Example 1 except that the addition of xS-6 was omitted. Further, Sample 8-2 was prepared in place of the emulsion prepared in Inventive Example 1B described in Inventive Example 1. The prepared sample is a Fuji FW type sensitometer (Fuji Photo Film Co., Ltd.)
Made by optical wedge and green filter
Exposure was performed for 00 seconds, color development was performed using the same processing steps and processing solution as described in Example 1 of the patent, and the magenta density was measured. The obtained results are summarized in Table 8, and the sensitivity is represented by the reciprocal of the exposure amount required to give the density of “coverage density + 0.2”, and is represented by a relative value based on Sample 8-1.

[0201]

[Table 8]

According to the constitution of the present invention, even when an emulsion in which the adsorption amount of the sensitizing dye is greatly increased as the multilayer adsorption on the surface of the silver halide grain is applied to a negative type multilayer constitution color photosensitive material, As shown in FIG. 8, the sensitivity was significantly increased.

In addition, when applied to various silver halide photographic light-sensitive materials such as a light-sensitive material for X-rays, a color light-sensitive material having an inverted multilayer structure and a color light-sensitive material having a heat-development multilayer structure, Examples 1 to 3, and Almost the same results as the results shown in FIGS.

[0204]

From Examples 1, 2, 3, 4, and 5 of the present invention, it is possible to obtain a high-sensitivity silver halide photographic material in which a sensitizing dye is adsorbed in multiple layers by the sensitizing dye of the present invention. I understand.

Claims (14)

[Claims] 2. The method according to claim 1, wherein the spectral absorption maximum wavelength is less than 500 nm and the light absorption intensity is 30 or more, or the spectral absorption maximum wavelength is 500.
A silver halide photographic emulsion containing silver halide grains having a light absorption intensity of 50 nm or more and a light absorption intensity of 50 or more and containing at least one sensitizing dye other than a cyanine dye. 2. 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
It contains silver halide grains having a light absorption intensity of 100 nm or more and a sensitizing dye other than a cyanine dye of at least 1 nm.
1. A silver halide photographic emulsion comprising: 3. The silver halide photographic emulsion according to claim 1, wherein the sensitizing dye other than the cyanine dye is a merocyanine dye or rhodacyanine dye. The photographic silver halide emulsion described in 1 above. 4. The halogen according to claim 1, wherein the sensitizing dye other than the cyanine dye is a merocyanine dye in the silver halide photographic emulsion according to claim 1, 2 or 3. Silver halide photographic emulsion. 5. The silver halide photographic emulsion according to claim 1, wherein the maximum value of the spectral absorption by the sensitizing dye of the emulsion is 50% of Amax. 5. The silver halide photographic emulsion according to claim 1, wherein a wavelength interval between the shortest wavelength and the longest wavelength is 120 nm or less. 6. The silver halide photographic emulsion according to claim 1, wherein the maximum value of the spectral absorption by a sensitizing dye of the emulsion is 80% of Amax. The wavelength interval between the shortest wavelength and the longest wavelength is 20 nm or more, and the wavelength interval between the shortest wavelength and the longest wavelength which shows 50% of Amax is 120 nm or less. Or the silver halide photographic emulsion according to 4. 7. The silver halide photographic emulsion according to claim 1, wherein when the maximum value of the spectral sensitivity of the emulsion by a sensitizing dye is Smax, 50% of Smax is obtained. 5. The silver halide photographic emulsion according to claim 1, wherein the wavelength interval between the short wavelength and the longest wavelength is 120 nm or less. 8. The silver halide photographic emulsion according to claim 1, wherein when the maximum value of the spectral sensitivity of the emulsion by a sensitizing dye is Smax, 80% of Smax is obtained. The wavelength interval between the shortest wavelength and the longest wavelength is 20 nm or more, and the wavelength interval between the shortest wavelength and the longest wavelength, which represents 50% of Smax, is 120 nm or less. Or the silver halide photographic emulsion according to 4. 9. The silver halide photographic emulsion according to claim 5, wherein the longest wavelength having a spectral absorption of 50% of Amax is from 460 nm to 510 nm, or 560 n.
7. The silver halide photographic emulsion according to claim 5, wherein the range is from m to 610 nm, or from 640 to 730 nm. 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 n.
9. The silver halide photographic emulsion according to claim 7, wherein the range is from m to 610 nm, or from 640 nm to 730 nm. 11. A sensitizing dye having multiple layers adsorbed on the surface of silver halide grains, and the structure of the sensitizing dye other than cyanine in the second layer is different from the sensitizing dye other than cyanine in the first layer. And the sensitizing dye other than cyanine in the second layer contains both a cationic dye and an anionic dye. Or 1
0. The silver halide photographic emulsion described in 0. 12. The method of claim 1, 2, 3, 4, 5, 6, 7,
The silver halide grains of the silver halide photographic emulsion according to 8, 9, 10, or 11, wherein the silver halide grains are tabular grains having an aspect ratio of 2 or more.
12. The silver halide photographic emulsion according to 6, 7, 8, 9, 10, or 11. 13. The method of claim 1, 2, 3, 4, 5, 6, 7,
The silver halide grains of the silver halide photographic emulsion according to claim 8, 9, 10, 11, or 12, wherein the silver halide grains are selenium-sensitized. 7,
13. The silver halide photographic emulsion according to 8, 9, 10, 11 or 12. 14. A silver halide photographic light-sensitive material containing at least one silver halide photographic emulsion layer, wherein the silver halide photographic light-sensitive material comprises at least one silver halide photographic emulsion layer.
13. A silver halide photographic light-sensitive material comprising the silver halide photographic emulsion described in 1, 12, or 13.