DE60031203T2 - Silver halide photographic emulsion and photographic photosensitive material using the same - Google Patents

Abstract

A silver halide photographic emulsion is disclosed, comprising a silver halide grain having a spectral absorption maximum wavelength of less than 500 nm and a light absorption intensity of 60 or more or having a spectral absorption maximum wavelength of 500 nm or more and a light absorption intensity of 100 or more, wherein assuming that a maximum value of the spectral absorption factor of said emulsion by a sensitizing dye is Amax, the distance between the shortest wavelength showing 80% of Amax and the longest wavelength showing 80% of Amax is 20 nm or more and the distance between the shortest wavelength showing 50% of Amax and the longest wavelength showing 50% of Amax is 120 nm or less.

Description

Territory of invention

The The present invention relates to a spectrally sensitized photographic Silver halide emulsion and a photographic photosensitive Material in which the emulsion is used.

background the invention

So far Many efforts have been made to achieve higher sensitivity photographic silver halide photosensitive materials to reach. In a photographic silver halide emulsion absorbs a sensitizing dye which is attached to the surface of a Silberhalogenidkorns is absorbed, light in the photosensitive Material penetrates, and transmits the light energy to the silver halide grain, whereby sensitivity is achieved can. Accordingly, in the spectral sensitization of Silver halide believed that the transferred to the silver halide Light energy by increasing of the light absorption factor per unit grain surface of a Silver halide grain increased can be and thereby increases the spectral sensitivity can be. The light absorption factor on the surface of a Silver halide grain can be obtained by increasing the amount of a spectral sensitizing dye, the per unit grain surface is absorbed, increased.

however is the amount of one on the surface of a silver halide grain adsorbed sensitizing dye limited, and the dye chromophore can not over a single-layer saturation adsorption (namely single layer adsorption). Therefore point currently individual silver halide grains have a low absorption factor with respect to the amount of the incident light in the spectral sensitization region on.

Around to solve these problems the following methods have been proposed.

In Photographic Science and Engineering, Vol. 20, No. 3, page 97 (1976), P.B. Gilman, Jr. et al. is a technique disclosed in which cationic dye is adsorbed to the first layer and a anionic dye to the second layer using the electrostatic force is adsorbed.

In U.S. Patent 3,622,316 discloses G. B. Bird et al. a technique in a variety of dyes in multiple layers of silver halide is adsorbed and the excitation energy transfer from the Forster type contribute to raising awareness.

In JP-A-63-138341 (the term "JP-A" as used herein) is an "unaudited published Japanese patent application ") and JP-A-64-84244 disclose Sugimoto et al. a technique in which spectral sensitization using energy transfer is performed by a light-emitting dye.

In Photographic Science and Engineering, Vol. 27, No. 2, page 59 (1983) disclose R. Steiger et al. a technique in which the spectral Sensitization using energy transfer from a gelatin-substituted Cyanine dye performed becomes.

In JP-A-61-251842 disclose Ikegawa et al. a technique in which the Spectral sensitization using energy transfer is carried out by a cyclodextrin-substituted dye.

In Referring to the so-called linked Dye having two separate chromophores that are not conjugated, but are linked by a covalent bond are examples thereof in U.S. Patents 2,393,351, 2,425,772, 2,518,732, 2,521,944 and U.S. Pat 2,592,196 and the European Patent 565,083. However, these are not used to improve the light absorption factor. In U.S. Patents 3,622,317 and 3,976,493, which aim to increase the light absorption factor G.B. Bird, A.L. Borror et al. a technique in the one molecule a linked one Sensitizing dye containing a variety of cyanine chromophores is adsorbed to increase the light absorption factor, and the energy transfer can contribute to the sensitization. In JP-A-64-91134 disclose Ukai, Okazaki and Sugimoto a technique in which at least one im essential non-adsorptive dye, such as a cyanine dye, Merocyanine dye and hemicyanine dye containing at least two Sulfo and / or carboxyl groups, to a sensitizing dye, which can adsorb to silver halide is bound.

In JP-A-6-57235 discloses to L.C. Vishwakarma a method of manufacturing a linked one Dye by a dehydration condensation reaction of two Dyes. Further, JP-A-6-27578 discloses that the linked dye from monomethine cyanine and pentamethine oxonol has red sensitivity. However, overlap in this case, the light emission of oxonol and the absorption of Cyanine does not, and the spectral sensitization using the excitation energy transfer The Forster type does not occur, resulting in failure to reach high sensitivity due to the light collecting effect of linked Oxonols leads.

In EP 887700A1 disclose RL Parton et al. a linked dye having a specific linking group.

In U.S. Patent 4,950,587 discloses M.R. Roberts et al. the spectral Sensitization by means of a cyanine dye polymer.

Consequently So far, many studies have been made to improve the light absorption factor Have been carried out. However, not enough effect on the improvement of the light absorption factor can be achieved, and neither can sufficiently high sensitivity can be achieved.

Especially For color-sensitive materials, the spectral sensitivity be designed to be within a target wavelength range falls. The spectral sensitization of a silver halide photosensitive material usually uses not the absorption of the sensitizing dye in the monomer state from, but takes advantage of the J-band, which is formed when the dye to the surface of a Silberhalogenidkorns is adsorbed. The J band is very useful for Set up the light absorption and the spectral sensitivity in a desired Wavelength range, because it has an absorption that is acutely shifted to the side of longer wavelengths is as in the monomer state. This means that, even if a sensitizing dye is adsorbed on the grain surface in multiple layers is and thus the light absorption factor can be increased, the absorption over a extends very broad range when indirectly to a Silberhalogenidkorn adsorbed dye, namely the dye in the second or subsequent layer, in the monomer state is adsorbed and this is called spectral sensitivity of a given photosensitive material inappropriate.

on the other hand Each color sensitizing region has a width of about 100 nm, and it is disadvantageous, unnecessarily large difference in sensitivity across from To cause light in this area.

Under these circumstances is a technique desired in which a sensitizing dye in several layers to the surface of a silver halide grain adsorbing the requirements fulfill can increase the integrated light absorption intensity per unit grain surface, the absorption and the spectral sensitivity to a desired Color sensitization are limited and that at the same time the change the spectral absorption factor and the sensitivity with respect reduced to light in this area as much as possible.

It it was further found that when a sensitizing dye is adsorbed on the grain surface in several layers, the Amount of adsorbed gelatin reduced; as a result decreases the protective colloid function, and in some cases the grains easily coagulate. Accordingly, a technique is desired in which a sensitizing dye is adsorbed in multiple layers, with the occurrence of coagulation the grains is avoided.

Summary the invention

It It is an object of the present invention to provide a photographic Silver halide emulsion available in which coagulation of grains is avoided and the has a high sensitivity.

It Another object of the present invention is a photographic one to provide photosensitive material in which the emulsion is used.

• (1) Photographische Silberhalogenidemulsion, die ein Silberhalogenidkorn mit einer Wellenlänge des spektralen Absorptionsmaximums von 500 nm oder mehr und einer Lichtabsorptionsintensität von 100 oder mehr umfasst, worin unter der Annahme, dass der maximale Wert des spektralen Absorptionsfaktors der Emulsion durch einen Sensibilisierungsfarbstoff Amax ist, der Abstand zwischen der kürzesten Wellenlänge, die 80% von Amax zeigt, und der längsten Wellenlänge, die 80% von Amax zeigt, 20 nm oder mehr ist und der Abstand zwischen der kürzesten Wellenlänge, die 50% von Amax zeigt, und der längsten Wellenlänge, die 50% von Amax zeigt, 120 nm oder weniger ist, und worin die photographische Silberhalogenidemulsion mehrschichtig adsorbierte Sensibilisierungsfarbstoffschichten aufweist und der Farbstoff in der zweiten oder nachfolgenden Schicht in den mehrschichtig adsorbierten Farbstoffschichten ein J-Aggregat bildet.
• (2) Photographische Silberhalogenidemulsion, die ein Silberhalogenidkorn mit einer Wellenlänge des spektralen Absorptionsmaximums von 500 nm oder mehr und einer Lichtabsorptionsintensität von 100 oder mehr umfasst, worin unter der Annahme, dass der maximale Wert der spektralen Empfindlichkeit der Emulsion durch einen Sensibilisierungsfarbstoff Smax ist, der Abstand zwischen der kürzesten Wellenlänge, die 80% von Smax zeigt, und der längsten Wellenlänge, die 80% von Smax zeigt, 20 nm oder mehr ist und der Abstand zwischen der kürzesten Wellenlänge, die 50% von Smax zeigt, und der längsten Wellenlänge, die 50% von Smax zeigt, 120 nm oder weniger ist, und worin die photographische Silberhalogenidemulsion mehrschichtig adsorbierte Sensibilisierungsfarbstoffschichten aufweist und der Farbstoff in der zweiten oder nachfolgenden Schicht in den mehrschichtig adsorbierten Farbstoffschichten ein J-Aggregat bildet.
• (3) Photographische Silberhalogenidemulsion gemäß Punkt 1, worin die längste Wellenlänge, die einen spektralen Absorptionsfaktor von 50% von Amax zeigt, im Bereich von 500 bis 510 nm, von 560 bis 610 nm oder von 640 bis 730 nm liegt.
• (4) Photographische Silberhalogenidemulsion gemäß Punkt 2, worin die längste Wellenlänge, die eine spektrale Empfindlichkeit von 50% von Smax zeigt, im Bereich von 500 bis 510 nm, von 560 bis 610 nm oder von 640 bis 730 nm liegt.
• (5) Photographische Silberhalogenidemulsion gemäß irgendeinem der Punkte 1, 2, 3 oder 4, worin die Silberhalogenidemulsion einen Farbstoff mit wenigstens einer aromatischen Gruppe enthält.
• (6) Photographische Silberhalogenidemulsion gemäß Punkt 1 oder 2, worin die Wellenlänge des Absorptionsmaximums des Farbstoffchromophors in der ersten Schicht in den mehrschichtig adsorbierten Farbstoffschichten länger als diejenige des Farbstoffchromophors in der zweiten oder nachfolgenden Schicht in den mehrschichtig adsorbierten Farbstoffschichten ist.
• (7) Photographische Silberhalogenidemulsion gemäß Punkt 1 oder 2, worin der Farbstoff in der zweiten oder nachfolgenden Schicht eine vom Farbstoff in der ersten Schicht in den mehrschichtig adsorbierten Farbstoffschichten unterschiedliche Struktur hat und die zweite oder nachfolgende Schicht sowohl einen kationischen als auch einen anionischen Farbstoff enthält.
• (8) Photographische Silberhalogenidemulsion gemäß einem der Punkte 1 bis 7, die einen Sensibilisierungsfarbstoff mit einem Grundkern enthält, der durch die Kondensation von drei oder mehr Ringen gebildet wird.
• (9) Photographische Silberhalogenidemulsion gemäß einem der Punkte 1 bis 8, worin das Silberhalogenidkorn mit einer Wellenlänge des spektralen Absorptionsmaximums von 500 nm oder mehr und einer Lichtabsorptionsintensität von 100 oder mehr ein tafelförmiges Korn mit einem Seitenverhältnis von 2 oder mehr ist.
• (10) Photographische Silberhalogenidemulsion gemäß einem der Punkte 1 bis 9, worin das Silberhalogenidkorn mit einer Wellenlänge des spektralen Absorptionsmaximums von 500 nm oder mehr und einer Lichtabsorptionsintensität von 100 oder mehr einer Selensensibilisierung unterworfen ist.
• (11) Photographisches lichtempfindliches Silberhalogenidmaterial, das wenigstens eine photographische Silberhalogenidemulsion umfasst, die eine in irgendeinem der Punkte 1 bis 10 beschriebene photographische Silberhalogenidemulsion enthält.

These tasks were solved by the following means.

• (1) A silver halide photographic emulsion comprising a silver halide grain having a wavelength of the absorption maximum of 500 nm or more and a light absorption intensity of 100 or wherein, assuming that the maximum value of the spectral absorption factor of the emulsion by a sensitizing dye is Amax, the distance between the shortest wavelength showing 80% of Amax and the longest wavelength showing 80% of Amax is 20 nm or more, and the distance between the shortest wavelength showing 50% of Amax and the longest wavelength showing 50% of Amax is 120 nm or less, and wherein the photographic silver halide emulsion has multi-layer adsorbed sensitizing dye layers and the dye in the second or subsequent layer in the multi-layer adsorbed dye layers forms a J-aggregate.
• (2) A silver halide photographic emulsion comprising a silver halide grain having a wavelength of the spectral absorption maximum of 500 nm or more and a light absorption intensity of 100 or more, wherein, assuming that the maximum value of the spectral sensitivity of the emulsion by a sensitizing dye is Smax Distance between the shortest wavelength showing 80% of Smax and the longest wavelength showing 80% of Smax being 20 nm or more and the distance between the shortest wavelength showing 50% of Smax and the longest wavelength which is 50% of Smax, 120 nm or less, and wherein the photographic silver halide emulsion has multi-layer adsorbed sensitizing dye layers and the dye forms a J aggregate in the second or subsequent layer in the multi-layer adsorbed dye layers.
• (3) The photographic silver halide emulsion according to item 1, wherein the longest wavelength showing a spectral absorption factor of 50% of Amax is in the range of 500 to 510 nm, 560 to 610 nm or 640 to 730 nm.
• (4) The silver halide photographic emulsion according to item 2, wherein the longest wavelength showing a spectral sensitivity of 50% of Smax is in the range of 500 to 510 nm, 560 to 610 nm or 640 to 730 nm.
• (5) The photographic silver halide emulsion according to any one of items 1, 2, 3 or 4, wherein the silver halide emulsion contains a dye having at least one aromatic group.
• (6) The silver halide photographic emulsion according to item 1 or 2, wherein the wavelength of absorption maximum of the dye chromophore in the first layer in the multi-layer adsorbed dye layers is longer than that of the dye chromophore in the second or subsequent layer in the multi-layer adsorbed dye layers.
• (7) The photographic silver halide emulsion according to item 1 or 2, wherein the dye in the second or subsequent layer has a different structure from the dye in the first layer in the multi-layer adsorbed dye layers and the second or subsequent layer contains both a cationic and an anionic dye ,
• (8) The silver halide photographic emulsion according to any one of items 1 to 7, which contains a sensitizing dye having a base nucleus formed by the condensation of three or more rings.
• (9) The silver halide photographic emulsion according to any one of items 1 to 8, wherein the silver halide grain having a wavelength of the spectral absorption maximum of 500 nm or more and a light absorption intensity of 100 or more is a tabular grain having an aspect ratio of 2 or more.
• (10) The silver halide photographic emulsion according to any one of items 1 to 9, wherein the silver halide grain having a wavelength of the spectral absorption maximum of 500 nm or more and a light absorption intensity of 100 or more is subjected to selenium sensitization.
• (11) A silver halide photographic light-sensitive material comprising at least one photographic silver halide emulsion containing a photographic silver halide emulsion described in any one of items 1 to 10.

Short description the drawings

1 shows a spectral absorption spectrum of only one dye. R: Infinite diffusion reflectance of a dye-absorbed emulsion. (1 - R) ² / 2R is proportional to the absorption factor.

2 shows a spectral sensitivity distribution. E: The exposure amount necessary to obtain a density of fog +0.2.

Precise description the invention

The The present invention will be described below in detail.

The present invention is a silver halide photographic light-sensitive material using a silver halide grain sensitized by a dye and having a large silver halide grain Having light absorption intensity, a spectral absorption waveform, and an appropriate sensitivity distribution.

In the present invention, the light absorption intensity is the integrated intensity of light absorption by a sensitizing dye per unit grain surface, and is defined as a value obtained on the assumption that the amount of light entering the unit surface of a grain is ₀ and that of a sensitizing dye the amount of light I absorbed on the surface is integrated by integrating the optical density Log (I ₀ / (I ₀ -I)) with respect to the wavenumber (cm ^-1 ). The integration range is from 5,000 cm ^-1 to 35,000 cm ^-1 .

in the Case of a silver halide grain having a wavelength of spectral absorption maximum of 500 nm or more contains the photographic invention Silver halide emulsion, preferably a silver halide grain a light absorption intensity of 100 or more in a proportion of half or more of the total projection all silver halide grains. In the case of a grain having a wavelength of the spectral absorption maximum of 500 nm or more the light absorption intensity preferably 150 or more, stronger preferably 170 or more, above In addition, 200 or more is preferable. The upper limit is not special limited, is but preferably 2,000 or less, more preferably 1,000 or less, about that In addition, 500 or less is preferable.

An example of a method of measuring the light absorption intensity is a measuring method using a microspectrophotometer. The microspectrophotometer is a device capable of measuring an absorption spectrum of a microscopic range and measuring the transmission spectrum of a grain. The measurement of the absorption spectrum of a grain by microspectrometry is described in the report by Yamashita et al. (Nippon Shashin Gakkai, 1996 Nendo Nenji Taikai Ko'en Yoshi Shu (Lecture Summary at Annual Meeting of Japan Photographic Association in 1996), page 15). From this absorption spectrum, the absorption intensity per grain can be obtained. However, the light passing through the grain is absorbed on two surfaces, the upper surface and the lower surface. Therefore, the absorption intensity per unit area of the grain surface can be obtained as half (1/2) of the absorption intensity per grain obtained by the method described above. At this time, the absorption spectrum integration segment is definable to be from 5,000 to 35,000 cm ^-1 . However, in experiments, the segment for integration may contain the range of 500 cm ^-1 shorter or longer than the segment having the absorption by the sensitizing dye.

The Light absorption intensity can also be obtained by not using microspectrometry but uses a method in which grains are aligned, wherein it avoids the grains lie on top of each other and measure the transmission spectrum.

The Light absorption intensity is a value indistinguishable from the oscillator strength of the sensitizing dye and the number of molecules, the per unit area are adsorbed, is determined. Therefore, it might be possible to determine the oscillator strength of the Sensitizing dye, the adsorbed amount of the dye and the surface to obtain the grain and convert it into the light absorption intensity.

The oscillatory strength of a sensitizing dye can be obtained experimentally as a value proportional to the integrated absorption intensity (optical density × cm ^-1 ) of a solution of a sensitizing dye. Therefore, assuming that the integrated absorption intensity of a dye is 1 MA (optical density × cm ^-1 ), the amount of adsorbed sensitizing dye B can be (mol / mol-Ag) and the surface of grain C (m ² / mol -Ag), the light absorption intensity is obtained in accordance with the following equation within an error range of about 10%: 0.156 × A × B / C.

The light absorption intensity calculated with this equation is substantially the same as the light absorption intensity based on the above-described definition (a value obtained by integrating Log (I ₀ / (I ₀ -I)) with respect to the wavenumber (cm -1) ^{. 1} )).

For increasing the light absorption intensity, a method in which a dye chromophore in one or more layers is adsorbed on the grain surface, a method in which the molecular extinction coefficient of the dye is increased, and a method in which the dye occupation area is reduced can be used. Any of these methods may be used, but the Ver in which a dye chromophore is adsorbed in one or more layers on the grain surface is preferred.

Here in denotes the state in which a dye chromophore in a or more layers adsorbed on the grain surface, that the in the vicinity of a Silberhalogenidkorns bound dye in one or more layers is present. Dyes in the dispersion medium are not of this dye includes. Also, the case where a dye chromophore with a substance is connected to the grain surface through a covalent bond is adsorbed, not as adsorption in one or more layers because the linking group is long if the dye chromophore in the dispersion medium is present, and the effect of increasing the light absorption intensity is small is. In the case of a so-called multi-layer adsorption, wherein a Dye chromophore adsorbed in one or more layers on the grain surface it is necessary that spectral sensitization by the Dye is generated, which does not adsorb directly to the grain surface is, and that the excitation energy of the dye, not directly adsorbed to the silver halide, to the dye, which is adsorbed directly to a grain is transmitted. In this sense is the transmission of excitation energy, which must necessarily run over 10 steps, not preferred, because the transmission efficiency the excitation energy is reduced. An example of such a case is a polymer dye described in JP-A-2-113239, wherein a plurality of dye chromophores in a dispersion medium are present and transmit the excitation energy over 10 steps must become.

In of the present invention the number of steps that are necessary to allow the dye one Color forms, per molecule preferably 1 to 3.

The "chromophore" as used herein is in Rikagaku Jiten (Physicochemical Dictionary), pages 985-986, 4th Edition, Iwanami Shoten (1987) defines and designates one atomic group, which is the main cause of the absorption band of a molecule acts. Any chromophore, e.g. an atomic group that an unsaturated one Binding, such as C = C or N = N, are used.

Examples of these include 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 dyes, croconium dyes, Azomethine dyes, Coumarin dyes, allylide dyes, anthraquinone dyes, Triphenylmethine dyes, azo dyes, Azomethine dyes, spiro compounds, metallocene dyes, Fluorenone dyes, fulgide dyes, Perylene dyes, phenazine dyes, phenothiazine dyes, Quinone dyes, indigo dyes, Diphenylmethane dyes, polyene dyes, acridine dyes, Acridinone dyes, diphenylamine dyes, quinacridone dyes, Quinophthalone dyes, phenoxazine dyes, phthaloperylene dyes, Porphyrin dyes, Chlorophilic dyes, phthalocyanine dyes and metal complex dyes.

From these are 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 dyes, Croconium dyes and polymethine chromophores, such as azamethine dyes, Cyanine dyes, merocyanine dyes, trinuclear merocyanine dyes, tetranuclear merocyanine dyes and rhodacyanine dyes stronger preferred, and cyanine dyes, merocyanine dyes and rhodacyanine dyes are still stronger preferred, and cyanine dyes are most preferred.

These Dyes are described in detail in F.M. Harmer, Heterocyclic Compounds-Cyanine Dyes and Related Compounds, John Wiley & Sons (1964), D.M. Sturmer, Heterocyclic Compounds - Special topics in heterocyclic chemistry, Chapter 18, Section 14, pp. 482-515. For the Cyanine dyes, merocyanine dyes and rhodacyanine dyes are the formulas (XI), (XII) and (XIII) described in US Patent 5,340,694, Columns 21 to 22, on the condition that prefers the numbers from n12, n15, n17 and n18 are not limited and each one whole Number is 0 or more (preferably 4 or less).

The Dye chromophore adsorbed to a silver halide grain is preferred in 1.5 or more layers, stronger preferably 1.7 or more layers, more preferably 2 or more Layers available. The upper limit of the number of layers is not special limited, however, is preferably 10 or less layers, more preferably 5 or less Layers.

In In the present invention, the state in which a chromophore means in one or more layers on the surface of a silver halide grain is adsorbed, that when the saturation adsorption, the through a dye with the smallest dye loading area a silver halide grain surface of reached to an emulsion added sensitizing dyes is, as a single-layer saturation coverage is defined, the adsorption amount of dye chromophore per unit layer, based on the single-layer saturation coverage, is great. The adsorption layer number refers to the adsorption amount, based on the single-layer saturation coverage. In the case of a dye in which dye chromophores by a covalent bond, the adsorption layer number on the dye-applying surface of the individual dyes in the state in which these dye chromophores not connected, be related.

The Dye occupying area may consist of an adsorption isotherm, which is the relationship between the free dye concentration and the dye adsorption amount shows, and the grain surface to be obtained. The adsorption isotherm may be e.g. in reference to to A. Herz et al., Adsorption from Aqueous Solution, Advances in chemistry Series, no. 17, page 173 (1968).

To the Determining the amount of a sensitizing dye attached to a Emulsion layer is adsorbed, two methods can be used be, namely One is a process in which an emulsion to which a dye is added is adsorbed, centrifuged to the emulsion grains of the supernatant aqueous gelatin solution to separate, the spectral absorption of the supernatant is measured to to obtain the concentration of unadsorbed dye, the concentration subtracted from the amount of dye added and thereby determining the dye adsorption amount, and another is a method in which precipitated emulsion grains are dried be a predetermined weight of the precipitate in a 1: 1 mixed solution of aqueous sodium thiosulfate and methanol dissolved is measured, the spectral absorption and thereby the Farbstoffadsorptionsmenge is determined. When a variety of dyes are used, The adsorption amount of the individual dyes can also be through a means, such as high-speed liquid chromatography, to be obtained. The method for determining the dye adsorption amount by quantifying the amount of the dye in the supernatant is e.g. in W. West et al., Journal of Physical Chemistry, Vol 56, page 1054 (1952). However, under conditions, at where the added amount of the dye is large, even non-adsorbed Dyes fail, and an accurate determination of the adsorption amount can by the method for quantifying the dye concentration in the supernatant can not be obtained. On the other hand, in accordance with the method, in which precipitated silver halide grains are dissolved and the dye adsorption amount is measured is the amount of only the dye adsorbed to the grains can be determined precisely because the emulsion grain has a far greater precipitation rate and with grains precipitated dye can be easily separated. This method is the most reliable for determining the dye adsorption amount.

When an example of the methods for measuring the surface of a silver halide grain For example, a method may be used in which a transmission electron micrograph Photography is taken by a replica process and the shape and the size of individual grains is calculated. In this case, the thickness of a tabular grain becomes from the length of the shadow of the replica. The transmission electron microscopic Photography may e.g. referring to Denshi Kenbikyo Shiryo Gijutsu Shu (Electron Microscopic Sample Technologies), Nippon Denshi Kenbikyo Gakkai Kanto Shibu (compiler), Seibundo Shinko Sha (1970), P. B. Hirsch et al., Electron Microscopy of Thin Crystals, Butterworths, London (1965).

Other Examples of the methods of measurement are in A.M. Kragin et al., The Journal of Photographic Science, Vol. 14, p. 185 (1966), J.F. Paddy, Transactions of the Faraday Society, Vol. 60, p. 1325 (1964), S. Boyer et al., Journal of Chemistry Physique et de Physicochimie Biologique, Vol. 63, page 1123 (1963), W. West et al., Journal of Physical Chemistry, Volume 56, page 1054 (1952), E. Klein et al., International Coloquium, compiled by H. Sauvernier and Scientific Photography, Liege (1959).

The dye-occupying area of individual grains can be experimentally determined by the methods described above, but the molecular occupation area of the sensitizing dyes which are usually used is usually 80 Å ² . Therefore, the Adsorptionsschichtzahl can be roughly estimated by a simple method by using the dye occupation area is counted as 80 a ^2.

In the present invention, when a dye chromophore is adsorbed on a silver halide grain in multiple layers, the dye chromophore that adsorbs directly to the silver halide grain can be adsorbed That is, the dye chromophore in the first layer and the dye chromophores in the second and subsequent layers have any reduction potential and oxidation potential. However, the reduction potential of the dye chromophore in the first layer is preferably more positive than the value obtained by subtracting 0.2 V from the reduction potential of the dye chromophore in the second or subsequent layer.

The Reduction potential and the oxidation potential can be due to different Method to be measured. However, these are preferably by second phase-distinction type harmonic alternating polarography to determine the exact values measured. The method for determining of potential through second harmonic alternating current polarography of the phase discrimination type is in Journal of Imaging Science, Volume 30, page 27 (1986).

The Dye chromophore in the second or subsequent layer is preferred a light-emitting dye. The light-emitting dye preferably has a backbone (i.e., a basic structure) of dyes for Dye laser can be used. These are e.g. in Mitsuo Maeda, Laser Kenkyu (Study of Laser), Volume 8, page 694, page 803 and Page 958 (1980), as well as volume 9, page 85 (1981) and F. Shaefer, Dye Lasers, Springer (1973).

The wavelength the absorption maximum of the dye chromophore in the first layer in a silver halide photographic light-sensitive material is preferably longer as the wavelength the absorption maximum of the dye chromophore in the second or following layer. Furthermore, overlaps the light emission of the dye chromophore in the second or following Layer preferably with the absorption of the dye chromophore in the first shift. additionally Preferably, the dye chromophore forms in the first layer a J-association product (i.e., a J-aggregate). To absorption and spectral sensitivity in a desired wavelength range The dye chromophores also form in the second and subsequent layers prefer a J-association product.

The Meanings of the terms used in the present invention described below.

Dye occupation area:

Occupancy area per one molecule of dye. This can be determined experimentally from the adsorption isotherm. In the case of a dye in which dye chromophores are linked by a covalent bond, the area is determined based on the dye occupation area of the individual, unjoined dyes. Simply speaking, 80 Å ² .

Single layer saturation coverage:

dye adsorption per unit grain surface at the time of monolayer saturation coverage. A reciprocal Value of the minimum dye occupation area of the added dyes.

Multischichtadsorption:

One State in which the adsorption amount of dye chromophores each Unit grain surface greater than the single-layer saturation coverage is.

Adsoroptionsschichtzahl:

adsorption of dye chromophores per unit grain surface area, based on the single-layer saturation coverage.

In the emulsion containing a photographic silver halide emulsion grain with a light absorption intensity contains 60 or more or 100 or more, the distance between the shortest Wavelength, the 50% of the maximum value Amax of the spectral absorption factor of a sensitizing dye and 50% of a maximum value Smax shows the spectral sensitivity, and the longest wavelength, the Shows 50% of Amax and 50% of Smax, preferably 120 nm or less, stronger preferably 100 nm or less.

The distance between the shortest wavelength showing 80% of Amax and 80% of Smax, and The longest wavelength showing 80% of Amax and 80% of Smax is 20 nm or more, and is preferably 100 nm or less, more preferably 80 nm or less, still more preferably 50 nm or less.

Of the Distance between the shortest Wavelength, which shows 20% of Amax and which shows 20% of Smax, and the longest wavelength, the 20% of Amax and 20% of Smax, is preferably 180 nm or less, stronger preferably 150 nm or less, more preferably 120 nm or more less, and the strongest preferably 100 nm or less.

The longest Wavelength, which shows 50% of Amax and 50% of Smax, is preferably 500 to 510 nm, from 560 nm to 610 nm or from 640 to 730 nm.

To the Realizing a silver halide grain having a wavelength of the spectral absorption maximum of 500 nm or more and a light absorption intensity of 100 or more, a first preferred method is a method in which a specific dye described below is used.

To the Example is a method in which a dye with an aromatic Group or a cationic dye having an aromatic group and an anionic dye can be used in combination in JP-A-10-239789, JP-A-8-269009, JP-A-10-123650 and JP-A-8-328189, a process in which a dye with a polyvalent electric Charge described in JP-A-10-171058 is used, a method in which a dye having a pyridinium group described in JP-A-10-104774, a method in which a dye with a hydrophobic group described in JP-A-10-186559 and a method in which a dye is bound with a coordinate Group described in JP-A-10-197980 is preferred.

From this is a process in which a dye with at least one aromatic group is used, preferably, and a method in which only a positively charged dye, a dye with within of the molecule balanced electric charge or a dye without electrical Charge is used, or a process by a positively charged Dye and a negatively charged dye used in combination wherein at least one of the positively charged dye and the negatively charged dye is a dye which is at least has an aromatic group as a substituent, more preferable.

The Aromatic group will be described in detail below. The aromatic Group includes an aromatic hydrocarbon group and a aromatic heterocyclic group. The group can be a polycyclic Condensation structure by condensing an aromatic Hydrocarbon rings and an aromatic heterocyclic ring or a polycyclic condensation structure, by combining an aromatic hydrocarbon group and an aromatic heterocyclic ring, and it may be substituted with a substituent V described later will be. Examples of the aromatic ring preferred in of the aromatic group include benzene, naphthalene, Anthracene, phenanthrene, fluorene, triphenylene, naphthacene, biphenyl, Pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyridine, pyrazine, Pyrimidine, pyridazine, indolizine, indole, benzofuran, benzothiophene, Isobenzofuran, quinolizine, quinoline, phthalazine, naphthylidine, quinoxaline, Quinoxazoline, quinoline, carbazole, phenanthridine, acridine, phenanthroline, Thianthrene, chromene, xanthene, phenoxathine, phenothiazine and phenazine.

From these are the aromatic hydrocarbon rings preferred, benzene and naphthalene are stronger preferred, and benzene is the strongest prefers.

Examples of the dye include the dyes exemplified above of the dye chromophore are described. Of these, the dyes are preferred as above as examples of the polymethine dye chromophore are described.

More preferred are 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 Dyes, Croconium Dyes and Azamethine Dyes, still stronger preferred are cyanine dyes, merocyanine dyes, trinuclear merocyanine dyes, tetranuclear merocyanine dyes and rhodacyanine dyes, especially preferred are cyanine dyes, merocyanine dyes and rhodacyanine dyes, and the strongest preferred are cyanine dyes.

The particularly preferred methods are detailed below Reference is made to structural formulas.

• (1) Ein Verfahren, in dem zumindest ein kationischer, Betain- oder nichtionischer Methin-Farbstoff, dargestellt durch die folgende Formel (I), verwendet wird; und
• (2) Ein Verfahren, in dem simultan zumindest ein kationischer Methin-Farbstoff, dargestellt durch die folgende Formel (I), und zumindest ein anionischer Methin-Farbstoff, dargestellt durch die folgende Formel (II), verwendet werden:
  
  worin Z₁ eine atomare Gruppe darstellt, die zum Bilden eines stickstoffhaltigen heterocyclischen Rings notwendig ist, vorausgesetzt, dass der Ring ferner mit Z₁ kondensiert sein kann, R₁ eine Alkylgruppe, eine Arylgruppe oder eine heterocyclische Gruppe darstellt, Q₁ eine Gruppe darstellt, die notwendig ist, um es der durch die Formel (I) dargestellten Verbindung zu ermöglichen, einen Methin-Farbstoff zu bilden, L₁ und L₂ jeweils eine Methingruppe darstellen, p₁ 0 oder 1 darstellt, vorausgesetzt, dass Z₁, R₁, Q₁, L₁ und L₂ jeweils einen Substituenten aufweisen, der es dem durch die Formel (I) dargestellten Methin-Farbstoff als Ganzem erlauben, einen kationischen Farbstoff, einen Betain-Farbstoff oder einen nichtionischen Farbstoff zu bilden, und wenn die Formel (I) ein Cyanin-Farbstoff oder ein Rhodacyanin-Farbstoff ist, Z₁, R₁, Q₁, L₁ und L₂ jeweils bevorzugt einen Substituenten aufweisen, der es dem durch die Formel (I) dargestellten Methin-Farbstoff als Ganzem ermöglich, einen kationischen Farbstoff zu bilden, M₁ ein Gegenion zum Ausgleichen der elektrischen Ladung darstellt, und m₁ eine ganze Zahl von 0 oder mehr darstellt, die zum Neutralisieren der elektrischen Ladung des Moleküls notwendig ist;
  
  worin Z₂ eine atomare Gruppe darstellt, die zum Bilden eines stickstoffhaltigen heterocyclischen Ringes notwendig ist, vorausgesetzt, dass ein Ring ferner mit Z₂ kondensiert sein kann, R₂ eine Alkylgruppe, eine Arylgruppe oder eine heterocyclische Gruppe darstellt, Q₂ eine Gruppe darstellt, die notwendig ist, um es der durch die Formel (II) dargestellten Verbindung zu ermöglichen, einen Methin-Farbstoff zu bilden, L₃ und L₄ jeweils eine Methingruppe darstellen, p₂ 0 oder 1 darstellt, vorausgesetzt, dass Z₂, R₂, Q₂, L₃ und L₄ jeweils einen Substituenten aufweisen, der es dem durch die Formel (II) dargestellten Methin-Farbstoff als Ganzem ermöglicht, einen anionischen Farbstoff zu bilden, M₂ ein Gegenion zum Ausgleichen der elektrischen Ladung darstellt und m₂ eine ganze Zahl von 0 oder mehr darstellt, die zum Neutralisieren der elektrischen Ladung des Moleküls notwendig ist.

The methods (1) and (2) are preferred. of the methods (1) and (2), the method (2) is more preferable.

• (1) A method in which at least one cationic, betaine or nonionic methine dye represented by the following formula (I) is used; and
• (2) A method in which at least one cationic methine dye represented by the following formula (I) and at least one anionic methine dye represented by the following formula (II) are simultaneously used:
  
  wherein Z _{1 represents} an atomic group necessary for forming a nitrogen-containing heterocyclic ring, provided that the ring may be further condensed with Z ₁ , R _{1 represents} an alkyl group, an aryl group or a heterocyclic group, Q _{1 represents} a group, which is necessary in order to enable the by the formula (I) compound shown to form a methine dye, L ₁ and L ₂ each represent a methine group, p ₁ represents 0 or 1, provided that Z ₁ R, ₁ , Q ₁ , L ₁ and L ₂ each have a substituent which allow the methine dye represented by the formula (I) as a whole to form a cationic dye, a betaine dye or a nonionic dye, and when the formula (I) is a cyanine dye or a rhodacyanine dye, Z ₁ , R ₁ , Q ₁ , L ₁ and L ₂ each preferably have a substituent which satisfies the methine dye represented by the formula (I) as a whole m is capable of forming a cationic dye, M _{1 represents} a counter ion for balancing the electric charge, and m _{1 represents} an integer of 0 or more necessary for neutralizing the electric charge of the molecule;
  
  wherein Z _{2 represents} an atomic group necessary for forming a nitrogen-containing heterocyclic ring, provided that a ring may be further condensed with Z ₂ , R _{2 represents} an alkyl group, an aryl group or a heterocyclic group, Q _{2 represents} a group, which is necessary to allow the compound represented by the formula (II) to form a methine dye, L ₃ and L ₄ each represent a methine group, p _{2 represents} 0 or 1, provided that Z ₂ , R ₂ , Q ₂ , L ₃ and L ₄ each have a substituent which enables the methine dye represented by the formula (II) as a whole to form an anionic dye, M _{2 represents} a counter ion for balancing the electric charge, and m ₂ represents an integer of 0 or more necessary to neutralize the electric charge of the molecule.

When the compound represented by the formula (I) is used alone, R _{1 is} preferably a group having an aromatic ring.

When the compound represented by the formula (I) and the compound represented by the formula (II) are used in combination, at least one of R ₁ and R ₂ is preferably a group having an aromatic ring, and more preferably, both are R ₁ and R _2, a group having an aromatic ring.

The cationic dye for use in the present invention may be any one as long as the electric charge of the dye except the counter ion is cationic, but a dye having no anionic substituent is preferred. The anionic dye for use in the present invention may be any one as long as the electric charge of the dye except for the counter ion is anionic, but a dye having one or more anionic substituents is preferable. The betaine dye for use in the present invention is a dye having an electric charge within the molecule, thereby forming an inner salt, and wherein the Mo lekül as a whole has no electrical charge. The nonionic dye for use in the present invention is a dye that has no electric charge at all within the molecule.

Of the Expression "anionic Substituent ", like as used herein denotes a substituent containing a has negative charge. Examples thereof include a proton dissociating one acidic group with a dissociation rate of 90% or more a pH of 5 to 8. Specific examples thereof include a sulfo group, a carboxyl group, a sulfate group, a phosphoric acid group, a boric acid group, an alkylsulfonylcarbamoylalkyl group (e.g., methanesulfonylcarbamoylmethyl group), an acylcarbamoylalkyl group (e.g., acetylcarbamoylmethyl group), an acylsulfamoylalkyl group (e.g., acetylsulfamoylmethyl group) and an alkylsulfonylsulfamoylalkyl group (e.g., methanesulfonylsulfamoylmethyl group). Of these, a sulfo group and a carboxyl group are preferred, and a sulfo group is stronger prefers.

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

worin L₅, L₆, L₇, L₈, L₉, L₁₀ und L₁₁ jeweils eine Methingruppe darstellen, p₃ und p₄ jeweils 0 oder 1 darstellen, n₁ 0, 1, 2, 3 oder 4 darstellt, Z₃ und Z₄ jeweils eine atomare Gruppe darstellen, die zum Bilden eines stickstoffhaltigen heterocyclischen Ringes notwendig ist, vorausgesetzt, dass ein Ring mit Z₃ und Z₄ kondensiert sein kann, R₃ und R₄ jeweils eine Alkylgruppe, eine Arylgruppe oder eine heterocyclische Gruppe darstellen, und M₁ und m₁ die gleichen Bedeutungen wie in Formel (I) haben, vorausgesetzt, dass R₃, R₄, Z₃, Z₄ und L₅ bis L₁₁ jeweils keinen anionischen Substituenten aufweisen, wenn die Verbindung (I-1) ein kationischer Farbstoff ist, und einen anionischen Substituenten aufweisen, so dass die elektrische Ladung innerhalb des Farbstoffsmoleküls ausgeglichen ist, vorzugsweise einen (1) anionischen Substituenten, wenn die Verbindung (I-1) ein Betain-Farbstoff ist;

worin L₁₂, L₁₃, L₁₄ und L₁₅ jeweils eine Methingruppe darstellen, p₅ 0 oder 1 darstellt, n₂ 0, 1, 2, 3 oder 4 darstellt, Z₅ und Z₆ jeweils eine atomare Gruppe darstellen, die zum Bilden eines stickstoffhaltigen heterocyclischen Rings notwendig ist, vorausgesetzt, dass ein Ring mit Z₅ und Z₆ kondensiert sein kann, R₅ und R₆ jeweils eine Alkylgruppe, eine Arylgruppe oder eine heterocyclische Gruppe darstellen, und M₁ und m₁ die gleichen Bedeutungen wie in Formel (I) haben, vorausgesetzt, dass R₅, R₆, Z₅, Z₆ und L₁₂ bis L₁₅ jeweils einen kationischen Substituenten aufweisen, wenn die Verbindung (I-2) ein kationischer Farbstoff ist, einen kationischen Substituenten und einen anionischen Substituenten aufweisen, vorzugsweise einen (1) kationischen Substituenten und einen (1) anionischen Substituenten, so dass die elektrische Ladung ausgeglichen ist, wenn die Verbindung (I-2) ein Betain-Farbstoff ist, und weder einen kationischen Substituenten noch einen anionischen Substituenten aufweisen, wenn die Verbindung (I-2) ein nichtionischer Farbstoff ist; oder

worin L₁₆, L₁₇, L₁₈, L₁₉, L₂₀, L₂₁, L₂₂, L₂₃ und L₂₄ jeweils eine Methingruppe darstellen, p₆ und p₇ jeweils 0 oder 1 darstellen, n₃ und n₄ jeweils 0, 1, 2, 3 oder 4 darstellen, Z₇, Z₈ und Z₉ jeweils eine atomare Gruppe darstellen, die zum Bilden eines stickstoffhaltigen heterocyclischen Rings notwendig ist, vorausgesetzt, dass ein Ring mit Z₇ und Z₉ kondensiert sein kann, R₇, R₈ und R₉ jeweils eine Alkylgruppe, eine Arylgruppe oder eine heterocyclische Gruppe darstellen, und M₁ und m₁ die gleichen Bedeutungen wie in Formel (I) haben, vorausgesetzt, dass R₇, R₈, R₉, Z₇, Z₈, Z₉ und L₁₆ bis L₂₄ jeweils keinen anionischen Substituenten aufweisen, wenn die Verbindung (I-3) ein kationischer Farbstoff ist, und einen anionischen Substituenten aufweisen, um so die elektrische Ladung innerhalb des Farbstoffmoleküls auszugleichen, vorzugsweise einen (1) anionischen Substituenten, wenn die Verbindung (I-3) ein Betain-Farbstoff ist.The dye represented by the formula (I) is more preferably represented by the following formulas (I-1), (I-2) or (I-3):

wherein L ₅ , L ₆ , L ₇ , L ₈ , L ₉ , L ₁₀ and L ₁₁ each represent a methine group, p ₃ and p ₄ each represent 0 or 1, n _{1 represents} 0, 1, 2, 3 or 4, Each of Z ₃ and Z ₄ represents an atomic group necessary for forming a nitrogen-containing heterocyclic ring, provided that a ring having Z ₃ and Z ₄ may be condensed, R ₃ and R ₄ each represent an alkyl group, an aryl group or a heterocyclic one And M ₁ and m _{1 have} the same meanings as in formula (I), provided that R ₃ , R ₄ , Z ₃ , Z ₄ and L ₅ to L ₁₁ each have no anionic substituent, when the compound ( I-1) is a cationic dye and has an anionic substituent such that the electrical charge within the dye molecule is balanced, preferably an (1) anionic substituent when the compound (I-1) is a betaine dye;

wherein L ₁₂ , L ₁₃ , L ₁₄ and L ₁₅ each represent a methine group, p _{5 represents} 0 or 1, n _{2 represents} 0, 1, 2, 3 or 4, Z ₅ and Z ₆ each represent an atomic group belonging to Forming a nitrogen-containing heterocyclic ring is necessary, provided that a ring with Z ₅ and Z ₆ may be condensed, R ₅ and R ₆ each represent an alkyl group, an aryl group or a heterocyclic group, and M ₁ and m _{1 have} the same meanings as in formula (I), provided that R ₅ , R ₆ , Z ₅ , Z ₆ and L ₁₂ to L ₁₅ each have a cationic substituent, when the compound (I-2) is a cationic dye, a cationic substituent and have an anionic substituent, preferably one (1) cationic substituent and one (1) anionic substituent, so that the electric charge is balanced when the compound (I-2) is a betaine dye and neither a cationic substituent nor an anionic one Substituents have, when the compound (I-2) is a nonionic dye; or

wherein L ₁₆ , L ₁₇ , L ₁₈ , L ₁₉ , L ₂₀ , L ₂₁ , L ₂₂ , L ₂₃ and L ₂₄ each represent a methine group, p ₆ and p _{7 are} each 0 or 1, n ₃ and n _{4 are} each 0 , 1, 2, 3 or 4, Z ₇ , Z ₈ and Z ₉ each represent an atomic group, which is necessary for forming a nitrogen-containing heterocyclic ring, provided that a ring may be condensed with Z ₇ and Z ₉ , R ₇ , R ₈ and R ₉ each represent an alkyl group, an aryl group or a heterocyclic group, and M ₁ and m _{1 have} the same meanings as in formula (I), provided that R ₇ , R ₈ , R ₉ , Z ₇ , Z ₈ , Z ₉ and L ₁₆ to L ₂₄ each have no anionic substituent, if the compound (I- 3) is a cationic dye and has an anionic substituent so as to balance the electric charge within the dye molecule, preferably one (1) anionic substituent when the compound (I-3) is a betaine dye.

worin L₂₅, L₂₆, L₂₇, L₂₈, L₂₉, L₃₀ und L₃₁ jeweils eine Methingruppe darstellen, p₈ und p₉ jeweils 0 oder 1 darstellen, n₅ 0, 1, 2, 3 oder 4 darstellt, Z₁₀ und Z₁₁ jeweils eine atomare Gruppe darstellen, die zum Bilden eines stickstoffhaltigen heterocyclischen Ringes notwendig ist, vorausgesetzt, dass ein Ring mit Z₁₀ und Z₁₁ kondensiert sein kann, R₁₀ und R₁₁ jeweils eine Alkylgruppe, eine Arylgruppe oder eine heterocyclische Gruppe darstellen, und M₂ und m₂ die gleichen Bedeutungen wie in Formel (II) haben, vorausgesetzt, dass R₁₀ und R₁₁ jeweils einen anionischen Substituenten aufweisen;

worin L₃₂, L₃₃, L₃₄ und L₃₅ jeweils eine Methingruppe darstellen, p₉ 0 oder 1 darstellt, n₆ 0, 1, 2, 3 oder 4 darstellt, Z₁₂ und Z₁₃ jeweils eine aromare Gruppe darstellen, die zum Bilden eines stickstoffhaltigen heterocyclischen Rings notwendig ist, vorausgesetzt, dass ein Ring mit Z₁₂ und Z₁₃ kondensiert sein kann, R₁₂ und R₁₃ jeweils eine Alkylgruppe, eine Arylgruppe oder eine heterocyclische Gruppe darstellen, und M₂ und m₂ die gleichen Bedeutungen wie in Formel (II) haben, vorausgesetzt, dass zumindest eines von R₁₂ und R₁₃ einen anionischen Substituenten aufweist; oder

worin L₃₆, L₃₇, L₃₈, L₃₉, L₄₀, L₄₁, L₄₂, L₄₃ und L₄₄ jeweils eine Methingruppe darstellen, p₁₀ und p₁₁ jeweils 0 oder 1 darstellen, n₇ und n₈ jeweils 0, 1, 2, 3 oder 4 darstellen, Z₁₄, Z₁₅ und Z₁₆ jeweils eine atomare Gruppe darstellen, die zum Bilden eines stickstoffhaltigen heterocyclischen Ringes notwendig ist, vorausgesetzt, dass ein Ring mit Z₁₄ und Z₁₅ kondensiert sein kann, R₁₄, R₁₅ und R₁₆ jeweils eine Alkylgruppe, eine Arylgruppe oder eine heterocyclische Gruppe darstellen, und M₂ und m₂ die gleichen Bedeutungen wie in Formel (II) haben, vorausgesetzt, dass zumindest zwei von R₁₄, R₁₅ und R₁₆ einen anionischen Substituenten aufweisen.The anionic dye represented by the formula (II) is more preferably represented by the following formulas (II-1), (II-2) or (II-3):

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

wherein L ₃₂ , L ₃₃ , L ₃₄ and L ₃₅ each represent a methine group, p _{9 represents} 0 or 1, n _{6 represents} 0, 1, 2, 3 or 4, Z ₁₂ and Z ₁₃ each represent an aromatic group which belongs to Forming a nitrogen-containing heterocyclic ring, provided that a ring may be condensed with Z ₁₂ and Z ₁₃ , R ₁₂ and R ₁₃ each represent an alkyl group, an aryl group or a heterocyclic group, and M ₂ and m _{2 have} the same meanings as in formula (II), provided that at least one of R ₁₂ and R _{13 has} an anionic substituent; or

wherein 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 represent 0 or 1, n ₇ and n ₈ each represents 0 , 1, 2, 3 or 4, Z ₁₄ , Z ₁₅ and Z ₁₆ each represent an atomic group necessary for forming a nitrogen-containing heterocyclic ring, provided that a ring may be condensed with Z ₁₄ and Z ₁₅ , R ₁₄ , R ₁₅ and R ₁₆ each represent an alkyl group, an aryl group or a heterocyclic group, and M ₂ and m _{2 have} the same meanings as in formula (II), provided that at least two of R ₁₄ , R ₁₅ and R ₁₆ have an anionic substituent.

When the compound represented by the formula (I-1), (I-2) or (I-3) is used alone, at least one and preferably both of R ₃ and R ₄ are (are) an aromatic ring group at least one and preferably both of R ₅ and R ₆ is (are) a group having an aromatic ring and is at least one, preferably two or more, preferably all three of R ₇ , R ₈ and R ₉ ) a group having an aromatic ring.

When the compound represented by the formula (I-1), (I-2) or (I-3) and the compound represented by the formula (II-1), (II-2) or (II-3) in combination is at least one, preferably two, more preferably three, and more preferably four or more of R ₃ to R ₉ or R ₁₀ to R _{16 is} a group having an aromatic group.

By The preferred method described above can be a silver halide grain with one wavelength the spectral absorption maximum of 500 nm or more and a Light absorption intensity of 100 or more. However, the dye becomes in the second layer usually adsorbed in the state of a monomer, and its absorption width and spectral sensitivity widths are broader in most cases than the appropriate ones desired Areas. To realize high sensitivity in the desired Wavelength range For example, the dye adsorbed in the second layer must have a J-association product (i.e., a J-aggregate). The J-aggregate has a high fluorescence yield and a small Stokes shift. Therefore, this is the transfer the light energy absorbed by the dye in the second layer to the dye in the first layer advantageous in the Light absorption wavelength approximated are, the energy transfer exploited by the Forster type.

In of the present invention denotes the dye in the second and subsequent layers of a dye attached to a silver halide grain is adsorbed, but not adsorbed directly to the silver halide.

In the present invention is the J-aggregate of a dye in the second or subsequent layer is defined as such a product, that the absorption width on the longer wavelength side of the Absorption by one in the second or following layer adsorbed dye is shown twice or less of the absorption width on the side longer Wavelengths, that from the dye solution is shown in the monomer state, wherein is no interaction occurs between the dye chromophores. The absorption width on the side longer Wavelengths, As used herein, the energy width between the wavelength the maximum absorption and the wavelength longer than the wavelength of the maximum absorption and shows an absorption that is so small how 1/2 of the absorption maximum is. It is well known that if a J-aggregate is formed, the absorption width on the side longer wavelength is generally reduced in comparison with the monomer state. If the dye adsorbed to the second layer is still is in the monomer state, increases the absorption width up to twice or more of the absorption width on the side longer wavelength the absorption shown by a dye solution in the monomer state is because the adsorption site and the adsorption state is not are even. Accordingly, the dye may be in the second or following Layer as defined above.

The spectral absorption of a dye attached to the second or following Adsorbed layers can be obtained by subtracting the spectral Absorption attributed to the dye in the first layer of the total spectral absorption of the emulsion can be obtained.

The spectral absorption attributed to the dye in the first layer can be determined by measuring the absorption spectrum, when only the dye is added in the first layer. The Spectral absorption spectrum can also be achieved by adding a dye desorbent to the emulsion to which a sensitizing dye in multiple Adsorbed layers, and thereby desorbing the dyes be measured in the second and subsequent layers.

In an experiment for desorbing a dye from the grain surface Use of a dye desorbent For example, the dye in the first layer is usually desorbed after desorbs the dyes in the second and subsequent layers are. Therefore, by selecting suitable desorption conditions the spectral absorption, the attributable to the dye in the first layer and thereby the spectral absorption of the dyes obtained in the second and subsequent layers. The procedure in which a dye desorbent is used is in Asanuma et al., Journal of Physical Chemistry B, volume 101, pages 2149-2153 (1997) described.

Around using a J-aggregate of dyes in the second layer the cationic dye represented by the formula (I), Betaine dye or nonionic dye and by the Formula (II) anionic dye to be formed the dye that is adsorbed to form the first layer, and the dye that is adsorbed to the second or following Layers, preferably added separately, and it is stronger preferred that for the first layer used dye and that for the second or following Layer used dye mutually different structures exhibit. The dye in the second or subsequent layer comprises preferably alone a cationic dye, a betaine dye or a nonionic dye, or it comprises a combination of a cationic dye and an anionic dye.

As the dye in the first layer, any dye can be used, but is by the Preferably, the dye represented by formula (I) or (II) is preferred, and the dye represented by the formula (I) is more preferable.

When Dye in the second layer is preferably the one through which Formula (I) shown cationic dye, betaine dye or nonionic dye used alone. If a cationic Dye and an anionic dye used in combination What is another preferred embodiment of the dye in the second layer is preferably one of the dyes used the cationic dye represented by the formula (I) or the anionic dye represented by the formula (II), and it is stronger preferred that the cationic represented by the formula (I) Dye and the anionic represented by the formula (II) Dye are both included. The ratio cationic dye / anionic dye as the dye in the second layer is preferably 0.5 to 2, more preferably 0.75 to 1.33, the strongest preferably 0.9 to 1.11.

According to the invention can Be added to the dye of the formulas (I) and (II) dyes. However, he does preferred dye represented by the formula (I) or (II) 50% or more, stronger preferably 70% or more, the strongest preferably 90% or more, of the total amount of the added dyes out.

By Addition of the dye in the second layer as such may Increased interaction between the dyes in the second layer, whereby the rearrangement of the dyes in the second layer is promoted, and thereby the J-association product (i.e., J-aggregate) be formed.

When the dye represented by the formula (I) or (II) is used as the dye in the first layer, Z ₁ and Z _{2 are} preferably a nucleus substituted with an aromatic group or a nucleus resulting from the condensation of three or more rings results. When the dye represented by the formula (I) or (II) is used as the dye in the second or subsequent layer, Z ₁ and Z _{2 are} preferably a core nucleus resulting from the condensation of three or more rings.

The number of rings condensed in the nucleus is, for example, in the benzoxazole nucleus 2 and in the naphthoxazole nucleus 3. Even if the benzoxazole nucleus is substituted with a phenyl group, the number of fused rings is 2. The nucleus resulting from the condensation of three or more more rings, any may be as long as it is a condensation type polycyclic heterocyclic core obtained by condensation of three or more rings. However, a condensation type tricyclic heterocyclic ring and a condensation type tetracyclic heterocyclic ring are preferable. Preferred examples of the condensation type tricyclic heterocyclic ring include naphtho [2,3-d] oxazole, naphtho [1,2-d] oxazole, naphtho [2,1-d] oxazole, naphtho [2,3-d] thiazole, Naphtho [1,2-d] thiazole, naphtho [2,1-d] thiazole, naphtho [2,3-d] imidazole, naphtho [1,2-d] imidazole, naphtho [2,1-d] imidazole, naphtho [2,3-d] selenazole, naphtho [1,2-d] selenazole, naphtho [2,1-d] selenazole, indolo [5,6-d] oxazole, indolo [6,5-d] oxazole, indolo [2,3-d] oxazole, indolo [5,6-d] thiazole, indolo [6,5-d] thiazole, indolo [2,3-d] thiazole, benzofuro [5,6-d] oxazole, benzofuro [6,5-d] oxazole, benzofuro [2,3-d] oxazole, benzofuro [5,6-d] thiazole, benzofuro [6,5-d] thiazole, benzofuro [2,3-d] thiazole, benzothieno [5,6-d] oxazole, benzothieno [6,5-d] oxazole and benzothieno [2,3-d] oxazole. Preferred examples of the condensation type tetracyclic heterocyclic ring include 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] oxazole, 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, tetrahydrocarbazole [7,6-d] oxazole, dibenzothieno [3,2-d] thiazole, dibenzothieno [3,2-d] thiazole and tetrahydrocarbazolo [6,7-d] thiazole. More preferred examples of the nucleus resulting from the condensation of three or more rings include 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 and dibenzothieno [3,2-d] oxazole. Of these, 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 continue to be more preferred.

One another preferred example of the method for realizing such an adsorption state that a dye chromophore in multiple Layers coated on the silver halide grain surface is a Method in which a dye compound is used, the two or more Farbstoffchromophoreinheiten by covalent Ties over a linking group are connected. The dye chromophore that can be used may be any and examples thereof include those above described dye chromophores. Of these, the above described polymethine dye chromophores for the Dye chromophore preferred, more preferred are cyanine dyes, Merocyanine dyes, Rhodacyanine dyes and oxonol dyes, beyond stronger preferred are cyanine dyes, rhodacyanine dyes and merocyanine dyes, and cyanine dyes are most preferred.

preferred Examples of the method described above include a method in which a dye is used by a methine chain disclosed in JP-A-9-265144, a method in which a dye is used to which an oxonol dye is attached is a method in which a linked dye is described in JP-A-10-226758 is used, which has a specific structure described in JP-A-10-110107, JP-A-10-307358, JP-A-10-307359 and JP-A-10-310715, a procedure in which a linked Dye is used which has a specific linking group disclosed in JP-A-9-189986 and JP-A-10-204306, a method in which a linked Dye is used which has a specific structure, described in JP-A-2000-231174, JP-A-2000-231172 and JP-A-2000-231173 and a method in which a dye is used which has a having reactive group and in an emulsion a linked dye forms described in JP-A-2000-81678.

The linked dye is preferably a dye represented by the following formula (III): D ₁ - (La- [D ₂ ] _q ) _r (III) wherein D ₁ and D ₂ each represent a dye chromophore, La represents a linking group or a single bond, q and r each represent an integer of 1 to 100, M _{3 represents} a charge balancing counterion, and m _{3 represents} a number to neutralize the electric charge of the molecule is required.

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

The chromophore represented by D ₁ or D ₂ may be any. Specific examples thereof include the above-described dye chromophores. Of these, the above polymethine dye chromophores are preferred as the dye chromophore, more preferred are cyanine dyes, merocyanine dyes, rhodacyanine dyes and oxonol dyes, moreover, more preferred are cyanine dyes, merocyanine dyes and rhodacyanine dyes, and cyanine Dyes are most preferred.

In the present invention, when a linked dye represented by the formula (III) is adsorbed to a silver halide grain, D _{2 is} preferably a chromophore which is not directly adsorbed to silver halide.

In other words, D ₂ preferably has a lower adsorption strength to a silver halide grain than D ₁ . The adsorption strength to a silver halide grain is most preferably in the order D ₁ >La> D ₂ .

As such, D _{1 is} preferably a sensitizing dye unit having adsorptivity to a silver halide grain. However, adsorption can also be achieved by either physical adsorption or chemical adsorption.

D ₂ preferably has a weak adsorptivity to a silver halide grain, and it is preferably also a light-emitting dye. As the light-emitting dye, those having a skeletal structure (ie, basic structure) of dyes used for dye lasers are vorzugt. These are described, for example, in Mitsuo Maeda, Laser Kenkyu (Study of Laser), Volume 8, page 694, page 803 and page 958 (1980), also Volume 9, page 85 (1981) and F. Shaefer, Dye Lasers, Springer (1973 ).

The wavelength of the absorption maximum of D ₁ in a silver halide photographic light-sensitive material is preferably longer than the wavelength of the absorption maximum of D ₂ . Furthermore, the absorption of D ₁ preferably overlaps with the light emission of D ₂ . In addition, D ₁ preferably forms a J-aggregate. In order to enable the linked dye represented by the formula (I) to exhibit absorption and spectral sensitivity in a desired wavelength range, D ₂ also preferably forms a J-aggregate.

D ₁ and D ₂ may each have any reduction potential and any oxidation potential, but the reduction potential of D _{1 is} preferably more positive than the value obtained by subtracting 0.2 V from the reduction potential of D ₂ .

La represents a linkage group (preferably a divalent linking group) or a single bond This linking group preferably comprises an atom or an atomic group which is at least one of a carbon atom, nitrogen atom, sulfur atom and Contains oxygen atom. La preferably represents a linking group of 0 to 100 Carbon atoms, stronger preferably 1 to 20 carbon atoms, represented by one or a combination of two or more of an alkylene group (e.g. Methylene, ethylene, propylene, butylene, pentylene), an arylene group (e.g., phenylene, naphthylene), an alkenylene group (e.g., ethenylene, Propenylene), an alkynylene group (e.g., ethynylene, propynylene), an amide group, an ester group, a sulfoamido group, a sulfonic, a ureido group, a sulfonyl group, a sulfinyl group, a thioether group, an ether group, a carbonyl group, -N (Va) - (wherein Va represents a hydrogen atom or a monovalent substituent represents; Examples of the monovalent group include those which are represented by V, which will be described later) and one heterocyclic divalent group (e.g., 6-chloro-1,3,5-triazine-2,4-diyl, Pyrimidine-2,4-diyl, quinoxaline-2,3-diyl).

The the linking group described above each may have a substituent represented by V, the later is described. Furthermore, can these linking groups each ring (aromatic or non-aromatic hydrocarbon or heterocyclic ring).

La makes stronger preferably a divalent linking group with 1 to 10 carbon atoms, by one or a combination of two or more of an alkylene group having 1 to 10 carbon atoms (e.g., methylene, ethylene, propylene, butylene), an arylene group with 6 to 10 carbon atoms (e.g., phenylene, naphthylene), one Alkenylene group of 2 to 10 carbon atoms (e.g., ethenylene, Propenylene), an alkynylene group having 2 to 10 carbon atoms (e.g., ethynylene, propynylene), an ether group, an amide group, an ester group, a sulfonamido group and a sulfonic acid ester group is built. These linking groups can each substituted with V, which will be described later.

La is a linking group, the one energy transfer or electron transfer through interaction over the bond (through-bond) may afford. The interaction over the Binding involves a tunneling interaction and a super-exchange interaction. Of these, an interaction is via the binding that occurs on the Super-exchange interaction based, preferred. The interaction via binding and the super-exchange interaction are in Shammai Speiser, Chem. Rev., Vol. 96, pp. 1960-1963 (1996) Are defined. As a linking group, the occurrence of an energy transfer or electron transfer through such an interaction are those in Shammai Speiser, Chem. Rev., Vol. 96, pp. 1967-1969 (1996). are described.

Each of q and r represents an integer of 1 to 100, preferably 1 to 5, more preferably 1 to 2, more preferably 1, more. When q and r are each 2 or more, a plurality of linking groups La, may be different, and a variety of dye chromophores D ₂ contained may also be different.

Of the The dye represented by the formula (III) is preferable as a whole an electric charge of -1 on.

worin jedes von L₄₅, L₄₆, L₄₇, L₄₈, L₄₉, L₅₀ und L₅₁ eine Methingruppe darstellt, jedes p₁₂ und p₁₃ 0 oder 1 darstellt, n₉ 0, 1, 2, 3 oder 4 darstellt, jedes Z₁₇ und Z₁₈ eine atomare Gruppe darstellt, die zum Bilden eines stickstoffhaltigen heterocyclischen Rings notwendig ist, vorausgesetzt, dass ein Ring mit Z₁₇ und Z₁₈ kondensiert sein kann, M₄ stellt ein ladungsausgleichendes Gegenion dar, m₄ stellt eine Zahl von 0 oder mehr, die zum Neutralisieren der elektrischen Ladung des Moleküls notwendig ist, dar, und R₁₇ und R₁₈ stellen jeweils eine Alkylgruppe, eine Arylgruppe oder eine heterocyclische Gruppe dar;

worin jedes L₅₂, L₅₃, L₅₄ und L₅₅ eine Methingruppe darstellt, p₁₄ 0 oder 1 darstellt, n₁₀ 0, 1, 2, 3 oder 4 darstellt, Z₁₉ und Z₂₀ jeweils eine atomare Gruppe, die zum Bilden eines stickstoffhaltigen heterocyclischen Ringes notwendig ist, darstellen, vorausgesetzt, dass ein Ring mit Z₁₉ kondensiert sein kann, M₅ stellt ein ladungsausgleichendes Gegenion dar, m₅ stellt eine Zahl von 0 oder mehr, die zum Neutralisieren der elektrischen Ladung des Moleküls notwendig ist, dar, und R₁₉ und R₂₀ stellen jeweils eine Alkylgruppe, eine Arylgruppe oder eine heterocyclische Gruppe dar; oder

worin jedes L₅₆, L₅₇, L₅₈, L₅₉, L₆₀, L₆₁, L₆₂, L₆₃ und L₆₄ eine Methingruppe darstellt, p₁₅ und p₁₆ jeweils 0 oder 1 darstellen, n₁₁ und n₁₂ jeweils 0, 1, 2, 3 oder 4 darstellen, Z₂₁, Z₂₂ und Z₂₃ jeweils eine atomare Gruppe, die zum Bilden eines stickstoffhaltigen heterocyclischen Ringes notwendig ist, darstellen, vorausgesetzt, dass ein Ring mit Z₂₁ und Z₂₃ kondensiert sein kann, M₆ stellt ein ladungsausgleichendes Gegenion dar, m₆ stellt eine Zahl von 0 oder mehr, die zum Neutralisieren der elektrischen Ladung des Moleküls notwendig ist, dar, und R₂₁, R₂₂ und R₂₃ stellen jeweils eine Alkylgruppe, eine Arylgruppe oder eine heterocyclische Gruppe dar.The dye is more preferably a methine dye wherein D ₁ and D ₂ in formula (III) are each independently represented by the following formulas (IV), (V) or (VI):

wherein each of L ₄₅ , L ₄₆ , L ₄₇ , L ₄₈ , L ₄₉ , L ₅₀ and L _{51 represents} a methine group, each p ₁₂ and p _{13 represents} 0 or 1, n _{9 represents} 0, 1, 2, 3 or 4 each Z ₁₇ and Z _{18 represents} an atomic group necessary for forming a nitrogen-containing heterocyclic ring, provided that a ring may be fused with Z ₁₇ and Z ₁₈ , M ₄ represents a charge-balancing counterion, m ₄ represents a number of 0 or more necessary for neutralizing the electric charge of the molecule, and R ₁₇ and R ₁₈ each represents an alkyl group, an aryl group or a heterocyclic group;

wherein each of L ₅₂ , L ₅₃ , L ₅₄ and L _{55 represents} a methine group, p _{14 represents} 0 or 1, n represents ₁₀ , 1, 2, 3 or 4, Z ₁₉ and Z ₂₀ each represent an atomic group to be formed a nitrogen-containing heterocyclic ring is necessary, provided that a ring may be condensed with Z ₁₉ , M ₅ represents a charge-balancing counterion, m ₅ represents a number of 0 or more necessary to neutralize the electric charge of the molecule, and R ₁₉ and R ₂₀ each represent an alkyl group, an aryl group or a heterocyclic group; or

wherein each of L ₅₆ , L ₅₇ , L ₅₈ , L ₅₉ , L ₆₀ , L ₆₁ , L ₆₂ , L ₆₃ and L _{64 represents} a methine group, p ₁₅ and p _{16 are} each 0 or 1, n ₁₁ and n _{12 are} each 0 , 1, 2, 3 or 4, Z ₂₁ , Z ₂₂ and Z ₂₃ each represent an atomic group necessary for forming a nitrogen-containing heterocyclic ring, provided that a ring may be condensed with Z ₂₁ and Z ₂₃ , M ₆ represents a charge-balancing counter ion, m ₆ represents a number of 0 or more necessary for neutralizing the electric charge of the molecule, and R ₂₁ , R ₂₂ and R ₂₃ each represents an alkyl group, an aryl group or a heterocyclic one Group dar.

From the process in which the compounds represented by the formulas (I) and (II) Dyes are used, and the method in which by The dye represented by formula (III) is used Process in which those represented by formulas (I) and (II) Dyes used are preferred.

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

In formulas (I) and (II), Q ₁ and Q ₂ each represents a group necessary for forming a methine dye. Groups of any of Q ₁ and Q ₂ may form any methine dye, but include Examples of these are the methine dyes described above as examples of the dye chromophore.

From these are cyanine dyes, merocyanine dyes, rhodacyanine dyes, trinuclear merocyanine dyes, tetranuclear merocyanine dyes, Allopolar dyes, hemicyanine dyes and styryl dyes cyanine dyes, merocyanine dyes and rhodacyanine dyes are more preferred, and cyanine dyes are further more preferred. These dyes are detailed in F.M. Harmer, Heterocyclic Compounds-Cyanine Dyes and Related Compounds, John Wiley & Sons, New York, London (1964), D. M. Sturmer, Heterocyclic Compounds - Special topics in heterocyclic chemistry, chapter 18, section 14, pages 482-515.

As cyanine dyes, merocyanine dyes and rhodacyanine dyes, the formulas (XI), (XII) and (XIII) described in US Patent 5,340,694, columns 21 to 22, on the condition that the numbers of n ₁₂ , n ₁₅ , n ₁₇ and n _{18 are} not limited and each is an integer of 0 or more (preferably 4 or less).

When a cyanine dye or rhodacyanine dye of Q ₁ or Q _{2 is} formed, the formulas (I) and (II) can be expressed by the following resonance formulas:

In the formulas (I), (II), (IV), (V) and (VI) Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ , Z ₇ , Z ₈ , Z ₁₀ , Z ₁₁ , Z ₁₂ , Z ₁₄ , Z ₁₆ , Z ₁₇ , Z ₁₈ , Z ₁₉ , Z ₂₁ and Z _{23 are} each an atomic group necessary for forming a nitrogen-containing heterocyclic ring, preferably a 5- or 6-membered nitrogen-containing heterocyclic ring However, a ring may be fused to each of these groups. The ring may be either an aromatic ring or a non-aromatic ring, but an aromatic ring is preferred, and examples thereof include aromatic hydrocarbon rings such as a benzene ring and a naphthalene ring, and heteroaromatic rings such as a pyrazine ring and a thiophene ring.

Examples of the nitrogen-containing heterocyclic ring include a thiazole nucleus, Thiazole nucleus, benzothiazole nucleus, oxazoline nucleus, oxazole nucleus, benzoxazole nucleus, Selenazoline nucleus, selenazole nucleus, benzoselenazole nucleus, 3,3-dialkylindolenine nucleus (e.g., 3,3-dimethylindolenine), imidazoline nucleus, imidazole nucleus, benzimidazole nucleus, 2-pyridine core, 4-pyridine core, 2-quinoline nucleus, 4-quinoline nucleus, 1-isoquinoline nucleus, 3-isoquinoline nucleus, imidazo [4,5-b] quinoxaline nucleus, oxadiazole nucleus, Thiadiazole nucleus, tetrazole nucleus and pyrimidine nucleus. Of these are a benzothiazole nucleus, benzoxazole nucleus, 3,3-dialkylindolenine nucleus (e.g. 3,3-dimethylindolenine), benzimidazole nucleus, 2-pyridine nucleus, 4-pyridine nucleus, 2-quinoline nucleus, 4-quinoline nucleus, 1-isoquinoline nucleus, and 3-isoquinoline nucleus prefers; stronger preferred are a benzothiazole nucleus, benzoxazole nucleus, 3,3-dialkylindolenine nucleus (e.g., 3,3-dimethylindolenine) and benzimidazole nucleus; still more preferred are a benzoxazole nucleus, benzothiazole nucleus and benzimidazole nucleus and the strongest preferred are a benzoxazole nucleus and benzothiazole nucleus.

However, assuming that the substituent on the nitrogen-containing heterocyclic ring is V, the substituent represented by V is not particularly limited. Examples thereof include a halogen atom (eg, chlorine, bromine, iodine, fluorine), a mercapto group, a cyano group, a carboxy group, a phosphoric acid group, a sulfo group, a hydroxy group, a carbamoyl group having 1 to 10, preferably 2 to 8, more preferably 2 to 5 carbon atoms, (eg, methylcarbamoyl, ethylcarbamoyl, morpholinocarbonyl), a sulfamoyl group having 0 to 10, preferably 2 to 8, more preferably 2 to 5 carbon atoms (eg, methylsulfamoyl, ethylsulfamoyl, piperidinosulfonyl), a nitro group, an alkoxy group having 1 to 20, preferably 1 to 10, more preferably 1 to 8 carbon atoms (eg, methoxy, ethoxy, 2-methoxyethoxy, 2-phenylethoxy), an aryloxy group having 6 to 20, preferably 6 to 12, more preferably 6 to 10 carbon atoms (eg, phenoxy, p-methylphenoxy , p-chlorophenoxy, naphthoxy), an acyl group having 1 to 20, preferably 2 to 12, more preferably 2 to 8 carbon atoms (eg, acetyl, benzoyl, trichloroacetyl), an acyloxyg group having 1 to 20, preferably 2 to 12, more preferably 2 to 8 carbon atoms (eg, acetyloxy, benzoyloxy), an acylamino group having 1 to 20, preferably 2 to 12, more preferably 2 to 8 carbon atoms (eg, acetylamino), a sulfonyl group having 1 to 20, preferably 1 to 10, more preferably 1 to 8 carbon atoms (eg methanesulfonyl, ethanesulfonyl, benzenesulfonyl), a sulfinyl group having 1 to 20, preferably 1 to 10, more preferably 1 to 8 carbon atoms (eg methanesulfinyl, ethanesulfinyl, benzenesulfinyl) a sulfonylamino group having 1 to 20, preferably 1 to 10, more preferably 1 to 8 carbon atoms (eg, methanesulfonylamino, ethanesulfonylamino, benzenesulfonylamino), an amino group, a substituted amino group having 1 to 20, preferably 1 to 12, more preferably 1 to 8 carbon atoms (eg, methylamino, dimethylamino, dibenzylamino, anilino, diphenylamino), an ammonium group of 0 to 15, preferably 3 to 10, more preferably 3 to 6 carbon atoms (eg trimethylammonium, trieth hylammonium), a hydrazino group having 0 to 15, preferably 1 to 10, more preferably 1 to 6 carbon atoms (eg trimethylhydrazino), a ureido group having 1 to 15, preferably 1 to 10, more preferably 1 to 6 carbon atoms (eg ureido, N, N-dimethylureido), an imido group having 1 to 15, preferably 1 to 10, more preferably 1 to 6 carbon atoms (eg succinimido), an alkylthio group having 1 to 20, preferably 1 to 12, more preferably 1 to 8 carbon atoms (eg methylthio, Ethylthio, propylthio), an arylthio group having 6 to 20, preferably 6 to 12, more preferably 6 to 10 carbon atoms (eg, phenylthio, p-methylphenylthio, p-chlorophenylthio, 2-pyridylthio, naphthylthio), an alkoxycarbonyl group having 2 to 20, preferably 2 to 12, more preferably 2 to 8 carbon atoms (eg, methoxycarbonyl, ethoxycarbonyl, 2-benzyloxycarbonyl), an aryloxycarbonyl group having 6 to 20, preferably 6 to 12, more preferably 6 to 10 carbon atoms (eg, phenoxycarbonyl), an unsubstituted alkyl group having 1 to 18, preferably 1 to 10, more preferably 1 to 5 carbon atoms (eg, methyl, ethyl, propyl, butyl), a substituted alkyl group having 1 to 18, preferably 1 to 10, more preferably 1 to 5 carbon atoms (eg, hydroxymethyl, trifluoromethyl, benzyl, carboxyethyl, ethoxycarbonylmethyl, acetylaminomethyl; the substituted alkyl group includes an unsaturated hydrocarbon group having 2 to 18, preferably 3 to 10, more preferably 3 to 5 carbon atoms (eg, vinyl, ethynyl, 1-cyclohexenyl, benzylidyne, benzylidene), a substituted or unsubstituted aryl group having 6 to 20, preferably 6 to 15, more preferably 6 to 10 carbon atoms (eg, phenyl, naphthyl, p-carboxyphenyl, p-nitrophenyl, 3,5-dichlorophenyl, p-cyanophenyl, m-fluorophenyl, p-tolyl) and 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, tetrahydrofurfuryl). These may have such a structure that a ring (an aromatic or non-aromatic hydrocarbon or heterocyclic ring, eg, a benzene ring, a naphthalene ring, an anthracene ring, a quinoline ring) is condensed thereon.

Of the V represented by V may be further substituted with V. be.

From these substituents are the alkyl group, the aryl group, the alkoxy group, the halogen atom, the aromatic ring condensation product, the Sulfo group, the carboxy group and the hydroxy group preferred.

The substituent V of Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ , Z ₇ , Z ₉ , Z ₁₀ , Z ₁₁ , Z ₁₂ , Z ₁₄ and Z ₁₆ is more preferably the aromatic group and the aromatic ring condensation product.

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

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

Z ₆ , Z ₁₃ and Z ₂₀ each represent an atomic group necessary for forming an acidic nucleus, but also the form of an acidic nucleus may be formed of any general merocyanine dye. As used herein, the term "acidic core" is defined, for example, in James (compiler), Theory of the Photographic Process, 4th Edition, page 198, Macmillan (1977). Specific examples thereof include those described in U.S. Patents 3,567,719, 3,575,869, 3,804,634, 3,837,862, 4,002,480 and 4,925,777 and JP-A-3-167546.

The acidic nucleus preferably forms a 5 or 6 membered nitrogen containing heterocyclic ring comprising carbon, nitrogen and chalcogen (typically oxygen, sulfur, selenium or tellurium) atoms. Examples of these include the following cores:
Nuclei of 2-pyrazolin-5-one, pyrazolidine-3,5-dione, imidazolin-5-one, hydantoin, 2- or 4-thiohydantoin, 2-iminooxazolidin-4-one, 2-oxazolin-5-one, 2 Thiooxazoline-2,4-dione, isooxazolin-5-one, 2-thiazolin-4-one, thiazolidin-4-one, thiazolidine-2,4-dione, thodanine, thiazolidine-2,4-dione, isorhodanine, indane -1,3-dione, thiophen-3-one, thiophen-3-one-1,1-dioxide, indolin-2-one, indolin-3-one, 2-oxoindazolinium, 3-oxoindazolinium, 5,7-dioxo 6,7-dihydrothiazolo [3,2-a] pyrimidine, cyclohexane-1,3-dione, 3,4-dihydroisoquinolin-4-one, 1,3-dioxane-4,6-dione, barbituric acid, 2-thiobarbituric acid , Chroman-2,4-dione, indazolin-2-one, pyrido [1,2-a] pyrimidine-1,3-dione, pyrazolo [1,5-b] quinazolone, pyrazolo [1,5-a] benzimidazole , Pyrazolopyridone, 1,2,3,4-tetrahydroquinoline-2,4-dione, 3-oxo-2,3-dihydrobenzo [d] thiophene-1,1-dioxide and 3-dicyanomethyne-2,3-dihydrobenzo [d ] thiophene-1,1-dioxide.

Z ₆ , Z ₁₃ and Z ₂₀ are each preferably hydantoin, 2- or 4-thiohydantoin, 2-oxazolin-5-one, 2-thioo xazoline-2,4-dione, thiazolidine-2,4-dione, rhodanine, thiazolidine-2,4-dione, barbituric acid or 2-thiobarbituric acid, more preferably hydantoin, 2- or 4-thiohydantoin, 2-oxazolin-5-one , Rhodanine, barbituric acid or 2-thiobarbituric acid, more preferably 2- or 4-thiohydantoin, 2-oxazolin-5-one, rhodanine or barbituric acid.

The 5- or 6-membered nitrogen-containing heterocyclic ring formed by Z ₈ , Z ₁₅ or Z ₂₂ is the heterocyclic ring represented by Z ₆ , Z ₁₃ or Z _{20 of} which an oxo or thioxo group is excluded , preferably hydantoin, 2- or 4-thiohydantoin, 2-oxazolin-5-one, 2-thiooxazoline-2,4-dione, thiazolidine-2,4-dione, rhodanine, thiazolidine-2,4-dithione, barbituric acid or 2 Thiobarbituric acid, of which an oxo or thioxo group is excluded, more preferably hydantoin, 2- or 4-thiohydantoin, 2-oxazolin-5-one, rhodanine, barbituric acid or 2-thiobarbituric acid of which an oxo or thioxo group is excluded preferably 2- or 4-thiohydantoin, 2-oxazolin-5-one or rhodanine, of which one oxo or thioxo group is excluded.

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 each represents an alkyl group, an aryl group or a heterocyclic group. Specific examples thereof include an unsubstituted alkyl group having 1 to 18, preferably 1 to 7, more preferably 1 to 4 carbon atoms (eg, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl), a substituted alkyl group having 1 to 18, preferably 1 to 7, more preferably 1 to 4 carbon atoms {eg, an alkyl group which is substituted by the substituent V described above, preferably an aralkyl group (eg benzyl, 2-phenylethyl), an unsaturated hydrocarbon group (eg allyl), a hydroxyalkyl group (eg 2-hydroxyethyl, 3-hydroxypropyl), a carboxyalkyl group (eg. Carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, carboxymethyl), an alkoxyalkyl group (eg 2-methoxyethyl, 2- (2-methoxyethoxy) ethyl), aryloxyalkyl group (eg, 2-phenoxyethyl, 2- (1-naphthoxy) ethyl), an alkoxycarbonylalkyl group (eg, ethoxycarbonylmethyl, 2-benzyloxycarbonylethyl), an aryloxycarbonylalkyl group (eg, 3-phenoxycarbonylpropyl), an acyloxyalkyl group ( eg 2-acetyloxyethyl), an acylalkyl group (eg 2-acetylethyl), a carbamoylalkyl group (eg 2-morpholinocarbonylethyl), a sulfamoylalkyl group (eg N, N-dimethylsulfamoylmethyl), a sulfoalkyl group (eg 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl , 4-sulfobutyl, 2- [3-sulfopropoxy] ethyl, 2-hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl), a sulfoalkenyl group, a sulfatoalkyl group, (eg 2-sulfatoethyl, 3-sulfatopropyl, 4-sulfato-butyl), one with a heterocyclic ring-substituted alkyl group (eg, 2- (pyrrolidin-2-one-1-yl) ethyl, tetrahydrofurfuryl), an alkylsulfonylcarbamoylalkyl group (eg, methanesulfonylcarbamoylmethyl), an acylcarbamoylalkyl group (eg, acetylcarbamoylmethyl), an acylsulfamoylalkyl group (eg, acetyls ulfamoylmethyl) and an alkylsulfonylsulfamoylalkyl group (eg, methanesulfonylsulfamoylmethyl)}, an unsubstituted aryl group having 6 to 20, preferably 6 to 10, more preferably 6 to 8 carbon atoms (eg, phenyl, 1-naphthyl), a substituted aryl group having 6 to 20, preferably 6 to 10 carbon atoms, more preferably 6 to 8 carbon atoms (eg, an aryl group substituted with the above-described V as examples of the substituent; specifically p-methoxyphenyl, p -methylphenyl, p-chlorophenyl), an unsubstituted heterocyclic group having 1 to 20, preferably 3 to 10, more preferably 4 to 8 carbon atoms (eg 2-furyl, 2-thienyl, 2-pyridyl, 3 Pyrazolyl, 3-isooxazolyl, 3-isothiazolyl, 2-imidazolyl, 2-oxazolyl, 2-thiazolyl, 2-pyridazyl, 2-pyrimidyl, 3-pyrazyl, 2- (1,3,5-triazolyl), 3- (1 , 2,4-triazolyl), 5-tetrazolyl) and a substituted heterocyclic group having 1 to 20, preferably 3 to 10, more preferably 4 to 8 carbon atoms (eg, a heterocyclic group substituted with the above-described V as examples of the substituent specifically 5-methyl-2-thienyl, 4-methoxy-2-pyrimidyl).

R ₁ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ each preferably represents a group having an aromatic ring. Examples of the aromatic ring include an aromatic hydrocarbon ring and a heteroaromatic ring. These rings may each be a polycyclic condensation ring resulting from the condensation of aromatic hydrocarbon rings or heteroaromatic rings with each other, or a polycyclic condensation ring resulting from the joining of an aromatic hydrocarbon ring and an aromatic heterocyclic ring. These rings may each be substituted with the above-described substituent V or the like. Preferred examples of the aromatic ring include those described above as examples of the aromatic ring for the aromatic group.

The group having an aromatic ring may also be expressed by -Lb-A ₁ wherein Lb represents a single bond or a linking group and A _{1 represents} an aromatic group. Preferred examples of the linking group represented by Lb include the linking groups described above for La and the like. Examples of the aromatic group represented by A ₁ include those described above as examples of the group having an aromatic ring.

preferred Examples of the group having an aromatic ring, the contains no anionic group, include an alkyl group which is an aromatic hydrocarbon ring such as an aralkyl group (e.g., benzyl, 2-phenylethyl, naphthylmethyl, 2- (4-biphenyl) ethyl), an aryloxyalkyl group (e.g., 2-phenoxyethyl, 2- (1-naphthoxy) ethyl, 2- (4-biphenyloxy) ethyl, 2- (o-, m- or p-halophenoxy) ethyl, 2- (o-, m- or p-methoxyphenoxy) ethyl) and an aryloxycarbonylalkyl group (e.g., 3-phenoxycarbonylpropyl, 2- (1-naphthoxycarbonyl) ethyl); a Alkyl group having a heteroaromatic ring, such as 2- (2-pyridyl) ethyl, 2- (4-pyridyl) ethyl, 2- (2-furyl) ethyl, 2- (2-thienyl) ethyl and 2- (2-pyridylmethoxy) ethyl; an aromatic hydrocarbon group such as 4-methoxyphenyl, phenyl, Naphthyl and biphenyl; and a heteroaromatic group such as 2-thienyl, 4-chloro-2-thienyl, 2-pyridyl and 3-pyrazolyl.

From these are the alkyl groups which are a substituted or unsubstituted one aromatic hydrocarbon ring or the heteroaromatic ring have, stronger preferred, and the alkyl groups having a substituted or unsubstituted aromatic hydrocarbon ring are further more preferred.

Each R ₂ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ is preferably a group having an aromatic ring. Both of R ₁₀ and R ₁₁ , 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 an aromatic hydrocarbon ring and a heteroaromatic ring. These rings may be a polycyclic condensation ring resulting from the condensation of aromatic hydrocarbon rings or heteroaromatic rings with each other, or a polycyclic condensation ring resulting from the joining of an aromatic hydrocarbon ring and an aromatic heterocyclic ring. These rings may each be substituted with the above-described substituent V or the like. Preferred examples of the aromatic ring include those described above as examples of the aromatic ring for the aromatic group.

The group having an aromatic ring may also be expressed by -Lc-A ₂ wherein Lc represents a single bond or a linking group and A _{2 represents} an aromatic group. Preferred examples of the linking group represented by Lc include the linking groups described for La. Preferred examples of the aromatic group represented by A ₂ include those described above as examples of the aromatic group. Lc or A ₂ is preferably substituted with at least one anionic substituent.

Preferred examples of the group having an aromatic ring substituted with an anionic substituent include an alkyl group having an aromatic hydrocarbon ring such as an aralkyl group substituted with a sulfo group, a phosphoric acid group or a carboxyl group (eg, 2-sulfobenzyl , 4-sulfobenzyl, 4-sulfophenethyl, 3-phenyl-3-sulfopropyl, 3-phenyl-2-sulfopropyl, 4,4-diphenyl-3-sulfobutyl, 2- (4'-sulfo-4-biphenyl) -ethyl, 4 Phasphobenzyl), an aryloxycarbonylalkyl group substituted with a sulfo group, a phosphoric acid group or a carboxyl group (eg 3-sulfophenoxycarbonylpropyl) and an aryloxyalkyl group containing a sulfo group, a phosphoric acid group or a carboxyl group (eg 2- (4-sulfophenoxy) ethyl, 2- (2-phosphenoxy) ethyl, 4,4-diphenoxy-3-sulfobutyl);
an alkyl group having a heteroaromatic ring such as 3- (2-pyridyl) -3-sulfopropyl, 3- (2-furyl) -3-sulfopropyl and 2- (2-thienyl) -2-sulfopropyl;
an aryl group having an aromatic hydrocarbon group such as an aryl group substituted with a sulfo group, a phosphoric acid group or a carboxyl group (eg, 4-sulfophenyl, 4-sulfonaphthyl); and
a heteroaromatic group such as a heteroaromatic group substituted with a sulfo group, a phosphoric acid group or a carboxyl group (eg, 4-sulfo-2-thienyl, 4-sulfo-2-pyridyl).

From these are the alkyl groups which are an aromatic hydrocarbon or heteroaromatic group containing a sulfo group, a phosphoric acid group or a carboxyl group, more preferably, and further are the alkyl groups which are an aromatic hydrocarbon ring having a sulfo group, a phosphoric acid group or a carboxyl group is further more preferred, and the strongest preferred are 2-sulfobenzyl, 4-sulfobenzyl, 4-sulfophenethyl, 3-phenyl-3-sulfopropyl and 4-phenyl-4-sulfobutyl.

When the chromophore represented by D ₁ in the formula (III) is the methine dye represented by the formula (IV), (V) or (VI), the substituents represented by R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ and R ₂₃ shown each preferably the above-described unsubstituted alkyl group or substituted alkyl group (an alkyl group such as carboxyalkyl, sulfoalkyl, aralkyl and aryloxyalkyl).

When the chromophore represented by D ₂ in the formula (III) is the methine dye represented by the formula (IV), (V) or (VI), those represented by R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ and R ₂₃ are each preferably the above-described unsubstituted alkyl group or substituted alkyl group, more preferably an alkyl group having an anionic substituent (an alkyl group such as carboxyalkyl and sulfoalkyl), 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 to L ₆₄ represented methine group may have a substituent. Examples of the substituent include the above-described v, such as a substituted or unsubstituted alkyl group having 1 to 15, preferably 1 to 10, more preferably 1 to 5 carbon atoms (eg, methyl, ethyl, 2-carboxyethyl), a substituted or unsubstituted aryl group having 6 to 20, preferably 6 to 15, 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, more preferably 6 to 10 carbon atoms (eg N, N). Dimethyl barbituric acid), a halogen atom (eg, chlorine, bromine, iodine, fluorine), an alkoxy group having 1 to 15, preferably 1 to 10, more preferably 1 to 5 carbon atoms (eg, methoxy, ethoxy), an amino group having 0 to 15, preferably 2 to 10, more preferably 4 to 10 carbon atoms (eg, methylamino, N, N-dimethylamino, N-methyl-N-phenylamino, N-methylpiperazino), an alkylthio group having 1 to 15, preferably 1 to 10, more preferably 1 to 2 s 5 carbon atoms (eg, methylthio, ethylthio) and an arylthio group having 6 to 20, preferably 6 to 12, more preferably 6 to 10 carbon atoms (eg, phenylthio, p-methylphenylthio). There may be formed a ring with another methine group, or a ring may be formed together with Z ₁ to Z ₂₃ or 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 Each ₆₄ preferably represents an unsubstituted methine group.

n _1, n _2, n _3, n _4, n _5, n _6, n _7, n _8, n _9, n _10, n ₁₁ and n ₁₂ each independently 0, 1, 2, 3 or 4, preferably 0 , 1, 2 or 3, more preferably 0, 1 or 2, even more preferably 0 or 1. When n is ₁ , n ₂ , n ₃ , n ₄ , n ₅ , n ₆ , n ₇ , n ₈ , n ₉ , n ₁₀ , n ₁₁ and n _{12 are} each 2 or more, the methine group repeats, but these methine groups need not be the same.

p ₁ , p ₂ , p ₃ , p ₄ , p ₅ , p ₆ , p ₇ , p ₈ , p ₉ , p ₁₀ , p ₁₁ , p ₁₂ , p ₁₃ , p ₁₄ , p ₁₅ and p ₁₆ each independently 0 or 1, preferably 0, is.

M ₁ , M ₂ , M ₃ , M ₄ , M ₅ and M ₆ are each included in the formula so as to indicate the presence of a cation or anion when the ionic charge of the dye needs to be balanced. Typical examples of the cation include inorganic cations such as a hydrogen ion (H ⁺ ), alkali metal ions (eg, sodium ion, potassium ion, lithium ion), and alkaline earth metal ions (eg, calcium ion) and organic cations such as an ammonium ion (eg, ammonium ion, tetraalkylammonium ion, pyridinium ion, ethylpyridinium ion). The anion may be either an inorganic anion or an organic anion, and examples thereof include halogen anions (eg, fluoride ion, chloride ion, iodide ion), substituted aryl sulfonate ion (eg, p-toluenesulfonate ion, p-chlorobenzenesulfonate ion), aryl disulfonate ion (eg, 1,3-benzenesulfonate ion, 1 , 5-naphthalene disulfonation, 2,6-naphthalenedisulfonation), alkyl sulfations (eg methylsulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate, picration, acetate ion and trifluoromethanesulfonate ion. An ionic polymer or other dye having a charge opposite to the dye may also be used. When the counterion is a hydrogen ion, CO ₂ ^- and SO ₃ ^{- can be} referred to as CO ₂ H and SO ₃ H, respectively.

m ₁ , m ₂ , m ₃ , m ₄ , m ₅ and m ₆ each represent a number of 0 or greater, which is necessary to balance the electric charge, preferably a number from 0 to 4, more preferably 0 to 1, and they are 0 when an inner salt is formed.

below specific examples of only the dyes that are in the preferred Techniques described in the detailed description of the invention are given, but the present invention is of course in no way limited to this.

Specific Examples of the Compound of the Invention Represented by Formula (I) (Including Subconceptual Structures)

Specific Examples of the Compound of the Invention Represented by Formula (II) (Including Subconceptual Structures)

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

worin Z24 eine atomare Gruppe, die zum Bilden eines 5- oder 6-gliedrigen stickstoffhaltigen heterocyclischen Rings notwendig ist, darstellt, Z25 eine atomare Gruppe, die zum Bilden eines aliphatischen oder aromatischen Rings notwendig ist und die zum Bilden einer polycyclischen Kondensationsstruktur notwendig ist, die drei oder mehr Ringe, inklusive des stickstoffhaltigen heterocyclischen Rings, der durch Z24 gebildet wird, umfasst, Q eine Gruppe darstellt, die notwendig ist, um es der Verbindung, die durch die Formel (IV') dargestellt wird, zu ermöglichen, einen Methin-Farbstoff zu bilden, R24 eine Alkylgruppe, eine Arylgruppe oder eine heterocyclische Gruppe darstellt, L65 und L66 jeweils eine Methingruppe darstellen, p17 0 oder 1 darstellt, M7 ein Gegenion zum Ausgleichen der elektrischen Ladung darstellt und m7 eine Zahl von 0 bis 10 darstellt, die zum Neutralisieren der elektrischen Ladung des Moleküls notwendig ist.Besides the above-described method in which a sensitizing dye having a specific wavelength of the spectral absorption maximum or the spectral sensitivity distribution is used, in the present invention, by using a dye represented by the following formula (IV '), both the midpoint sensitivity (FIG. midpoint sensitivity) and the foot sensitivity on the photographic characteristic curve are increased, and a sharp spectral sensitivity spectrum can be obtained.

wherein Z24 represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring, Z25 represents an atomic group necessary for forming an aliphatic or aromatic ring and necessary for forming a polycyclic condensation structure three or more rings, including the nitrogen-containing heterocyclic ring formed by Z24, Q represents a group necessary to allow the compound represented by the formula (IV ') to form a methine Dye, R24 represents an alkyl group, an aryl group or a heterocyclic group, L65 and L66 each represents a methine group, p17 represents 0 or 1, M7 represents a counter ion for balancing the electric charge, and m7 represents a number of 0 to 10; necessary to neutralize the electrical charge of the molecule.

• (1) Von den Verbindungen, die durch die Formel (IV') dargestellt werden, wird ein Farbstoff, der keinen anionischen Substituenten aufweist, nämlich ein Farbstoff, der einen Substituenten zum Bilden eines kationischen Farbstoffes als Gesamtheit aufweist, verwendet (dieser Farbstoff ist als "Farbstoff IV'c" definiert). Wenn jedoch der Farbstoff IV'c allein verwendet wird, ist R24 vorzugsweise eine Alkylgruppe, die mit einer aromatischen Gruppe (eine Arylgruppe oder eine aromatische heterocyclische Gruppe) substituiert ist, eine Arylgruppe oder eine aromatische heterocyclische Gruppe.
• (2) Von den Verbindungen, die durch die Formel (IV') dargestellt werden, wird ein Farbstoff, der einen Substituenten zum Bilden eines anionischen Farbstoffs als Gesamtheit aufweist, verwendet (dieser Farbstoff ist als "Farbstoff IV'a" definiert).
• (3) Es werden zumindest ein Methin-Farbstoff, der durch die folgende Formel (IV'-1) dargestellt wird, und zumindest ein Farbstoff IV'a simultan verwendet:
  
  worin Z26 eine atomare Gruppe, die zum Bilden eines stickstoffhaltigen heterocyclischen Ringes notwendig ist, darstellt, vorausgesetzt, dass ein aromatischer Ring mit Z26 kondensiert sein kann, R25 stellt eine Alkylgruppe, eine Arylgruppe oder eine heterocyclische Gruppe dar, Q3 stellt eine Gruppe dar, die notwendig ist, um es der durch die Formel (IV'-1) dargestellten Verbindung zu ermöglichen, eine Methingruppe zu bilden, L67 und L68 stellen jeweils eine Methingruppe dar, p18 stellt 0 oder 1 dar, vorausgesetzt, dass Z26, R25, Q3, L67 und L68 jeweils einen Substituenten aufweisen, um es dem durch die Formel (IV'-1) dargestellten Methin-Farbstoff zu ermöglichen, als Gesamtheit einen kationischen Farbstoff zu bilden (d.h., keines weist einen anionischen Substituenten auf), M8 stellt ein Anion zum Ausgleichen der elektrischen Ladung dar, und m8 stelt eine Zahl von 0 bis 10 dar, die notwendig ist, um die molekulare Ladung zu neutralisieren. Der Farbstoff IV'a ist von dem Methin-Farbstoff, der durch die folgende Formel (IV'-2) dargestellt wird (anionischer Farbstoff), umfasst. Spezifischer entspricht der Farbstoff, bei dem der von Z27 gebildete stickstoffhaltige heterocyclische Ring eine polycyclische Kondensationsstruktur, die drei oder mehr Ringe umfasst, aufweist, dem Farbstoff IV'a.
• (4) Es werden zumindest ein Farbstoff IV'c und zumindest ein Methin-Farbstoff, der durch die folgende Formel (IV'-2) dargestellt wird, simultan verwendet:
  
  worin Z27 eine atomare Gruppe, die zum Bilden eines stickstoffhaltigen heterocyclischen Rings notwendig ist, darstellt, vorausgesetzt, dass ein aromatischer Ring mit Z27 kondensiert sein kann, R26 eine Alkylgruppe, eine Arylgruppe oder eine heterocyclische Gruppe darstellt, Q4 eine Gruppe darstellt, die notwendig ist, um es der durch die Formel (IV'-2) dargestellten Verbindung zu ermöglich, eine Methingruppe zu bilden, L69 und L70 jeweils eine Methingruppe darstellen, p19 0 oder 1 darstellt, vorausgesetzt, dass Z27, R26, Q4, L69 und L70 jeweils einen Substituenten aufweisen, um es dem durch die Formel (IV'-2) dargestellten Methin-Farbstoff zu ermöglichen, als Gesamtheit einen anionischen Farbstoff zu bilden, M9 ein Kation zum Ausgleichen der elektrischen Ladung darstellt und m9 eine Zahl von 0 bis 10 darstellt, die zum Neutralisieren der molekularen Ladung notwendig ist. Der Farbstoff IV'c ist von dem obigen, durch die Formel (IV'-1) dargestellten Methin-Farbstoff (kationischer Farbstoff) umfasst. Spezifischer entspricht der Farbstoff, bei dem der von Z26 gebildete stickstoffhaltige heterocyclische Ring eine polycyclische Kondensationsstruktur aufweist, die drei oder mehr Ringe umfasst, dem Farbstoff IV'c. Wenn ein durch die Formel (IV'-1) dargestellter Methin-Farbstoff und ein Farbstoff IV'a in Kombination verwendet werden, ist vorzugsweise zumindest eines von R24 und R25 eine Alkylgruppe, die mit einer aromatischen Gruppe (eine Arylgruppe oder eine aromatische heterocyclische Gruppe) substituiert ist, eine Arylgruppe oder eine aromatische heterocyclische Gruppe. In einer stärker bevorzugten Ausführungsform sind R24 und R25 beide eine Alkylgruppe, die mit einer aromatischen Gruppe (eine Arylgruppe oder eine aromatische heterocyclische Gruppe) substituiert ist, eine Arylgruppe oder eine aromatische heterocyclische Gruppe. Wenn ein Farbstoff IV'c und ein durch die Formel (IV'-2) dargestellter Methin-Farbstoff in Kombination verwendet werden, ist vorzugsweise zumindest eines von R24 und R26 eine Alkylgruppe, die mit einer aromatischen Gruppe (eine Arylgruppe oder eine aromatische heterocyclische Gruppe) substituiert ist, eine Arylgruppe oder eine aromatische heterocyclische Gruppe. In einer stärker bevorzugten Ausführungsform sind R24 und R26 beide eine Alkylgruppe, die mit einer aromatischen Gruppe (eine Arylgruppe oder eine aromatische heterocyclische Gruppe) substituiert ist, eine Arylgruppe oder eine aromatische heterocyclische Gruppe. Die Verbindung der Formel (IV'-1) wird stärker bevorzugt durch die folgende Formel (IV'-3) dargestellt:
  
  worin L71, L72, L73, L74, L75, L76 und L77 jeweils eine Methingruppe darstellen, p20 und p21 jeweils 0 oder 1 darstellen, n13 0, 1, 2, 3 oder 4 darstellt, Z28 und Z29 jeweils eine atomare Gruppe, die zum Bilden eines 5- oder 6-gliedrigen stickstoffhaltigen heterocyclischen Ringes notwendig ist, darstellen, vorausgesetzt, dass ein aromatischer Ring mit Z28 oder Z29 kondensiert sein kann, R27 und R28 jeweils eine Alkylgruppe, eine Arylgruppe oder eine heterocyclische Gruppe darstellen, vorausgesetzt, dass R27, R28, Z28, Z29, L71, L72 und L73 keinen anionischen Substituenten aufweisen, d.h., jedes weist einen Substituenten zum Bilden eines kationischen Farbstoffs als Gesamtheit auf, und M8 und m8 haben die gleichen Bedeutungen wie in Formel (IV'-1). Die Verbindung der Formel (IV'-2) wird stärker bevorzugt durch die folgende Formel (IV'-4) dargestellt:
  
  worin L78, L79, L80, L81, L82, L83 und L84 jeweils eine Methingruppe darstellen, p22 und p23 jeweils 0 oder 1 darstellen, n14 0, 1, 2, 3 oder 4 darstellt, Z30 und Z31 jeweils eine atomare Gruppe, die zum Bilden eines 5- oder 6-gliedrigen stickstoffhaltigen heterocyclischen Rings notwendig ist, darstellen, vorausgesetzt, dass ein aromatischer Ring mit Z30 oder Z31 kondensiert sein kann, R29 und R30 jeweils eine Alkylgruppe, eine Arylgruppe oder eine heterocyclische Gruppe darstellen, vorausgesetzt, dass R29 und R30 jeweils einen anionischen Substituenten aufweisen, und M9 und m9 haben die gleichen Bedeutungen wie in Formel (IV'-2). Wenn ein durch die Formel (IV'-3) dargestellter Methin-Farbstoff, der von dem Farbstoff IV'c umfasst ist, allein verwendet wird, ist vorzugsweise zumindest eines von R27 und R28 eine Alkylgruppe, die mit einer aromatischen Gruppe (eine Arylgruppe oder eine aromatische heterocyclische Gruppe) substituiert ist, eine Arylgruppe oder eine aromatische heterocyclische Gruppe. In einer stärker bevorzugten Ausführungsform sind R27 und R28 beide eine Alkylgruppe, die mit einer aromatischen Gruppe (eine Arylgruppe oder eine aromatische heterocyclische Gruppe) substituiert ist, eine Arylgruppe oder eine aromatische heterocyclische Gruppe. Wenn ein durch die Formel (IV'-3) dargestellter Methin-Farbstoff, der von dem Farbstoff IV'c umfasst ist, und ein durch die Formel (IV'-4) dargestellter Methin-Farbstoff, der von dem Farbstoff IV'a umfasst ist, in Kombination verwendet werden, ist vorzugsweise zumindest eines von R27, R28, R29 und R30 eine Alkylgruppe, die mit einer aromatischen Gruppe (eine Arylgruppe oder eine aromatische heterocyclische Gruppe) substituiert ist, eine Arylgruppe oder eine aromatische heterocyclische Gruppe. In einer stärker bevorzugten Ausführungsform sind zumindest zwei von R27, R28, R29 und R30 eine Alkylgruppe, die mit einer aromatischen Gruppe (eine Arylgruppe oder eine aromatische heterocyclische Gruppe) substituiert ist, eine Arylgruppe oder eine aromatische heterocyclische Gruppe; in einer weiterhin stärker bevorzugten Ausführungsform sind zumindest drei von 27, R28, R29 und R30 eine Alkylgruppe, die mit einer aromatischen Gruppe (eine Arylgruppe oder eine aromatische heterocyclische Gruppe) substituiert ist, eine Arylgruppe oder eine aromatische heterocyclische Gruppe; und in einer besonders bevorzugten Ausführungsform sind R27, R28, R29 und R30 alle eine Alkylgruppe, die mit einer aromatische Gruppe (einer Arylgruppe oder eine aromatische heterocyclische Gruppe) substituiert ist, eine Arylgruppe oder eine aromatische heterocyclische Gruppe.
• (5) Es wird ein durch die folgende Formel (V') dargestellter Spektralsensibilisierer (der eine polycyclische Kondensationsstruktur, die drei Ringe umfasst, aufweist) verwendet:
  
  worin Y1 und Y2 jeweils O oder S darstellen, Za und Zb jeweils eine atomare Gruppe, die zum Bilden eines Benzolrings notwendig ist, darstellen, die numerischen Werte (4, 5, 6 und 7) in der Formel jeweils die Stelle anzeigen, an die ein Benzolring gebunden ist, der Benzolring an irgendeines von (4,5), (5,6) und (6,7) gebunden ist, Ra und Rb jeweils die gleiche Bedeutung wie R24 in Formel (IV') haben, La, Lb und Lc jeweils eine Methingruppe darstellen und die gleiche Bedeutung wie L73 haben, n 0, 1 oder 2 darstellt, und M10 und m10 die gleichen Bedeutungen wie M7 bzw. m7 haben.
• (i) In einer bevorzugten Ausführungsform der Formel (V') ist n 1, La und Lc sind jeweils eine unsubstituierte Methingruppe und Lb ist eine Methingruppe, die mit einer Alkylgruppe substituiert ist, die 1 bis 5 Kohlenstoffatome aufweist (vorzugsweise eine Methylgruppe oder eine Ethylgruppe).
• (ii) In (i) ist der durch Za oder Zb gebildete Benzolring stärker bevorzugt an (4, 5) oder (5, 6) gebunden. In diesem Fall sind Y1 und Y2 beide besonders bevorzugt 0.
• (iii) In (ii) sind Ra und Rb beide eine Alkylgruppe, die mit einer aromatischen Gruppe substituiert ist, eine Arylgruppe oder eine aromatische heterocyclische Gruppe.
• (iv) In (iii) ist der Substituent so ausgewählt, dass der Spektralsensibilisierer als Ganzes einen kationischen Farbstoff oder einen anionischen Farbstoff bildet.
• (v) Darüber hinaus werden bevorzugt ein kationischer Farbstoff, der zu dem durch die Formel (V') dargestellten Spektralsensibilisierer gehört, und ein anionischer Farbstoff, der zu dem durch die Formel (V') dargestellten Spektralsensibilisierer gehört, gleichzeitig verwendet.

Hereinafter, preferred examples of the dye represented by the formula (IV ') will be described in practice.

• (1) Of the compounds represented by the formula (IV '), a dye having no anionic substituent, namely, a dye having a substituent for forming a cationic dye as a whole is used (this dye is described as "Dye IV'c" defined). However, when the dye IV'c is used alone, R24 is preferably an alkyl group substituted with an aromatic group (an aryl group or an aromatic heterocyclic group), an aryl group or an aromatic heterocyclic group.
• (2) Of the compounds represented by the formula (IV '), a dye having a substituent for forming an anionic dye as a whole is used (this dye is defined as "dye IV'a").
• (3) At least one methine dye represented by the following formula (IV'-1) and at least one dye IV'a are used simultaneously:
  
  wherein Z26 is an atomic group necessary for forming a nitrogen-containing heterocyclic ring provided that an aromatic ring may be condensed with Z26, R25 represents an alkyl group, an aryl group or a heterocyclic group, Q3 represents a group necessary to satisfy the formula represented by the formula (IV'-1 L67 and L68 each represent a methine group, p18 represents 0 or 1, provided that Z26, R25, Q3, L67 and L68 each have a substituent to give it the formula represented by the formula (IV'-1) to form a cationic dye as a whole (ie, none has an anionic substituent), M8 represents an anion to balance the electric charge, and m8 represents a number from 0 to 10, which is necessary to neutralize the molecular charge. The dye IV'a is comprised of the methine dye represented by the following formula (IV'-2) (anionic dye). More specifically, the dye in which the nitrogen-containing heterocyclic ring formed by Z27 has a polycyclic condensation structure comprising three or more rings corresponds to the dye IV'a.
• (4) At least one dye IV'c and at least one methine dye represented by the following formula (IV'-2) are simultaneously used:
  
  wherein Z27 represents an atomic group necessary for forming a nitrogen-containing heterocyclic ring, provided that an aromatic ring may be condensed with Z27, R26 represents an alkyl group, an aryl group or a heterocyclic group, Q4 represents a group which is necessary to allow the compound represented by the formula (IV'-2) to form a methine group, L69 and L70 each represent a methine group, p19 represents 0 or 1, provided that Z27, R26, Q4, L69 and L70 respectively have a substituent to allow the methine dye represented by the formula (IV'-2) to form an anionic dye as a whole, M9 represents a cation for balancing the electric charge, and m9 represents a number from 0 to 10, which is necessary to neutralize the molecular charge. The dye IV'c is comprised of the above methine dye (cationic dye) represented by the formula (IV'-1). More specifically, the dye in which the nitrogen-containing heterocyclic ring formed by Z26 has a polycyclic condensation structure comprising three or more rings corresponds to the dye IV'c. When a methine dye represented by the formula (IV'-1) and a dye IV'a are used in combination, at least one of R24 and R25 is preferably an alkyl group having an aromatic group (an aryl group or an aromatic heterocyclic group ), an aryl group or an aromatic heterocyclic group. In a more preferred embodiment, R24 and R25 are both an alkyl group substituted with an aromatic group (an aryl group or an aromatic heterocyclic group), an aryl group or an aromatic heterocyclic group. When a dye IV'c and a methine dye represented by the formula (IV'-2) are used in combination, at least one of R24 and R26 is preferably an alkyl group having an aromatic group (an aryl group or an aromatic heterocyclic group ), an aryl group or an aromatic heterocyclic group. In a more preferred embodiment, R24 and R26 are both an alkyl group substituted with an aromatic group (an aryl group or an aromatic heterocyclic group), an aryl group or an aromatic heterocyclic group. The compound of the formula (IV'-1) is more preferably represented by the following formula (IV'-3):
  
  wherein L71, L72, L73, L74, L75, L76 and L77 each represents a methine group, p20 and p21 each represents 0 or 1, n13 represents 0, 1, 2, 3 or 4, Z28 and Z29 each represent an atomic group belonging to Forming a 5- or 6-membered nitrogen-containing heterocyclic ring, provided that an aromatic ring may be condensed with Z28 or Z29, R27 and R28 are each an alkyl group, an aryl group or a heterocyclic group, provided that R27, R28, Z28, Z29, L71, L72 and L73 have no anionic substituent, that is, each has a substituent for forming a cationic dye as a whole, and M8 and m8 have the same meanings as in formula (IV'-1). The compound of the formula (IV'-2) is more preferably represented by the following formula (IV'-4):
  
  wherein L78, L79, L80, L81, L82, L83 and L84 each represents a methine group, p22 and p23 each represent 0 or 1, n14 represents 0, 1, 2, 3 or 4, Z30 and Z31 each represent an atomic group belonging to Forming a 5- or 6-membered nitrogen-containing heterocyclic ring, provided that an aromatic ring may be condensed with Z30 or Z31, R29 and R30 each represents an alkyl group, an aryl group or a heterocyclic group, provided that R29 and R30 each have an anionic substituent, and M9 and m9 have the same meanings as in formula (IV'-2). When a methine dye represented by the formula IV'-3 represented by the formula (IV'-3) is used alone, at least one of R27 and R28 is preferably an alkyl group having an aromatic group (an aryl group or an aromatic heterocyclic group), an aryl group or an aromatic heterocyclic group. In a more preferred embodiment, R 27 and R 28 are both an alkyl group substituted with an aromatic group (an aryl group or an aromatic heterocyclic group), an aryl group or an aromatic heterocyclic group. When a methine dye represented by the formula (IV'-3) represented by the dye IV'c and a methine dye represented by the formula (IV'-4) comprising the dye IV'a when used in combination, preferably, at least one of R 27, R 28, R 29 and R 30 is an alkyl group substituted with an aromatic group (an aryl group or an aromatic heterocyclic group), an aryl group or an aromatic heterocyclic group. In a more preferred embodiment, at least two of R 27, R 28, R 29 and R 30 are an alkyl group substituted with an aromatic group (an aryl group or an aromatic heterocyclic group), an aryl group or an aromatic heterocyclic group; in a still more preferred embodiment, at least three of 27, R28, R29 and R30 are an alkyl group substituted with an aromatic group (an aryl group or an aromatic heterocyclic group), an aryl group or an aromatic heterocyclic group; and in a particularly preferred embodiment, R 27, R 28, R 29 and R 30 are all an alkyl group substituted with an aromatic group (an aryl group or an aromatic heterocyclic group), an aryl group or an aromatic heterocyclic group.
• (5) A spectral sensitizer represented by the following formula (V ') (having a polycyclic condensation structure comprising three rings) is used.
  
  wherein Y1 and Y2 each represent O or S, Za and Zb each represent an atomic group necessary for forming a benzene ring, the numerical values (4, 5, 6, and 7) in the formula indicate, respectively, the site to which a benzene ring is attached, the benzene ring is bonded to any of (4,5), (5,6) and (6,7), Ra and Rb are each the same as R24 in formula (IV '), La, Lb and Lc each represent a methine group and have the same meaning as L73, n represents 0, 1 or 2, and M10 and m10 have the same meanings as M7 and m7, respectively.
• (i) In a preferred embodiment of formula (V '), n is 1, La and Lc are each an unsubstituted methine group and Lb is a methine group substituted with an alkyl group having 1 to 5 carbon atoms (preferably a methyl group or a ethyl).
• (ii) In (i), the benzene ring formed by Za or Zb is more preferably attached to (4, 5) or (5, 6). In this case, Y1 and Y2 are both more preferably 0.
• (iii) In (ii), Ra and Rb are both an alkyl group substituted with an aromatic group Aryl group or an aromatic heterocyclic group.
• (iv) In (iii), the substituent is selected so that the spectral sensitizer as a whole forms a cationic dye or an anionic dye.
• (v) In addition, a cationic dye belonging to the spectral sensitizer represented by the formula (V ') and an anionic dye belonging to the spectral sensitizer represented by the formula (V') are preferably used simultaneously.

In The present invention refers to a cationic dye a dye which does not have an anionic substituent, and the anionic dye refers to a dye which has a having anionic substituents.

The anionic substituent referred to in the present invention is a substituent having a negative charge, and this substituent is an atomic group capable of easily dissociating, more particularly, under neutral or weakly alkaline conditions Substituent having a hydrogen atom. Examples thereof include a sulfo group (-SO ₃ ^- ), a sulfuric acid group (-OSO ₃ ^- ), a carboxyl group (-CO ₂ ^- ), a phosphoric acid group (-PO ₃ ^- ), an alkylsulfonylcarbamoylalkyl group (eg, methanesulfonylcarbamoylmethyl), an acylcarbamoylalkyl group (eg Acetylcarbamoylmethyl), an acylsulfamoylalkyl group (eg, acetylsulfamoylmethyl), and an alkylsulfonylsulfamoylalkyl group (eg, methanesulfonylsulfamoylmethyl).

Photosensitive Materials Using Silver Halide Grains Which by adsorbing a dye chromophore in one or more Layers are obtained on a silver halide grain, as above described, show in many cases a broad spectral sensitivity distribution. The inventors have found that this problem can be reduced by by adding the dye in the first layer and also the dyes in the second and subsequent layers is made possible a spectral To possess sensitivity due to absorption, that of J-association (i.e., J-aggregation).

The by the formulas (IV '), (IV'-1), (IV'-2), (IV'-3) and (IV'-4) shown Compounds for use in the present invention are described in detail below.

According to the structure of Q, Q3 and Q4 in formulas (IV '), (IV'-1) and (IV'-2) may be any Methine dye are formed. Preferred examples thereof include Cyanine dyes, merocyanine dyes, rhodacyanine dyes, Oxonol dyes, trinuclear merocyanine dyes, tetranuclear merocyanine dyes, Allopolar Dyes, Styryl Dyes, styryl based dyes, hemicyanine dyes, streptocyanine dyes and hemioxonol dyes. Among them are cyanine dyes, merocyanine dyes and rhodacyanine dyes stronger and, furthermore, cyanine dyes (in which the electrical Charge of any of cation, anion and betaine) is more preferred. These dyes are described in detail in F.M. Harmer, Heterocyclic Compounds - Cyanine Dyes and Related Compounds, John Wiley & Sons, New York, London (1964) and D.M. Stunner, Heterocyclic Compounds - Special Topics in Heterocyclic Chemistry, Chapter 18, Section 14, pages 482-515, John Wiley & Sons, New York, London (1977).

For merocyanine dyes and Rhodacyanin dyes are the formulas (XII) and (XIII), the in U.S. Patent 5,340,694, pages 21 and 22 are preferred.

If When a cyanine dye is formed by Q, the formula (IV ') can be represented by the following Expressed in resonance formula become:

The number of methine groups in Q, Q3 or Q4 is preferably 0 to 7, more preferably 0 to 5, even more preferably 3. As long as Q, Q3 or Q4 form the dye described above (eg cyanine dye, merocyanine dye, rhodacyanine Dye, trinuclear merocyanine dye, allopolar dye, hemicyanine dye, styryl dye) here can be the number of methine groups 0 (eg, simple merocyanine). The methine group is preferably substituted with a substituent (eg, a heterocyclic group, an aliphatic group, an aromatic group) used to form a methine dye necessary is. The substituent is preferably a heterocyclic group, an aliphatic group or an aromatic group, more preferably a heterocyclic group.

The aromatic group includes a substituted or unsubstituted one aromatic group (e.g., 4-dimethylaminophenyl, 4-methoxyphenyl, Phenyl, 4-dimethylaminonaphthyl).

preferred Examples of the aliphatic group include an alkoxycarbonyl group (e.g., ethoxycarbonyl) and an acyl group (e.g., acetyl). Other Examples include the substituents represented by the above-described V are shown. Of these, e.g. a substituted or unsubstituted amino group (e.g., amino, dimethylamino), a cyano group, an alkoxycarbonyl group (e.g., ethoxycarbonyl), a substituted one or unsubstituted alkylsulfonyl group (e.g., methylsulfonyl) and a substituted or unsubstituted acyl group (e.g., acetyl) prefers.

In Formula (IV ') provides Z24 is an atomic group that is used to form a 5- or 6-membered atom nitrogen-containing heterocyclic ring is necessary nitrogen-containing heterocyclic ring formed by Z24 may be condensed with an aromatic ring. Examples of this include a thiazole nucleus, a thiazole nucleus, an oxazoline nucleus, an oxazole nucleus, a selenazoline nucleus, a selenazole nucleus, a 3,3-dialkyl-3H-pyrrole nucleus (e.g. 3,3-dimethyl-3H-pyrrole), an imidazoline nucleus, an imidazole nucleus, a 2-pyridine nucleus, a 4-pyridine nucleus, an imidazo [4,5-b] quinoxaline nucleus, an oxadiazole nucleus, a thiadiazole nucleus, a tetrazole nucleus, one Pyrimidine nucleus, a pyridazine nucleus and a pyrazine nucleus. Of these are a thiazole nucleus, an oxazole nucleus, a selenazole nucleus, a 3,3-dialkyl-3H-pyrrole nucleus, an imidazole nucleus and a 2-pyridine nucleus, and a thiazole nucleus, an oxazole nucleus, an imidazole nucleus and a 2-pyridine nucleus are more preferable.

Assuming that the substituent on the nitrogen-containing heterocyclic ring is V, the substituent represented by V is not particularly limited. Examples thereof include a halogen atom (eg, chlorine, bromine, iodine, fluorine), a mercapto group, a cyano group, a carboxyl group, a phosphoric acid group, a sulfo group, a hydroxy group, a carbamoyl group having 1 to 10, preferably 2 to 8, more preferably 2 to 5 carbon atoms (eg, methylcarbamoyl, ethylcarbamoyl, morpholinocarbonyl), a sulfamoyl group having 0 to 10, preferably 2 to 8, more preferably 2 to 5 carbon atoms (eg, methylsulfamoyl, ethylsulfamoyl, piperidinosulfonyl), a nitro group, an alkoxy group having 1 to 20, preferably 1 to 10, more preferably 1 to 8 carbon atoms (eg methoxy, ethoxy, 2-methoxyethoxy, 2-phenylethoxy), an aryloxy group having 6 to 20, preferably 6 to 12, more preferably 6 to 10 carbon atoms (eg phenoxy, p-methylphenoxy, p-chlorophenoxy, naphthoxy), an acyl group having 1 to 20, preferably 2 to 12, more preferably 2 to 8 carbon atoms (eg, acetyl, benzoyl, trichloroacetyl), an acyloxy group having 1 to 20, preferably 2 to 12, more preferably 2 to 8 carbon atoms (eg acetyloxy, benzoyloxy), an acylamino group having 1 to 20, preferably 2 to 12, more preferably 2 to 8 carbon atoms (eg acetylamino), a sulfonyl group having 1 to 20, preferably 1 to 10, more preferably 1 to 8 carbon atoms (eg methanesulfonyl, ethanesulfonyl, benzenesulfonyl), a sulfinyl group having 1 to 20, preferably 1 to 10, more preferably 1 to 8 carbon atoms (eg methanesulfinyl, ethanesulfinyl, benzenesulfinyl), a sulfonylamino group 1 to 20, preferably 1 to 10, more preferably 1 to 8 carbon atoms (eg methanesulfonylamino, ethanesulfonylamino, benzenesulfonylamino), an amino group, a substituted amino group having 1 to 20, preferably 1 to 12, more preferably 1 to 8 carbon atoms (eg methylamino, Dimethylamino, dibenzylamino, anilino, diphenylamino), an ammonium group having 0 to 15, preferably 3 to 10, more preferably 3 to 6 carbon atoms (eg, trimethyl lammonium, triethylammonium), a hydrazino group having 0 to 15, preferably 1 to 10, more preferably 1 to 6 carbon atoms (eg trimethylhydrazino), a ureido group having 1 to 15, preferably 1 to 10, more preferably 1 to 6 carbon atoms (eg ureido, N, N-dimethylureido), an imido group having 1 to 15, preferably 1 to 10, more preferably 1 to 6 carbon atoms (eg succinimido), an alkylthio group having 1 to 20, preferably 1 to 12, more preferably 1 to 8 carbon atoms (eg Methylthio, ethylthio, propylthio), an arylthio group having 6 to 20, preferably 6 to 12, more preferably 6 to 10 carbon atoms (eg, phenylthio, p-methylphenylthio, p-chlorophenylthio, 2-pyridylthio, naphthylthio), an alkoxycarbonyl group having 2 to 20 , preferably 2 to 12, more preferably 2 to 8 carbon atoms (eg, methoxycarbonyl, ethoxycarbonyl, 2-benzyloxycarbonyl), an aryloxycarbonyl group having 6 to 20, preferably 6 to 12, more preferably 6 to 10 carbon atoms (eg, P henoxycarbonyl), an unsubstituted alkyl group having 1 to 18, preferably 1 to 10, more preferably 1 to 5 carbon atoms (eg, methyl, ethyl, propyl, butyl), a substituted alkyl group having 1 to 18, preferably 1 to 10, more preferably 1 to 5 carbon atoms {eg hydroxymethyl, trifluoromethyl, benzyl, carboxyethyl, ethoxycarbonylmethyl, acetylaminomethyl; the substituted alkyl group includes an unsaturated hydrocarbon group having 2 to 18, preferably 3 to 10, more preferably 3 to 5 carbon atoms (eg, vinyl, ethynyl, 1-cyclohexenyl, benzylidine, benzylidene)}, a substituted or unsubstituted aryl group having 6 to 20, preferably 6 to 15, stronger preferably 6 to 10 carbon atoms (eg, phenyl, naphthyl, p-carboxyphenyl, p-nitrophenyl, 3,5-dichlorophenyl, p-cyanophenyl, m-fluorophenyl, p-tolyl) and a substituted or unsubstituted heterocyclic group of 1 to 20, preferably 2 to 10, more preferably 4 to 6 carbon atoms (eg, pyridyl, 5-methylpyridyl, thienyl, furyl, morpholino, tetrahydrofurfuryl). These may have such a structure that a benzene ring or a naphthalene ring is condensed thereon. In addition, these substituents may be further substituted with V.

From these substituents are the alkyl group, the aryl group, the alkoxy group, the halogen atom and benzene ring condensation products thereof, and the methyl group, phenyl group, methoxy group, the chlorine atom, the bromine atom, the iodine atom and benzene ring condensation products these are stronger prefers.

Z25 represents an atomic group that is used to form an aliphatic or aromatic cyclic compound is necessary and to form a polycyclic condensation structure containing three or more rings, including the nitrogenous heterocyclic formed by Z24 Rings, includes, is necessary. Examples of those formed by Z25 cyclic structure include an unsubstituted aliphatic cyclic Structure with a bicyclic or larger polycyclic condensation ring structure (e.g., decahydronaphthalene), a substituted aliphatic cyclic Structure with a bicyclic or larger polycyclic condensation structure (Examples of the substituent include those described above as examples of the substituent V), an unsubstituted one aromatic cyclic structure with a bicyclic or larger polycyclic Condensation ring structure (e.g., pentals, indene, naphthalene, azulene, Anthracene, phenanthrene, anthracene), a substituted aromatic cyclic structure with a bicyclic or larger polycyclic Condensation ring structure (examples of the substituent include those described above as examples of the substituent V. are), an unsubstituted heterocyclic structure with a bicyclic or larger polycyclic ones Condensation ring structure (e.g., quinolizine, purine, naphthylidine), a substituted heterocyclic structure with a bicyclic or larger polycyclic ones Condensation ring structure (examples of the substituent include those described above as examples of the substituent V. are) and a structure with a bicyclic or larger polycyclic Condensation ring structure resulting from the condensation of two or more of an aliphatic ring structure, an aromatic ring structure and a heterocyclic ring (e.g., benzofuran, benzothiophene, Indole, oxathiin, quinoline, thiazine, phenothiazine, phenoxathiin, Phenazine, indoline, benzomorpholine, benzopyran, cyclopentapyran, Dithianaphthalene, benzoxazine, benzofuran, dibenzothiophene, carbazole, Chroman, Coumarin, Xanthen, Thianthren) results with a Substituents V may be substituted.

From the ring structures formed by Z25 are unsubstituted aromatic ring structure with a bicyclic or larger polycyclic Condensation ring structure (e.g., pentals, indene, naphthalene, azulene, Anthracene, phenanthrene), a substituted aromatic ring structure with a bicyclic or larger polycyclic Condensation ring structure and a structure with a bicyclic or larger polycyclic ones Condensation ring structure resulting from the condensation of two or more of an aliphatic ring structure, an aromatic ring structure and a heterocyclic ring structure (e.g., benzofuran, benzothiophene, Indole, thioxathiin, quinoline, thiazine, phenothiazine, phenoxathiin, Phenazine, indoline, benzomorpholine, benzopyran, cyclopentapyran, Dithianaphthalene, benzoxazine, dibenzofuran, dibenzothiophene, carbazole, Chroman, coumarin, phenoxathiin, xanthene, thianthrene, including substitution products thereof), preferably, stronger preferred are a structure having a tricyclic or larger polycyclic condensation ring structure, that from the condensation of three or more of an aliphatic ring structure, an aromatic ring structure and a heterocyclic structure (e.g., anthracene, phenanthrene, dibenzofuran, dibenzothiophene, carbazole, Phenoxathiin, xanthene, thianthrene, including substitution products of it) results, and above In addition, anthracene, dibenzofuran, dibenzothiophene and carbazole still stronger prefers.

In formulas (IV'-1), (IV'-2), (IV'-3) and (IV'-4), Z26, Z27, Z28, Z29, Z30 and Z31 each represent an atomic group capable of forming a nitrogen-containing heterocyclic ring, provided that an aromatic ring may be condensed thereon. Examples of the aromatic ring include a benzene ring, a naphthalene ring and a heteroaromatic ring such as a pyrazine ring and a thiophene 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 benzoxazole nucleus, a selenazole nucleus, a selenazole nucleus, a benzoselenazole nucleus, a 3,3-dialkylindolenine nucleus (eg, 3,3-dimethylindolenine), an imidazoline nucleus , an imidazole nucleus, a benzimidazole nucleus, a 2-pyridine nucleus, a 4-pyridine nucleus, a 2-quinoline nucleus, a 4-quinoline nucleus, a 1-isoquinoline nucleus, a 3-isoquinoline nucleus, an imidazo [4,5-b] quinoxaline nucleus, an oxadiazole nucleus , a thiadiazole nucleus, a tetrazole nucleus and a Pyrimidine. Of these, a benzothiazole nucleus, a benzoxazole nucleus, a 3,3-dialkylindolenine nucleus (eg, 3,3-dimethylindolenine), a benzimidazole nucleus, a 2-pyridine nucleus, a 4-pyridine nucleus, a 2-quinoline nucleus, a 4-quinoline nucleus, a 1 Isoquinoline nucleus and a 3-isoquinoline nucleus are preferred; more preferred are a benzothiazole nucleus, a benzoxazole nucleus, a 3,3-dialkylindolenine nucleus (eg 3,3-dimethylindolenine) and a benzimidazole nucleus; more preferred are a benzoxazole nucleus, a benzothiazole nucleus and a benzimidazole nucleus, and most preferred are a benzoxazole nucleus and a benzothiazole nucleus.

Of the nitrogen-containing heterocyclic ring may further be substituted with a substituent V, which is described above, be substituted. The substituent V at Z26, Z27, Z28, Z29, Z30 or Z31 is preferably an aryl group, an aromatic heterocyclic ring or an aromatic ring condensation product.

L65 to L84 each independently a methine group. The methine group shown from L65 to L84 may have a substituent, and examples of the substituent include a substituted or unsubstituted alkyl group with 1 to 15, preferably 1 to 10, more preferably 1 to 5 carbon atoms (e.g., methyl, ethyl, 2-carboxyethyl), a substituted or unsubstituted one Aryl group having 6 to 20, preferably 6 to 15, more preferably 6 to 10 carbon atoms (e.g., phenyl, o-carboxyphenyl), a substituted or unsubstituted one heterocyclic group of 3 to 20, preferably 4 to 15, more preferably 6 to 10 carbon atoms (e.g., N, N-dimethylbarbituric acid) Halogen atom (e.g., chlorine, bromine, iodine, fluorine), an alkoxy group 1 to 15, preferably 1 to 10, stronger preferably 1 to 5 carbon atoms (e.g., methoxy, ethoxy), one Amino group of 0 to 15, preferably 2 to 10, more preferably 4 to 10 carbon atoms (e.g., methylamino, N, N-dimethylamino, N -methyl-N-phenylamino, N -methylpiperazino), an alkylthio group having 1 to 15, preferably 1 to 10, more preferably 1 to 5 carbon atoms (e.g., methylthio, ethylthio) and an arylthio group with 6 to 20, preferably 6 to 12, more preferably 6 to 10 carbon atoms (e.g., phenylthio, p -methylphenylthio). It can also be a ring with another methine group or an auxochrome.

L65 to L72, L76 to L79, L83 and L84 are each preferably one unsubstituted methine group.

p17, p18, p19, p20, p21, p22 and p23 are each 0 or 1 and preferred 0 dar.

R24, R25, R26, R27, R28, R29 and R30 each represent an alkyl group, an aryl group or a heterocyclic group. Specific Examples thereof include an unsubstituted alkyl group with 1 to 18, preferably 1 to 7, stronger preferably 1 to 4 carbon atoms (for example methyl, ethyl, propyl, Isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl), a substituted alkyl group having 1 to 18, preferably 1 to 7, more preferably 1 to 4 carbon atoms {e.g. an alkyl group associated with V, the described above as examples of the substituent is; preferably an aralkyl group (e.g., benzyl, 2-phenylethyl), an unsaturated one Hydrocarbon group (e.g., allyl), a hydroxyalkyl group (e.g. 2-hydroxyethyl, 3-hydroxypropyl), a carboxyalkyl group (e.g. 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, carboxymethyl), an alkoxyalkyl group (e.g., 2-methoxyethyl, 2- (2-methoxyethoxy) ethyl), an aryloxyalkyl group (e.g., 2-phenoxyethyl, 2- (1-naphthoxy) ethyl), an alkoxycarbonylalkyl group (e.g., ethoxycarbonylmethyl, 2-benzyloxycarbonylethyl), an aryloxycarbonylalkyl group (e.g., 3-phenoxycarbonylpropyl), an acyloxyalkyl group (e.g., 2-acetyloxyethyl), an acylalkyl group (e.g., 2-acetylethyl), a carbamoylalkyl group (e.g., 2-morpholinocarbonylethyl), a sulfamoylalkyl group (e.g., N, N-dimethylcarbamoylmethyl), a Sulfoalkyl group (e.g., 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2- [3-sulfopropoxy] ethyl, 2-hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl), a sulfoalkenyl group, a sulfatoalkyl group (e.g., 2-sulfatoethyl, 3-sulfatopropyl, 4-sulfato-butyl), a heterocyclic substituted ring alkyl group (e.g., 2- (pyrrolidin-2-one-1-yl) ethyl, Tetrahydrofurfuryl), an alkylsulfonylcarbamoylmethyl group (e.g. Methanesulfonylcarbamoylmethyl)}, an unsubstituted aryl group with 6 to 20, preferably 6 to 10, more preferably 6 to 8 carbon atoms (e.g., phenyl, 1-naphthyl), a substituted aryl group having 6 to 20, preferably 6 to 10, stronger preferably 6 to 8 carbon atoms (e.g., an alkyl group, the with V, described above as examples of the substituent is, is substituted; specifically p-methoxyphenyl, p-methylphenyl, p-chlorophenyl), an unsubstituted heterocyclic group with 1 to 20, preferably 3 to 10, stronger preferably 4 to 8 carbon atoms (e.g., 2-furyl, 2-thienyl, 2-pyridyl, 3-pyrazolyl, 3-isooxazolyl, 3-isothiazolyl, 2-imidazolyl, 2-oxazolyl, 2-thiazolyl, 2-pyridazyl, 2-pyrimidyl, 3-pyrazyl, 2- (1,3,5-triazolyl), 3- (1,2,4-triazolyl), 5-tetrazolyl), a substituted heterocyclic group with 1 to 20, preferably 3 to 10, more preferably 4 to 8 carbon atoms (For example, a heterocyclic group represented by V, as described above Examples of the substituent described is substituted; specifically 5-methyl-2-thienyl, 4-methoxy-2-pyridyl).

It is preferable that in formulas (IV'-1) and (IV'-3) R25 and at least one of R27 and R28, an alkyl group having an aromatic group (an aryl group or an aromatic heterocyclic group pe), an aryl group or an aromatic heterocyclic group, and that R25 and both of R27 and R28 have no anionic substituent. Examples of the substituent include the substituents V. At this time, the dye in formula (IV'-1) or (IV'-3) must form a cationic dye.

preferred Examples of the aryl-substituted alkyl group include an aralkyl group (e.g., benzyl, 2-phenylethyl, naphthylmethyl, 2- (4-biphenyl) ethyl), an aryloxyalkyl group (e.g., 2-phenoxyethyl, 2- (1-naphthoxy) ethyl, 2- (4-biphenyloxy) ethyl, 2- (o, m, p -halophenoxy) ethyl, 2- (o, m, p -methoxyphenoxy) ethyl) and an aryloxycarbonylalkyl group (e.g., 3-phenoxycarbonylpropyl, 2- (1-naphthoxycarbonyl) ethyl). Preferred examples of having an aromatic heterocyclic Ring-substituted alkyl group include 2- (2-pyridyl) ethyl, 2- (4-pyridyl) ethyl, 2- (2-Furyl) ethyl, 2- (2-thienyl) ethyl and 2- (2-pyridylmethoxy) ethyl. Preferred examples of the aryl group include 4-methoxyphenyl, phenyl, Naphthyl and biphenyl. Preferred examples of the aromatic heterocyclic Group include 2-thienyl, 4-chloro-2-thienyl, 2-pyridyl and 3-pyrazolyl.

From these are the alkyl group having an aromatic group (aryl group or aromatic heterocyclic group), and the substituted or unsubstituted aryl group more preferred.

It it is preferred that in formulas (IV'-2) and (IV'-4) R26 and at least one of R29 and R30 is an alkyl group associated with an aromatic group (a Aryl group or an aromatic heterocyclic group) is an aryl group or an aromatic heterocyclic group and R26 and both of R29 and R30 are anionic Substituents have. Examples of the substituent include the Substituents V. At this time, the dye must be in formulas (IV'-2) or (IV'-4) an anionic Form a dye.

preferred Examples of the alkyl group include an alkyl group of 1 to 15, preferably 1 to 10 carbon atoms which have a sulfo group, a phosphoric acid group or a carboxyl group (e.g., sulfomethyl, sulfoethyl, 2,2-difluoro-2-carboxyethyl, 2-phosphoethyl), an unsaturated one Hydrocarbon group containing a sulfo group, a phosphoric acid group or a carboxyl group (e.g., 3-sulfo-2-propenyl), an alkoxyalkyl group having a sulfo group, a phosphoric acid group or a carboxyl group is substituted (e.g., 2-sulfomethoxyethyl), an alkoxycarbonylalkyl group containing a sulfo group, a phosphoric acid group or a carboxyl group (e.g., sulfoethoxycarbonylethyl, 2-sulfobenzyloxycarbonylethyl), an acyloxyalkyl group containing a sulfo group, a phosphoric acid group or a carboxyl group is substituted (e.g., 2-phosphoacetyloxyethyl), and an acylalkyl group with a sulfo group, a phosphoric acid group or a carboxyl group is substituted (e.g., 2-sulfoacetylethyl). Preferred examples the alkyl group substituted with an aryl group an aralkyl group having a sulfo group, a phosphoric acid group or a carboxyl group (e.g., 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), an aryloxycarbonylalkyl group containing a Sulfo group, a phosphoric acid group or a carboxyl group (e.g., 3-sulfophenoxycarbonylpropyl), an aryloxyalkyl group having a sulfo group and a phosphoric acid group or a carboxyl group (e.g., 2- (4-sulfophenoxy) ethyl, 2- (2-Phosphenoxy) ethyl, 4,4-diphenoxy-3-sulfobutyl). preferred Examples of the alkyl group having an aromatic heterocyclic group substituted with an aromatic heterocyclic one Group substituted alkyl group containing a sulfo group, a phosphoric acid group or a carboxyl group (e.g., 3- (2-pyridyl) -3-sulfopropyl, 3- (2-furyl) -3-sulfopropyl, 2- (2-thienyl) -2-sulfopropyl).

preferred Examples of the aryl group include an aryl group containing a Sulfo group, a phosphoric acid group or a carboxyl group (e.g., 4-sulfophenyl, 4-sulfonaphthyl). Preferred examples of the aromatic heterocyclic Group include an aromatic heterocyclic group with a sulfo group, a phosphoric acid group or a carboxyl group is substituted (e.g., 4-sulfo-2-thienyl, 4-sulfo-2-pyridyl).

From these are the aralkyl group containing a sulfo group, a phosphoric acid group or a carboxyl group, and the aryloxyalkyl group, those having a sulfo group, a phosphoric acid group or a carboxyl group is substituted, preferably, stronger preferred are 2-sulfobenzyl, 4-sulfobenzyl, 4-sulfophenethyl, 3-phenyl-3-sulfopropyl, 4-phenyl-4-sulfobutyl, 3-phenyl-2-sulfopropyl, 4,4-diphenyl-3-sulfobutyl, 2- (4'-sulfo-4-biphenyl) ethyl, 4-phosphobenzyl, 3-sulfo-2-propenyl and 2- (4-sulfophenoxy) ethyl, and most preferably are 2-sulfobenzyl, 4-sulfobenzyl, 4-sufophenethyl, 3-phenyl-3-sulfopropyl and 4-phenyl-4-sulfobutyl.

n13 and n14 each independently 0, 1, 2, 3 or 4, preferably 0, 1, 2 or 3, more preferably 0, 1 or 2, still stronger preferably 0 or 1. If n13 and n14 are each 2 or more, repeat the methine group, however, have to these methine groups will not be the same.

p17, p18, p19, p20, p21, p22 and p23 each independently represent 0 or 1, preferably 0, is.

M7, M8 and M9 are each included in the formulas to indicate the presence of a cation or anion when it is necessary to neutralize the ionic charge of the dye. Typical examples of the cation include inorganic cations such as hydrogen ion (H ⁺ ), alkali metal ions (eg, sodium ion, potassium ion, lithium ion) and alkaline earth metal ions (eg, calcium ion), and organic cations such as ammonium ion (eg, ammonium ion, tetraalkylammonium ion, pyridinium ion, ethylpyridinium ion).

The anion may be either an inorganic anion or organic anion, and examples thereof include halogen anions (eg, fluoride ion, chloride ion, iodide ion), substituted aryl sulfonate ion (eg, p-toluene sulfonate ion, p-chlorobenzene sulfonate ion), aryl disulfonate ion (eg, 1,3-benzenesulfonate ion, 1, 5-naphthalene disulfonation, 2,6-naphthalenedisulfonate ion), alkyl sulfations (eg, methylsulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate, picration, acetate ion, and trifluoromethanesulfonate ion. Also, an ionic polymer or other dye having a charge opposite to the dye can be used. When the counterion is hydrogen ion, CO ₂ ^- and SO ₃ ^{- can be} referred to as CO ₂ H and SO ₃ H, respectively.

m7, m8 and m9 each represent a number that is used to equalize the Electric charge is necessary, and they are 0, if an internal Salt is formed.

specific Examples of in formulas (IV'c), (IV'-1), (IV'-3) and (V ') contained cationic Dyestuffs are given below, but the present Invention in no way limited thereto.

specific Examples of in formulas (IV'c), (IV'-1), (IV'-3) and (V ') contained anionic Dyestuffs are given below, but the present Invention in no way limited thereto.

The dyes of the invention can in accordance with the procedures Harmer, Heterocyclic Compounds - Cyanine Dyes and Related Compounds, John Wiley & Sons, New York, London (1964), D.M. Sturmer, Heterocyclic Compounds - Special topics in heterocyclic chemistry, chapter 18, section 14, pages 482-515, John Wiley & Sons, New York, London (1977), Rodd's Chemistry of Carbon Compounds, 2nd Edition, Volume IV, Part B, Chapter 15, pages 369-422, Elsevier Science Publishing Company Inc., New York (1977) and the patents and literatures described above Describing specific examples are cited) are described, be synthesized.

The present invention is not limited to the use of only sensitizing dyes of the present invention, but spectral sensitizing dyes may also be used in combination which differ from the invention.

at the dyes used in combination may be any core, usually used as a basic heterocyclic nucleus in cyanine dyes will be used. Namely Examples of the core include a pyrrole nucleus, a toxazoline nucleus, a thiazole nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus and a pyridine nucleus; Cores by fusing an alicyclic or aromatic hydrocarbon rings with those described above Cores (e.g., indolenine, gasoline olein, indole, Benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, Benzoselenazole nucleus, benzimidazole nucleus and quinoline nucleus. These cores can each substituted on a carbon atom.

at the merocyanine dye or composite merocyanine dye may include 5- or 6-membered heterocyclic core nucleus having a ketomethylene structure such as a pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thiooxazolidine-2,4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbituric acid nucleus and 2-thioselenazoline-2,4-dione nucleus can be used.

To the Example can the compounds described in Research Disclosure, Item 17643, page 23, Item IV (December, 1978), and the compounds described in the herein cited references may be used.

• a: 5,5'-Dichlor-3,3'-diethylthiacyaninbromid
• b: 5,5'-Dichlor-3,3'-di(4-sulfobutyl)-thiacyaninnatriumsalze
• c: 5-Methoxy-4,5-benzo-3,3'-di(3-sulfopropyl)thiacyaninnatriumsalz
• d: 5,5'-Dichlor-3,3'-diethylselenacyaniniodid
• e: 5,5'-Dichlor-9-ethyl-3,3'-di(3-sulfoprapyl)thiacarbocyaninpyridiniumsalz
• f: Anhydro-5,5'-dichlor-9-ethyl-3-(4-sulfobutyl)-3'-ethylhydroxid
• g: 1,1-Diethyl-2,2'-cyaninbromid
• h: 1,1-Dipentyl-2,2'-cyaninperchlorsäure
• i: 9-Methyl-3,3'-di(4-sulfobutyl)-thiacarbocyaninpyridiniumsalz
• j: 5,5'-Diphenyl-9-ethyl-3,3'-di(2-sulfoethyl)oxacarbocyaninnatriumsalz
• k: 5-Chlor-5'-phenyl-9-ethyl-3-(3-sulfopropyl)-3'-(2-sulfoethyl)oxacarbocyaninnatriumsalz
• l: 5,5'-Dichlor-9-ethyl-3,3'-di(3-sulfopropyl)oxacarbocyaninnatriumsalz
• m: 5,5'-Dichlor-6,6'-dichlor-1,1'-diethyl-3,3'-di(3-sulfopropyl)imidacarbocyaninnatriumsalz
• n: 5,5'-Diphenyl-9-ethyl-3,3'-di(3-sulfopropyl)thiacarbocyaninnatriumsalz.

The specific compounds used (dyes) are shown below:

• a: 5,5'-dichloro-3,3'-diethylthiacyanine bromide
• b: 5,5'-dichloro-3,3'-di (4-sulfobutyl) -thiacyanine sodium salts
• c: 5-Methoxy-4,5-benzo-3,3'-di (3-sulfopropyl) thiacyanine sodium salt
• d: 5,5'-dichloro-3,3'-diethylselenacyanine iodide
• e: 5,5'-dichloro-9-ethyl-3,3'-di (3-sulfoprapyl) thiacarbocyanine pyridinium salt
• f: Anhydro-5,5'-dichloro-9-ethyl-3- (4-sulfobutyl) -3'-ethylhydroxide
• g: 1,1-diethyl-2,2'-cyanine bromide
• h: 1,1-dipentyl-2,2'-cyanine perchloric acid
• i: 9-methyl-3,3'-di (4-sulfobutyl) thiacarbocyanine pyridinium salt
• j: 5,5'-diphenyl-9-ethyl-3,3'-di (2-sulfoethyl) oxacarbocyanine sodium salt
• k: 5-Chloro-5'-phenyl-9-ethyl-3- (3-sulfopropyl) -3 '- (2-sulfoethyl) oxacarbocyanine sodium salt
• l: 5,5'-dichloro-9-ethyl-3,3'-di (3-sulfopropyl) oxacarbocyanine sodium salt
• m: 5,5'-dichloro-6,6'-dichloro-1,1'-diethyl-3,3'-di (3-sulfopropyl) imidacarbocyanine sodium salt
• n: 5,5'-diphenyl-9-ethyl-3,3'-di (3-sulfopropyl) thiacarbocyanine sodium salt.

Of the Sensitizing dye for use in the present invention can in the photographic invention Silver halide emulsion by directly dispersing the sensitizing dye incorporated in the emulsion or it may be added to the emulsion after being dissolved in a solvent such as water, methanol, Ethanol, propanol, acetone, methyl cellosolve, 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, 1-methoxy-2-propanol, acetonitrile, tetrahydrofuran and N, N-dimethylformamide or a mixed solvent thereof was dissolved.

Also can a process in which a dye in a volatile organic solvent disbanded will, the solution is dispersed in water or a hydrophilic colloid and the Dispersion in the emulsion is added, described in US Patent 3,469,987, a method in which a water-insoluble dye in a water-soluble solvent is dispersed without dissolving the dye, and this dispersion to to the emulsion described in JP-B-64-24185 (the term "JP-B" as used herein) is called a "tested Japanese Patent Publication "), a method in which a dye in an acid disbanded will and the solution is added to the emulsion or an aqueous solution is formed while it is allows will that acid or base together, and the solution is added to the emulsion described in JP-B-44-23389, JP-B-44-27555 and JP-B-57-22091, a process in which an aqueous solution or colloid dispersion is formed by allowing it that a surfactant is present together, and the solution or dispersion to the Emulsion is added, described in US Patents 3,822,135 and 4,006,025, a method in which a dye directly in a hydrophilic Colloid is dispersed and the dispersion added to the emulsion described in JP-A-53-102733 and JP-A-58-105141, and a method in which a dye using a compound, the Redshift enabled is dissolved will and the solution is added to the emulsion described in JP-A-51-74624 become.

To the Dissolve The dye can also be used ultrasound.

The Method of use and the preferred embodiments of the dyes of the invention, represented by the formulas (IV '), (IV'-1) to (IV'-4), (V '), (IV'c) and (IV'a) are shown, are described below.

If the anionic dye and the cationic dye simultaneously are used, the anionic dye and the cationic form Dye both preferably 30% or more of the total amount of added Sensitizing dyes.

Furthermore it is preferred that any of the cationic dye and the anionic dye is added in an amount which 80% or more of the saturation coverage corresponds and is also admitted in such an amount that the Total amount of the sensitizing dyes added 160% or more of the saturation coverage equivalent.

The Dyes can be added after these two dyes previously mixed were. However, the cationic dye and the anionic Dye preferably added separately. In a preferred embodiment For example, the cationic dye is added earlier, in a more preferred embodiment the cationic dye is added in an amount that is 80% or more of the saturation coverage corresponds, and then the cationic dye is added, and in a continued stronger preferred embodiment the cationic dye is added in an amount that is 80% or more of the saturation coverage and then the anionic dye is added in an amount the 50% saturation coverage equivalent.

If the two dyes are added separately, the later added Dye preferably a fluorescence yield in a dry Gelatin film of 0.5 or more, more preferably 0.8 or more, on.

The Dyes can at some point during the preparation of an emulsion are added. Also, the Dyes are added at any temperature, but the emulsion temperature in the addition of the dyes, preferably 10 to 75 ° C, more preferably 30 to 65 ° C.

For the photographic Emulsion, the photosensitive mechanism in the present May be any of silver bromide, silver iodobromide, Silver chlorobromide, silver iodide, silver iodochloride, silver iodobromide chloride and silver chloride are used. However, the halogen composition has on the extreme surface of an emulsion grain preferably has an iodide content of 0.1 mol% or more, stronger preferably 1 mol% or more, still more preferably 5 mol% or more, making the multilayer adsorption structure more solid can be.

The Particle size distribution can be either wide or narrow, but is a narrow distribution prefers.

The Silver halide grain in the photographic emulsion can be a grain, the one regular Has crystal form, such as a cubic, octahedral, tetradecahedral or rhombic dodecahedral form, a grain that has an irregular crystal form has, like spherical or tabular form, a grain that has a (hkl) surface or a mixture of grains containing these crystal forms have, be. However, a tabular grain is preferred. The tabular Grain will be described in detail below. The grain with one (Hkl) surface is in Journal of Imaging Science, Vol. 30, pages 247-254 (1986) described.

For the photographic Silver halide emulsion for use in the present invention can the silver halide grains described above either individually or be used in a mixture of a variety of grains. The Silver halide grain can have different phases between the interior and the surface layer may have a multi-phase structure, e.g. with a conjugate Structure, may have a localized phase on the grain surface, or it can be a uniform Phase over have the whole grain. These grains can also be present together.

These different emulsions can each may be either a surface latent image type emulsion a latent image formed essentially on the surface will, or they can be an emulsion of the internal latent image type, where a latent image is formed within the grain.

The Silver halide emulsion for use in the present invention is preferably a tabular Silver halide grain, which is a higher relationship Surface / volume and to the one disclosed in the present invention Sensitizing dye is adsorbed. The aspect ratio of the grain is 2 or more (preferably 100 or less), preferably 5 to 80, stronger preferably 8 to 80, and the thickness of the tabular grain is preferably less than 0.2 μm, stronger preferably less than 0.1 μm, still stronger preferably less than 0.07 μm. To a tabular Grain with such a large aspect ratio and To produce a small thickness, the following technique is used.

In The present invention will be a tabular silver halide grain with a halogen composition of silver chloride, silver bromide, Silver chlorobromide, silver iodobromide, silver chloroiodobromide or silver iodochloride preferably used. The tabular Grain preferably has a major plane (100) or (111). The tabular Grain with a (111) major plane will be referred to as (111) tabular grain denotes, and this grain usually has a triangular or hexagonal surface on. As the distribution becomes more uniform, form tabular grains with a hexagonal surface generally a higher one Proportion of. JP-B-5-61205 describes the monodisperse hexagonal tabular grains.

The tabular Grain with a (100) surface as the major plane is hereinafter referred to as (100) tabular grain, and This grain has a rectangular or square shape. in the Case of this emulsion becomes a grain having a ratio of opposite Has sides of less than 5: 1, rather than tabular grain as a needle-shaped Grain called. If the tabular Grain consists of silver chloride or a grain with a high silver chloride content is (100) tabular Grain a higher stability the major plane as the (111) tabular grain on. Therefore, the (111) tabular Grain to be subjected to stabilization of the (111) major plane, and the method for this is described in JP-A-9-80660, JP-A-9-80656 and US Patent 5,298,388.

The (111) tabular grain for use in the present invention comprising silver chloride or having a high silver chloride content is disclosed in the following patents:
U.S. Patents 4,414,306, 4,400,463, 4,713,323, 4,783,398, 4,962,491, 4,983,508, 4,804,621, 5,389,509, 5,217,858 and 5,460,934.

The (111) tabular grain for use in the present invention having a high silver bromide content is described in the following patents:
U.S. Patents 4,425,425, 4,425,426, 4,434,266, 4,439,520, 4,414,310, 4,433,048, 4,647,528, 4,665,012, 4,672,027, 4,678,745, 4,684,607, 4,593,964, 4,722,886, 4,755,617, 4,755,456, 4,806,461, 4,801,522, 4,835,322, 4,839,268, 4,914,014, 4,962,015, 4,977,074, 4,985,350, 5,061,609 , 5,061,616, 5,068,173, 5,132,203, 5,272,048, 5,334,469, 5,334,495, 5,358,840 and 5,372,927.

The (100) tabular grain for use in the present invention is described in the following patents:
U.S. Patents 4,386,156, 5,275,930, 5,292,632, 5,314,798, 5,320,938, 5,319,635 and 5,356,764, European Patents 569,971 and 737,887, JP-A-6-308648 and JP-A-9-5911.

The Silver halide emulsion is generally prepared before use subjected to chemical sensitization. Chemical sensitization is determined using chalcogen sensitization (e.g., sulfur sensitization, Selenium sensitization, tellurium sensitization), noble metal sensitization (e.g., gold sensitization) and reduction sensitization, individually or in combination.

In In the present invention, the silver halide emulsion is preferably subjected at least to a selenium sensitization. More specific selenium sensitization alone or a combination of selenium sensitization and a chalcogen sensitization and / or noble metal sensitization (especially gold sensitization), and a combination selenium sensitization and noble metal sensitization is more preferable.

In selenium sensitization, a labile selenium compound is used as a sensitizer. The labile selenium compound is disclosed in JP-B-43-13489, JP-B-44-15748, JP-A-4-25832, JP-A-4-109240, JP-A-4-271341 and JP-A-5 -40324. Examples of the selenium sensitizer include colloidal selenium metal, selenoureas (eg, N, N-dimethylselenourea, trifluoromethylcarbonyltrimethylselenourea, acetyltrimethylselenourea), selenamides (eg, selenamide, N, N-diethylphenylselenamide), phosphine isenesides (eg, triphenylphosphine selenide, pentafluorophenyltriphenylphosphine selenide), selenium phosphates (eg, tri-p-tolylselenphosphate, Tri-n-butylselenphosphate), selenoketones (eg selenobenzophenone), isocyanates, selenocarboxylic acids, selenes ter and diacylselenides. In addition, relatively stable selenium compounds such as selenic acid, potassium selenocyanate, selenazoles and selenides (described in JP-B-46-4553 and JP-B-52-34492) can also be used as the selenium sensitizer.

at sulfur sensitization becomes a labile sulfur compound used as a sensitizer. The labile sulfur compound is in P. Glafkides, Chemistry et Physique Photographique, 5th Edition, Paul Montel (1987) and Research Disclosure, Vol. 307, Item 307105 described. Examples of the sulfur sensitizer include thiosulfates (e.g., hypo), thioureas (e.g., diphenylthiourea, triethylthiourea, N-ethyl-N '- (4-methyl-2-thiazolyl) thiourea, Carboxymethyltrimethylthiourea), thioamides (e.g., thioacetamide), Rhodanines (e.g., diethylrhodanine, 5-benzylidene-N-ethyl-rhodanine), phosphine sulfides (e.g., trimethylphosphine sulfide), Thiohydantoins, 4-oxo-oxazolidine-2-thiones, dipolysulfides (e.g., dimorpholine disulfide, Cystine, hexathiocan-thione), mercapto compounds (cysteine), polythionic acid salts and elemental sulfur. Also, an active gelatin can be used as a sulfur sensitizer be used.

at The Tellursensibilisierung becomes a labile Tellurverbindung as Sensitiser used. The labile tellurium compound is in the Canadian Patent 800,958, British Patents 1,295,462 and 1,396,696, JP-A-4-204640, JP-A-4-271341, JP-A-4-333043 and JP-A-5-303157. Examples of the tellurium sensitizer include tellurium ureas (e.g., tetramethyltellurourea, N, N'-dimethylethylenetellurourea, N, N'-diphenylethylenetellurourea), Phosphine tellurides (e.g., butyldiisopropylphosphine telluride, tributylphosphine telluride, Tributoxyphosphine telluride, ethoxydiphenylphosphine telluride), diacyl (di) tellurides (e.g., bis (diphenylcarbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) ditelluride, Bis (N-phenyl-N-methylcarbamoyl) telluride, bis (ethoxycarbonyl) telluride), Isotellurocyanates, telluramides, tellurium hydrazides, tellurium esters (e.g. Butylhexyl tellurate), tellurium ketones (e.g., tellurium acetophenone), colloidal Tellurium, (di) tellurides, and other tellurium compounds (e.g., potassium telluride, Tellurpentathionat sodium salt).

at the precious metal sensitization becomes a salt of a precious metal, such as gold, platinum, palladium and iridium, used as a sensitizer. The noble metal salt is described in P. Glafkides, Chemistry et Phisique Photographique, 5th Edition, Paul Montel (1987) and Research Disclosure, Volume 307, No. 307105. Of these, the gold sensitization prefers. As described above, the present invention is in the embodiment, in which the gold sensitization is performed, particularly effective.

In Photographic Science and Engineering, Vol. 19322 (1975) and Journal of Imaging Science, Vol. 3228 (1988) mentions that a solution that Contains potassium cyanide (KCN), Remove gold from a sensitizer core on an emulsion core can. According to these Publications becomes a gold atom or gold ion adsorbed on a silver halide grain is released as a cyanide complex by the cyanion, causing the Gold sensitization is inhibited. If the formation of cyan in accordance avoided with the present invention, the effect can of the gold sensitizer.

Examples of the gold sensitizer include chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide and gold selenide. The gold compounds disclosed in U.S. Patents 2,642,361, 5,049,484 and 5,049,485 can also be used.

at the reduction sensitization becomes a reducing compound used as a sensitizer. The reducing compound is in P. Glafkides, Chemistry et Phisique Photographique, 5th Edition, Paul Montel, (1987) and Research Disclosure, Vol. 307, No. 307105. Examples of the reducing sensitizer include aminoiminomethanesulfinic acid (i.e. Thiourea dioxide), borane compounds (e.g., dimethylaminoborane), Hydrazine compounds (e.g., hydrazine, p-tolylhydrazine), polyamine compounds (e.g., diethylenetriamine, triethylenetetramine), stannous chloride, silane compounds, Reductone (e.g., ascorbic acid), Sulfites, aldehyde compounds and hydrogen gas. The reduction sensitization can also be in an atmosphere high pH or excess silver ions (so-called silver tire) are performed. The reduction sensitization is preferably used in the formation of silver halide grains.

The The amount of sensitizer used will generally be appropriate the type of silver halide grain and the conditions of the chemical Sensitization determined.

The amount of the chalcogen sensitizer used is 10 ^-8 to 10 ^-2 mol, preferably 10 ^-7 to 5 x 10 ^-3 mol per mol of silver halide. The amount of the noble metal sensitizer used is preferably 10 ^-7 to 10 ^-2 mol per mol of silver halide.

The conditions for chemical sensitization are not particularly limited. The pAg is generally 6 to 11, preferably 7 to 10. The pH is preferably 4 to 10. The temperature is preferably 40 to 95 ° C, more preferably 45 to 85 ° C.

In Referring to the production method and the like of the photographic Emulsion for use in the present invention can be found in JP-A-10-239789, Column 63, line 36 to column 65, line 2.

Furthermore can respect the additives such as color couplers, additives for the photographic photosensitive Material, the type of photosensitive material to which the The present invention can be applied to the processing of the Photosensitive material and the like on JP-A-10-239789, Column 65, line 3 to column 73, line 13.

The The present invention will be described below in more detail with reference to FIG described on the examples. However, the present invention should not be construed as though limited to this.

example 1

Production of an octahedral Silver bromide emulsion (Emulsion A) and silver bromide tabular emulsions (Emulsion B and Emulsion C):

Into a reactor, 1,000 ml of water, 25 g of deionized ossein gelatin, 15 ml of aqueous 50% NH ₄ NO ₃ solution, and 7.5 ml of 25% aqueous NH ₃ solution were charged. The resulting solution was kept at 50 ° C and thoroughly stirred, and to this was added 750 ml of a 1N silver nitrate aqueous solution and 1 mol / l of an aqueous potassium bromide solution over 50 minutes. During the reaction, the silver potential was kept at -40 mV. The resulting silver bromide grain was octahedral and had an equivalent spherical diameter of 0.846 ± 0.036 μm. The temperature of the emulsion thus obtained was lowered, and after addition of a copolymer of isobutene and maleic acid sodium salt as a coagulating agent thereto, desalting by precipitation washing was performed. Subsequently, 95 g of deionized ossein gelatin and 430 ml of water were added thereto, and the resulting solution was adjusted to pH 6.5 and pAg of 8.3 at 50 ° C. To this end, potassium thiocyanate, chloroauric acid and sodium thiosulfate were added to obtain the optimum sensitivity, and then this emulsion was ripened at 55 ° C for 50 minutes. The resulting emulsion was designated Emulsion A.

In 1.2 L of water, 6.4 g of potassium bromide and 6.2 g of low-molecular weight gelatin having an average molecular weight of 15,000 or less were dissolved, and while the resulting solution was kept at 30 ° C, 8.1 ml of an aqueous solution was dissolved 16.4% silver nitrate solution and 7.2 ml of an aqueous 23.5% potassium bromide solution by means of a double jet process for 10 seconds. Subsequently, an aqueous 11.7% gelatin solution was further added, and after the temperature was raised to 75 ° C, the resulting solution was matured for 40 minutes. Thereafter, 370 ml of a 32.2% silver nitrate aqueous solution and an aqueous 20% potassium bromide solution were added over 10 minutes while maintaining the silver potential at -20 mV. After physical ripening for 1 minute, the temperature was lowered to 35 ° C. In this way, a silver bromide monodispersed tabular emulsion (specific gravity: 1.15) having an average projection area of 2.32 μm, a thickness of 0.09 μm and a coefficient of variation of the diameter of 15.1% was obtained. Thereafter, the soluble salts were removed by a coagulation precipitation method. While the temperature was again maintained at 40 ° C, 45.6 g of gelatin, 10 ml of a 1 mol / l aqueous sodium hydroxide solution, 167 ml of water and 1.66 ml of 35% phenoxyethanol were added, and the pAg Value and pH were adjusted to 8.3 and 6.20, respectively. To this end, potassium thiocyanate, chloroauric acid and sodium thiosulfate were added to achieve optimum sensitivity and then this emulsion was ripened at 55 ° C for 50 minutes. The resulting emulsion was designated Emulsion B. Also, an emulsion was prepared by carrying out the chemical sensitization using potassium thiocyanate, chloroauric acid, pentafluorophenyldiphenylphosphine selenide and sodium thiosulfate in place of potassium thiocyanate, chloroauric acid and sodium thiosulfate, and designated Emulsion C. Assuming that the dye-occupying area is 80 Å ² , the monolayer saturation coverage amounts of the emulsions A and B were 5.4 × 10 ^-4 mol / mol-Ag and 1.42 × 10 ^-3 mol / mol-Ag, respectively.

To Each of the emulsions thus obtained became one shown in Table 1 first dye added while the emulsion at 50 ° C and each emulsion was stirred for 30 minutes. After that a second dye and a third dye became continuous was added, and each emulsion was further stirred at 50 ° C for 30 minutes.

Table 1

The adsorbed amount of the dye was determined as follows. each obtained liquid Emulsion was centrifuged, and thereby at 10,000 rpm for 10 minutes precipitated the precipitate was freeze-dried, 25 ml of an aqueous 25% sodium thiosulfate solution and methanol were added to 0.05 g of the precipitate, by 50 ml of solution to form the resulting solution was analyzed by high speed liquid chromatography, and the dye density was quantified.

The light absorption intensity per unit area was measured as follows. The obtained emulsions were each thinly coated on a slide glass, and the transmission spectrum and the reflection spectrum of individual grains were determined by using a microspectrophotometer MSP65 manufactured by Karl Zeiss KK by the following method to determine the absorption spectrum. In the transmission spectrum, the region where no grains were present was used as a reference, and the reference for the reflection spectrum was obtained by measuring silicon carbide whose reflectance is known. The measured area is a circular opening portion with a diameter of 1 μm. After the position was adjusted so that the opening portion was not able to overlap with the contour of a grain, the transmission spectrum and the reflection spectrum in the wavenumber range from 14,000 cm ^-1 (714 nm) to 28,000 cm ^-1 (357 nm) measured. The absorption spectrum was determined from the absorption factor A, which is 1-T (transmissivity) -R (reflectance). Using the absorption factor A 'obtained by subtracting the absorption of silver halide, -log (1-A') was integrated with respect to the wavenumber (cm ^-1 ), and the obtained value was halved and used as the light absorption intensity per unit area , The integration range is from 14,000 to 28,000 cm ^-1 . At this time, the light source used was a tungsten lamp, and the light source voltage was 8V. In order to minimize the damage of the dye due to light irradiation, a monochromator on the primary side was used, and the wavelength distance and slit width were set to 2nm and 2, respectively. Set to 5 nm,

Around to determine the absorption spectrum of the emulsion became infinite Diffusion reflectance a finished emulsion according to the Kubelka-Munk equation using an emulsion as a control to which no dye was added, converted, and the absorption spectrum of only the dye was obtained.

The Spectral sensitivity of the coated film was determined from the Exposure that was necessary to a density of the veil +0.2 determines when using the exposure a spectral exposure machine was performed, which is set so was that the photon numbers of the corresponding wavelengths in the exposure wavelength range they can be the same.

In 1 and 2 "Present Invention" shows the absorption spectrum and the spectral sensitivity distribution of Invention 1, and "Comparative Example 3" shows the absorption spectrum and the spectral sensitivity of Comparative Example 3.

To each emulsion obtained, a gelatin hardener and a coating aid were added, and the emulsions were each coated on a cellulose acetate film support simultaneously with the gelatin protective layer to obtain a coated silver amount of 3.0 g-Ag / m ² . The formed film was exposed to a tungsten bulb (color temperature: 285 ° K) for 1 second through a continuous wedge color filter. By using Fuji Gelatin Filter SC-50 (manufactured by Fuji Photo Film Co., Ltd.) as a color filter capable of exciting the dye side, light of 500 nm or less was cut off upon irradiation of the samples. Each exposed sample was developed with the following surface developer MAA-1 at 20 ° C for 10 minutes.

Surface Developer MAA-1:

Of the developed film was re the optical density with a Fuji Automatic Densitometer. The sensitivity is the reciprocal of the light intensity necessary is to form an optical density of fog +0.2, and will indicated by a value assuming that the sensitivity, if only the first dye was added, 100.

The Results are shown in Table 2.

The absorption spectra of the emulsions prepared in Comparative Example 3 and Example 1 according to the invention are shown in FIG 1 shown. As shown in Table 2 and 2 As is apparent, according to the present invention, the sensitizing dye can be adsorbed in multiple layers on the grain surface to form a J aggregate, so that the light absorption intensity can be increased within a narrow wavelength range. By using a silver halide emulsion having such an absorpt Furthermore, the obtained photosensitive silver halide material can have a high sensitivity only in the target wavelength range and have good color separation and high color reproducibility.

at multilayer adsorption to achieve such wavelength characteristics the dye in the second or subsequent layers must be a J-aggregate form, and it was found that by realizing such a Adsorption state the effect is brought about that coagulation of grains is reduced. It is believed that this occurs because the Interaction of the grains on the surface as a result of formation of a J aggregate from the dye in the second or subsequent layers is reduced. This effect is a really surprising Result.

Example 2

An emulsion of tabular silver chloride grains was prepared in the same manner as Emulsion D in Example 2 of JP-A-8-227117. The particle surface area was 5.15 x 10 ² m ² / mol-Ag, and when the dye occupation area was taken as 80 Å ^2, the single layer saturation coverage was 1.07 × 10 ^-3 mol / mol-Ag. In place of the sensitizing dyes 2 and 3, 1.1 × 10 ^-3 mol / mol-Ag of the sensitizing dye I-6 was added at 56 ° C, and after the solution was stirred for 30 minutes, 6.0 × 10 ^-4 mol / mol-Ag of the sensitizing dye I-6 and 6.0 × 10 ^-4 mol / mol-Ag of the sensitizing dye II-7. The resulting solution was further stirred for 20 minutes and then subjected to chemical sensitization in the same manner as Emulsion D in Example 2 of JP-A-8-227117. The resulting emulsion was designated Emulsion 2A (Comparative). In place of the sensitizing dyes 2 and 3, 1.1 × 10 ^-3 mol / mol-Ag of the sensitizing dye I-6 was added at 56 ° C, and after the solution was stirred for 30 minutes, 6.0 × 10 ^-4 mol / mol. mol-Ag of the sensitizing dye I-4 and 6.0 × 10 ^-4 mol / mol-Ag of the sensitizing dye II-4. The resulting solution was further stirred for 20 minutes and then subjected to chemical sensitization in the same manner as Emulsion D in Example 2 of JP-A-8-227117. The resulting emulsion was designated Emulsion 2B (Reference). In addition, an emulsion was prepared by not adding I-4 and II-4 in the emulsion 2B, and it was referred to as emulsion 2C (comparative).

It Coated samples were processed in the same manner as the coated ones Sample F was prepared in Example 3 of JP-A-8-227117. A sample, those coated using Emulsion 2A instead of Emulsion F Sample F in Example 3 of JP-A-8-227117 was obtained as Sample 2A, and samples using similar emulsion 2B or Emulsion 2C instead of Emulsion F, were designated Sample 2B and Sample 2C, respectively.

The Amount of adsorbed dye, adsorption layer number and the light absorption intensity became determined in the same manner as in Example 1. Furthermore, that became Absorption spectrum and the spectral sensitivity distribution of each emulsion was measured in the same manner as in Example 1.

Around to examine the sensitivity of each coated sample the coated samples each by an optical wedge and a blue filter for 1/100 seconds using a Fuji FW Type Sensitometer (manufactured by Fuji Photo Film Co., Ltd.) exposed to processing with Fuji Photo Film CN16 and with respect to the photographic Properties compared.

The Sensitivity is the reciprocal of the amount of exposure that is necessary to give a density of fog +0.2, and it is indicated by a relative value based on the sensitivity the sample 2C is based.

The Results are shown in Table 3 below.

The highly sensitive photosensitive material with the desired Absorption and the desired Sensitivity waveform can be obtained by the dye addition method according to the present Invention can be obtained.

Example 3

The A method for producing a silver halide emulsion will be described below described.

It Seven kinds of silver halide emulsion grains [Emulsion A-1 and emulsions B to G] by the following method for production of silver halide grains produced.

Preparation of the emulsion A-1 (octahedral, internal latent image type direct positive emulsion):

To 1,000 ml of an aqueous Gelatin solution containing 0.05 M potassium bromide, 1 g of 3,6-dithia-1,8-octanediol, 0.034 mg lead acetate and 60 g deionized gelatin with a calcium content of 100 ppm or less, 0.4 M of an aqueous silver nitrate solution and 0.4 M of an aqueous Potassium bromide solution by means of of a controlled double jet process while the Temperature at 75 ° C wherein the rate of addition of the aqueous potassium was controlled to have a pBr of 1.60 and 300 ml of aqueous Silver nitrate solution were over 40 minutes added.

To Completion of the addition became octahedral silver bromide crystals (hereinafter referred to as "core grain") with a mean grain size (equivalent ball diameter) of about 0.7 μm and produced with balanced grain size.

The obtained core grains were subjected to chemical sensitization using the following container and subjected to the following formulation.

1st tank

One Tank with a hemispherical Floor of a metal whose surface is covered with the fluororesin material FEP manufactured by Du Pont with a thickness of 120 μm Teflon-coated was.

2. Stir

A seamless Integrated blade of the propeller type, made of a metal, its surface Teflon-coated was.

3. Formulation

To of the direct positive octahedral emulsion prepared above 3 ml of an aqueous Solution, by dissolving of 1 mg of sodium thiosulfate, 90 mg of potassium tetrachloroaurate and 1.2 Potassium bromide in 1,000 ml of water was added. The resulting solution was at 75 ° C for 80 Heated for minutes, to perform the chemical sensitization treatment. To the thus obtained chemically sensitized emulsion solution 0.15 M potassium bromide was added, and to this were added, similar to in the production of the core grains, 0.9 M of an aqueous Silver nitrate solution and 0.9 M of an aqueous potassium added by a controlled double jet process, while the Temperature maintained at 75 ° C. with the rate of addition of the aqueous potassium bromide solution being controlled was to have a pBr of 1.30 and 670 ml of the aqueous Silver nitrate solution were over 70 minutes added.

The resulting emulsion was mixed with water by means of a conventional Flokkulationsverfahrens washed, and this were the above-prepared Gelatin, 2-phenoxyethanol and methyl p-hydroxybenzoate added, octahedral silver bromide crystals having an average grain size (equivalent spherical diameter) of about 1.4 μm and get balanced grain size (hereinafter referred to as "core / shell particle from the internal latent image type ").

To this internal latent image type core / shell emulsion became 3 ml of an aqueous Solution, by dissolving of 100 mg of sodium thiosulfate and 40 mg of sodium tetraborate in 1,000 ml of water was added, and further 14 mg of poly (N-vinylpyrrolidone) added. The resulting emulsion was added under heating Matured at 60 ° C, and then 0.005 M potassium bromide was added thereto to thereby obtain a octahedral direct-positive internal latent image type emulsion manufacture.

Preparation of the emulsions B to G (octahedral direct-positive Emulsions of internal latent image type):

octahedral direct-positive internal latent image type silver halide emulsions, each having a mean grain size shown in Table 4 (equivalent ball diameter) and with respect balanced grain size were changed by the corresponding addition times of the aqueous silver nitrate solution and the aqueous potassium bromide, and further changing the chemicals added in the preparation of Emulsion A-1, receive.

Table 4

Under Use of Emulsions A-1 and B to G was a photosensitive Comparative element (Sample 101) having the structure shown below produced. The sensitizing dyes were at perfection added to the chemical sensitization of the peel, and the type of the dye, the dispersion form, the addition temperature and the Amount are shown in Table 5.

Structure of Comparative Photosensitive Element 101

Table 5 Sensitizing dye content per 1 kg emulsion

Yellow dye-releasing compound (1)

Magenta dye-releasing compound (1)

Cyan dye releasing compound (1)

Cyan dye releasing compound (2)

Additive (1)

Additive (2)

Additive (3)

Additive (4)

Additive (5)

Additive (6)

Additive (8)

Additive (8)

• carboxymethylcellulose (CMC CELLOGEN 6A, manufactured by Daiichi Kogyo Seiyaku K.K.)

Additive (9)

• Polyvinyl alcohol (PVA-220DE)
• Degree of polymerization: about 2,000, degree of saponification: 88%.

Additive (10)

Additive (11)

Additive (12)

Additive (13)

Additive (14)

Additive (15)

Additive (16)

Additive (17)

Additive (18)

Matting agent (1)

• spherical Polymethyl methacrylate latex (average particle size: 3 μm)

Surfactant (1)

Surfactant (2)

Surfactant (3)

Surfactant (4)

Surfactant (5)

Surfactant (6)

Surfactant (7)

Ultraviolet absorber (1)

Ultraviolet absorber (2)

Ultraviolet absorber (3)

Organic solvent (1) with high boiling point

Organic solvent (2) with high boiling point

Ultraviolet absorber (4)

Ultraviolet absorber (5)

Hardeners (1)

• CH ₂ = CHSO ₂ CH ₂ CONH (CH ₂ ) ₂ NHCOCH ₂ SO ₂ CH = CH ₂

Hardeners (2)

• CH ₂ = CHSO ₂ CH ₂ CONH (CH ₂ ) ₃ NHCOCH ₂ SO ₂ CH = CH ₂

Hardeners (3)

Hardeners (4)

Core Former (1)

Polymer stain (1)

(Menge von zugegebenem Farbstoff: g(Farbstoff)/1 kg (Emulsion))Emulsions A-2 to A-4 were prepared by adding dyes to the second and subsequent layers (first dye + second dye) after the addition of the dye of the first layer as shown in Table 6 instead of adding the dyes (7). , (4) and (6) to the fourteenth layer emulsion A-1, and the photosensitive elements obtained by using these emulsions were referred to as samples 102 and 104, respectively. Table 6

(Amount of added dye: g (dye) / 1 kg (emulsion))

each Sample in Table 6 was compared the amount of dye adsorbed on an emulsion grain per unit area measured by the method described above, and the obtained Values were each reported with single-layer saturation adsorption compared. For Samples 102, 103 and 104, the adsorption was confirmed by dyes in two or more layers. However, it was at the rehearsal 101, the dye is adsorbed in one layer.

It For example, a cover sheet was made as follows.

• (a) Eine neutralisierende Schicht, die 10,4 g/m² eines Acrylsäure/n-Butylacrylat-Copolymers (80/20 (mol%)) mit einem mittleren Molekulargewicht von 50.000 und 0,1 g/m² 1,4-Bis(2,3-epoxypropoxy)-butan enthielt,
• (b) eine Schicht, die 4,3 g/m² Celluloseacetat mit einem Acetylierungsgrad von 55% und 0,2 g/m² eines Methyl- Halbesters von Methylvinylether/Maleinsäureanhydrid-Copolymer (50/50 (mol%)) enthielt, und
• (c) eine neutralisierende Verzögerungsschicht (timing layer), die 0,3 g/m² eines n-Butylmethacrylat/2-Hydroxyethylmethacrylat/Acrylsäure-Copolymers (66,1/28,4/5,5 (Gew.-%)) mit einem mittleren Molekulargewicht von 25.000 und 0,8 g/m² eines Ethylmethacrylat/2-Hydroxyethylmethacrylat/Acrylsäure-Copolymers (66,1/28,4/5,5 (Gew.-%)) mit einem mittleren Molekulargewicht von 40.000 enthielt.

The following layers were formed on a polyethylene terephthalate support containing a light piping preventive dye and undercoated with gelatin:

• (a) A neutralizing layer containing 10.4 g / m ^{2 of} an acrylic acid / n-butyl acrylate copolymer (80/20 (mol%)) having an average molecular weight of 50,000 and 0.1 g / m ^2. Bis (2,3-epoxypropoxy) butane,
• (b) a layer containing 4.3 g / m ^{2 of} cellulose acetate having a degree of acetylation of 55% and 0.2 g / m ^{2 of} a methyl half-ester of methyl vinyl ether / maleic anhydride copolymer (50/50 (mol%)), and
• (c) a neutralizing timing layer containing 0.3 g / m ² of n-butyl methacrylate / 2-hydroxyethyl methacrylate / acrylic acid copolymer (66.1 / 28.4 / 5.5 (wt%)) having an average molecular weight of 25,000 and 0.8 g / m ^{2 of} an ethyl methacrylate / 2-hydroxyethyl methacrylate / acrylic acid copolymer (66.1 / 28.4 / 5.5 (wt.%)) having an average molecular weight of 40,000 ,

Of the The photoprotective dye used was a 3: 1 mixture KAYASET GREEN A-G, manufactured by Nippon Kayaku K.K., and the compound shown below:

Protective dye before light transmission

A Alkali processing composition was prepared as follows.

0.8 g of a processing solution with the following composition were placed in a container, the tear by pressure can.

Sulfinsäurepolymer

Anionic Surfactant (1)

Anionic Surfactant (2)

Alkyl-modified PVA

Cationic polymer

These Photosensitive elements (Samples 101 to 104) were respectively a spectrum exposure on the emulsion layer side by a continuous wedge in an Equi energy spectrum exposure machine exposed and then superimposed on the cover sheet prepared above. Between two materials, the processing solution described above was carried out a pressure roller is developed so that it has a thickness of 62 microns. The processing was at 25 ° C carried out, and after 10 minutes, the transmission density became measured with a color densitometer.

The Samples were analyzed in terms of the spectral equi-energy sensitivity spectrum, that was obtained compared. As a result, the samples according to the invention showed (Samples 103 and 104) a narrow distribution in the spectral sensitivity spectrum in comparison with the conventional multilayer system (sample 102) on.

Separately The photosensitive elements (Samples 101 to 104) were on the emulsion layer side by a continuous gray wedge exposed and superimposed on the cover sheet prepared above. The processing solution described above became between two materials developed by a pressure roller so that it has a thickness of 62 microns. The exposure was for 1/100 seconds, where the exposure lighting was controlled to a constant To reach the exposure amount. The processing was carried out at 25 ° C, and after 10 minutes, the transmission density became measured with a color densitometer. Subsequently, became a characteristic Curve by plotting the logarithm of the exposure amount on the Abscissa and each color density created on the ordinate. The color density in the unexposed area was obtained as maximum density, and the Color density in the range in which the exposure amount is sufficient is great was obtained as minimum density. The sensitivity, the one average density between the maximum density and the minimum density was obtained as the midpoint sensitivity, and the sensitivity when a density of 0.3 was reached, the reason was (foot) sensitivity receive. The results obtained with the sensitivity of sample 101 as 100 are shown in Table 7.

Table 7

Out Table 7 shows that in the samples according to the invention 103 and 104 both the midpoint sensitivity and the fundamental sensitivity elevated and the spectral sensitivity spectrum is sharper.

By Use of the photographic emulsion and photosensitive Material can be a highly sensitive photosensitive material with the desired Absorption and the desired Sensitivity waveform can be obtained.

While the Invention in detail and with reference to specific embodiments It will be apparent to those skilled in the art that different changes and modifications can be made thereto without departing from the scope of the invention as defined in the appended claims.

Claims (12)

Photographic silver halide emulsion containing a silver halide grain having a wavelength of the spectral absorption maximum of 500 nm or more and a light absorption intensity of 100 or more, wherein, assuming that the maximum value the spectral absorption factor of the emulsion by a sensitizing dye Amax is the distance between the shortest wavelength that 80% of Amax shows, and the longest Wavelength, which shows 80% of Amax, 20 nm or more, and the distance between the shortest Wavelength, which shows 50% of Amax, and the longest wavelength, the Shows 50% of Amax, 120 nm or less, and wherein the photographic Silver halide emulsion multi-layer adsorbed sensitizing dye layers and the dye in the second or subsequent layer in the multi-layer adsorbed dye layers, a J-aggregate forms. Photographic silver halide emulsion containing Silver halide grain having a wavelength of the spectral absorption maximum of 500 nm or more and a light absorption intensity of 100 or more, wherein, assuming that the maximum value the spectral sensitivity of the emulsion by a sensitizing dye Smax is the distance between the shortest wavelength that 80% of Smax shows, and the longest Wavelength, which shows 80% of Smax, 20 nm or more, and the distance between the shortest Wavelength, which shows 50% of Smax, and the longest wavelength, the 50% of Smax, 120 nm or less, and wherein the photographic silver halide emulsion having multi-layer adsorbed sensitizing dye layers and the dye in the second or subsequent layer in the multi-layer adsorbed dye layers forms a J-aggregate. A photographic silver halide emulsion according to claim 1, wherein the longest Wavelength, which shows a spectral absorption factor of 50% of Amax, in Range from 500 to 510 nm, from 560 to 610 nm or from 640 to 730 nm. A photographic silver halide emulsion according to claim 2, wherein the longest Wavelength, which shows a spectral sensitivity of 50% of Smax in the range from 500 to 510 nm, from 560 to 610 nm or from 640 to 730 nm. A photographic silver halide emulsion according to claim 1, 2, 3 or 4, wherein the silver halide emulsion is a dye containing at least one aromatic group. A photographic silver halide emulsion according to claim 1 or 2, wherein the wavelength the absorption maximum of the dye chromophore in the first layer longer than in the multi-layer adsorbed dye layers that of the dye chromophore in the second or subsequent Layer in the multi-layer adsorbed dye layers. A photographic silver halide emulsion according to claim 1 or 2, wherein the dye in the second or subsequent Layer one from the dye in the first layer into the multilayer adsorbed dye layers has different structure and the second or subsequent layer is both cationic and also contains an anionic dye. Photographic silver halide emulsion according to the claims 1 to 7, which contains a sensitizing dye having a core contains which is formed by the condensation of three or more rings. Photographic silver halide emulsion according to the claims 1 to 8, wherein the silver halide grain having a wavelength of spectral absorption maximum of 500 nm or more and a light absorption intensity of 100 or more is a tabular grain having an aspect ratio of 2 or more. Photographic silver halide emulsion according to the claims 1 to 9, wherein the silver halide grain having a wavelength of spectral absorption maximum of 500 nm or more and a light absorption intensity of 100 or more is subject to selenium sensitization. Photographic photosensitive silver halide material, which comprises at least one photographic silver halide emulsion and the one in any of the claims 1 to 10 described photographic silver halide emulsion. A silver halide photographic emulsion according to claim 1 or 2, wherein the sensitizing dye adsorbed in multiple layers is a linked dye represented by formula (III): D ₁ - (La- [D ₂ ] _q ) _r M ₃ m ₃ (III) wherein D ₁ and D ₂ each represent a dye chromophore, La represents a linking group or a single bond, q and r each represent an integer of 1 to 100, M _{3 represents} a charge-balancing counterion and m _{3 represents} a number which is used to neutralize the electrical Charge of the molecule is necessary.