EP0445627A1

EP0445627A1 - Silver halide photographic light-sensitive materials

Info

Publication number: EP0445627A1
Application number: EP91102835A
Authority: EP
Inventors: Shigeru C/O Fuji Photo Film Co. Ltd. Ohno; Yuji C/O Fuji Photo Film Co. Ltd. Mihara
Original assignee: Fuji Photo Film Co Ltd
Current assignee: Fujifilm Holdings Corp
Priority date: 1990-03-01
Filing date: 1991-02-26
Publication date: 1991-09-11
Anticipated expiration: 2011-02-26
Also published as: DE69121941T2; JPH03251841A; EP0445627B1; DE69121941D1

Abstract

A silver halide photographic light-sensitive material is disclosed having a silver halide emulsion layer comprised of silver halide grains which contain at least silver chloride and which have been spectrally sensitized to infrared using at least one tricarbocyanine dye and/or dicarbocyanine dye which contains a 4-quinoline nucleus, wherein there is at least one hydrophilic colloid layer which contains at least one dye which is represented by general formula (F-I) indicated below and at least one dye which is represented by general formula (F-II) indicated below:

wherein R¹, R², R³, R⁴, R⁵ and R⁶, which may be the same or different, each represents a substituted or unsubstituted alkyl group; Z¹ and Z² each represents a group of non-metal atoms which is required to form a substituted or unsubstituted benzo-condensed ring, naphtho-condensed ring or five or six membered heterocyclic condensed ring; provided that R¹, R², R³, R⁴, R⁵, R⁶, Z¹ and Z² are groups such that the dye molecule has at least three acid groups; L¹, L² and L³ represent substituted or unsubstituted methine groups; X represents an anion; and n is 1 or 2, and n is 1 when the dye forms an intramolecular salt,

wherein R₂₁ and R₂₄ each represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group; R₂₂ and R₂₅ each represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, COR₂₉ or SO₂R₂₉; R₂₃ and R₂₆ each represents a hydrogen atom, a cyano group, an alkyl group, an aryl group, -COOR₂₇, -OR₂₇, -NR₂₇R₂₈, -N(R₂₈)COR₂₉, -N(R₂₈)SO₂R₂₉, -CONR₂₇R₂₈ or -N(R₂₇)CONR₂₇R₂₈ (where R₂₉ represents an aliphatic group or an aromatic group and R₂₇ and R₂₈ each represents a hydrogen atom, an aliphatic group or an aromatic group); L₄, L₅, L₆, L₇ and L₈ represent methine groups; n₁ and n₂ each represents 0 or 1; and M^⊕ represents hydrogen or some other univalent cation; provided that at least one of R₂₁, R₂₂, R₂₃, R₂₄, R₂₅, R₂₆, L₄, L₅, L₆, L₇ or L₈ represents a group which has at least one carboxylic acid group or sulfonic acid group.

Description

FIELD OF THE INVENTION

The present invention relates to a silver halide photographic light-sensitive material which is spectrally sensitized to the infrared region, and in particular it relates to a silver halide photographic light-sensitive material which has improved sensitivity in the infrared region and which has improved safelight safety.

BACKGROUND OF THE INVENTION

Photographic emulsion layers and other layers are sometimes dyed in order to absorb light of a specified wavelength band in silver halide photographic light-sensitive materials.
A colored layer is established on the side further from the support than the photographic emulsion layer in the photographic light-sensitive material when it is necessary to control the spectral composition of the light which should be incident upon the photographic emulsion layer. A colored layer of this type is called a filter layer. In cases where there are a plurality of photographic emulsion layers, as in the case of a multi-layer color light-sensitive material, filter layers can also be established between these layers.
Colored layers have been established between the photographic emulsion layer and the support, or on the opposite surface of the support to that on which the photographic emulsion layer is located, in order to prevent image blurring (halation) which occurs as a result of light which is scattered when passing through a photographic emulsion layer or after transmission being reflected at the interface between the emulsion layer and the support or at the surface of the light-sensitive material on the opposite side of the emulsion layer and redirected into the photographic emulsion layer. Colored layers of this type are called anti-halation layers. In the case of multi-layer color light-sensitive materials, an anti-halation layer can also be located between the various layers.
The photographic emulsion layers may also be colored in order to prevent the loss of image sharpness which is caused by light which has been scattered within the photographic emulsion layer. This phenomenon is generally referred to as irradiation.
In many cases, the layer which is to be colored is composed of a hydrophilic colloid, and therefore, water soluble dyes are generally used in these layers. These dyes must satisfy the three requirements listed below.

(1) They must have the appropriate spectral absorbance for the intended application.
(2) They must be photochemically inert. Thus, they must not have any adverse effect, in a chemical sense, on the performance of the silver halide photographic emulsion layer. Such adverse effects include, for example, reducing the sensitivity, causing the latent image fading or causing fogging.
(3) They must be decolorized or removed by dissolution during the course of photographic processing, and unwanted coloration must not remain in the photographic light-sensitive material after processing.

Many dyes which absorb in the visible and ultraviolet regions and which satisfy these requirements are known. However, at the present time there are few dyes which have an absorbance in the infrared region of the spectrum which satisfy all of the three aforementioned requirements.
For example, cyanine dyes which have various heterocyclic rings have been disclosed in U.S. Patents 2,895,955 and 4,263,397, JP-A-58-179266, JP-A-59-191032 and JP-A-59-192242, but when these dyes are used for anti-irradiation purposes in the emulsion layers of silver halide light-sensitive materials which have been spectrally sensitized to the infrared region there are problems in that they sometimes provide spectral sensitization in regions where it is not required or they may cause desorption of the sensitizing dyes which results in a loss of sensitivity. (The term "JP-A" as used herein signifies an "unexamined published Japanese patent application".) Furthermore, although favorable results are obtained when these dyes are used in anti-halation layers and filter layers, there are problems with residual coloration after processing.
Furthermore, the dyes disclosed in JP-A-62-123454, JP-A-63-55544, JP-A-1-147451, JP-A-1-147539, JP-A-1-233439, JP-A-1-239548, JP-A-1-217454, JP-A-1-280750, JP-A-1-293342 and JP-A-1-287559 have a satisfactory effect in terms of preventing halation and irradiation when they are added to a silver halide photographic light-sensitive material which has been spectrally sensitized to the infrared region. Because the absorption waveform is sharp, however, fogging occurs when the materials are handled under the bright safelight lighting known as daylight lighting. Therefore, it is necessary to use dyes of shorter wavelength than these dyes conjointly.
A dye which has an absorbance in the safelight light wavelength region may be added to the light-sensitive material in order to reduce the level of fogging due to safelight lighting. However, the dyes known in the past, for example, the oxonol dyes which have a pyrazolone nucleus or a barbituric acid nucleus disclosed, for example, in British Patents 506,385, 1,177,429, 1,311,884, 1,338,799, 1,385,371, 1,467,214, 1,433,102 and 1,553,516, JP-A-48-85130, JP-A-49-114420, JP-A-50-147712, JP-A-55-161233, JP-A-58-143342, JP-A-59-38742, JP-A-59-111641, JP-A-59-111640, and U.S. Patents 3,247,127, 3,469,985 and 4,078,933, and other oxonol dyes disclosed, for example, in U.S. Patents 2,533,472 and 3,379,533, and British Patent 1,278,621, the azo dyes disclosed, for example, in British Patents 575,691, 680,631, 599,623, 786,907, 907,125 and 1,045,609, U.S. Patent 4,255,326 and JP-A-59-211043, the azomethine dyes disclosed, for example, in JP-A-50-100116, JP-A-54-118247, and British Patents 2,014,598 and 750,031, the anthraquinone dyes disclosed in British Patent 2,865,752, the arylidene dyes disclosed, for example, in U.S. Patents 2,538,009, 2,688,541 and 2,538,008, British Patents 584,609 and 1,210,252, JP-A-50-40625, JP-A-51-3623, JP-A-51-10927, JP-A-54-118247, JP-B-48-3286 and JP-B-59-37303, the styryl dyes disclosed, for example, in JP-B-44-16594 and JP-B-59-28898, the triarylmethane dyes disclosed, for example, in British Patents 446,583 and 1,335,422, and JP-A-59-228250, the merocyanine dyes disclosed, for example, in British Patents 1,075,653, 1,153,341, 1,284,730, 1,475,228 and 1,542,807, and the cyanine dyes disclosed, for example, in U.S. Patents 2,843,486 and 3,294,539, had virtually no effect in reducing the level of fogging due to safelight lighting when added to silver halide photographic light-sensitive materials which had been spectrally sensitized to the infrared region, and even when they did have such an effect they had to be added in large amounts in order to achieve the effect. (The term "JP-B" as used herein signifies an "examined Japanese patent publication".) In general, some dye inevitably remains in the light-sensitive material after photographic processing when the dye is added to the light-sensitive material in large amounts, and staining occurs which reduces the commercial value of the light-sensitive material. Proposals have been made in JP-A-61-174540 and JP-A-2-1837 to address these problems, but a satisfactory result is not always attained.

SUMMARY OF THE INVENTION

A first object of the present invention is to provide a silver halide photographic light-sensitive material having a hydrophilic colloid layer which has been colored with a water soluble dye which has no adverse effect on the photographic characteristics of the photographic emulsion and which can be easily decolorized by photographic processing.
A second object of the present invention is to provide a silver halide photographic light-sensitive material which provides good images, which has a sufficiently low sensitivity for visible light and a high sensitivity for infrared light.
The above and other objects of the present invention have been attained by providing a silver halide photographic light-sensitive material having a silver halide emulsion layer comprised of silver halide grains which contain at least silver chloride and which have been spectrally sensitized to infrared using at least one tricarbocyanine dye and/or dicarbocyanine dye which contains a 4-quinoline nucleus, wherein there is at least one hydrophilic colloid layer which contains at least one dye which is represented by general formula (F-I) indicated below and at least one hydrophilic colloid layer which contains at least one dye which is represented by general formula (F-II) indicated below.
In formula (F-I), R¹, R², R³, R⁴, R⁵ and R⁶ may be the same or different, each being a substituted or unsubstituted alkyl group, and Z¹ and Z² each represents a group of non-metal atoms which is required to form a substituted or unsubstituted benzo-condensed ring, naphtho-condensed ring or five or six membered heterocyclic condensed ring. However, R¹, R², R³, R⁴, R⁵, R⁶, Z¹ and Z² are groups such that the dye molecule has at least three acid groups. L¹, L² and L³ represent substituted or unsubstituted methine groups and X represents an anion. Moreover, n is 1 or 2, and n is 1 when the dye forms an intramolecular salt.
In formula (F-II), R₂₁ and R₂₄ each represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group; R₂₂ and R₂₅ each represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, COR₂₉ or SO₂R₂₉; R₂₃ and R₂₆ each represents a hydrogen atom, a cyano group, an alkyl group, an aryl group, -COOR₂₇, -OR₂₇, -NR₂₇R₂₈, -N(R₂₈)COR₂₉, -N(R₂₈)SO₂R₂₉, -CONR₂₇R₂₈ or -N(R₂₇)CONR₂₇R₂₈ (where R₂₉ represents an aliphatic group or an aromatic group and R₂₇ and R₂₈ each represents a hydrogen atom, an aliphatic group or an aromatic group); L₄, L₅, L₆, L₇ and L₈ represent methine groups; n₁ and n₂ represent 0 or 1; and M^⊕ represents hydrogen or some other univalent cation; provided that at least one of R₂₁, R₂₂, R₂₃, R₂₄, R₂₅, R₂₆, L₄, L₅, L₆, L₇ or L₈ represents a group which has at least one carboxylic acid group or sulfonic acid group.

DETAILED DESCRIPTION OF THE INVENTION

Any silver halide which contains silver chloride, such as silver chloride, silver chlorobromide, silver chloroiodide or silver chloroiodobromide for example, may be used as the silver halide which is employed in the present invention. The silver iodide content of the silver halide is preferably from 0 to 2 mol%, and most preferably from 0 to 1 mol%. The silver chloride content of the silver halide is preferably at least 1 mol%, more preferably at least 10 mol%, and most preferably from 25 to 100 mol%.
These emulsions may have coarse grains or fine grains, or mixtures of coarse and fine grains, but monodisperse silver halide emulsions in which the average grain size (measured using the projected area method, number average method) is from about 0.04 µm to about 4 µm, and especially not more than 0.7 µm, are preferred.
Moreover, the crystal structure of the silver halide grains may be uniform into the interior or the inner and outer parts may have different layer structures, or the grains may be of the conversion type as disclosed in British Patent 635,841 and U.S. Patent 3,622,318. Furthermore, the grains may be of the type in which the latent image is formed principally on the grain surface, or of the internal latent image type in which the latent image is formed principally within the grains.
Ammonia, potassium thiocyanate, ammonium thiocyanate, thioether compounds (as disclosed, for example, in U.S. Patents 3,271,157, 3,574,628, 3,704,130, 4,297,439, 4,276,374), thione compounds (as disclosed, for example, in JP-A-53-144319, JP-A-53-82408 and JP-A-55-77737), and amine compounds (as disclosed, for example, in JP-A-54-100717) can be used as silver halide solvents for controlling grain growth during the formation of these silver halide grains.
Furthermore, water soluble rhodium and/or water soluble iridium can be added during the formation of the silver halide grains, or before or after the formation of the grains.
The silver halide emulsions can be subjected to various methods of chemical sensitization which are conventionally employed in the art. For example, gold sensitization (for example, as disclosed in U.S. Patents 2,540,085, 2,597,876, 2,597,915 and 2,399,083), sensitization with group VIII metal ions (for example, as disclosed in U.S. Patents 2,448,060, 2,540,086, 2,566,245, 2,566,263 and 2,598,079), sulfur sensitization (for example, as disclosed in U.S. Patents 1,574,944, 2,278,947, 2,440,206, 2,521,926, 3,021,215, 3,038,805, 2,410,689, 3,189,458, 3,415,649 and 3,635,717), reduction sensitization (for example, as disclosed in U.S. Patents 2,518,698, 2,419,974, 2,983,610, Research Disclosure, Vol. 176 (December 1978) RD-17643, section III), sensitization with thioether compounds (for example, as disclosed in U.S. Patents 2,521,926, 3,021,215, 3,038,805, 3,046,129, 3,046,132, 3,046,133, 3,046,134, 3,046,135, 3,057,724, 3,062,646, 3,165,552, 3,189,458, 3,192,046, 3,506,443, 3,671,260, 3,574,709, 3,625,697, 3,635,717 and 4,198,240), or combinations of these methods of sensitization can be employed.
Moreover, examples of specific chemical sensitizing agents which can be used include sulfur sensitizing agents, such as, allyl thiocarbamide, thiourea, thiosulfate, thioether and cysteine; noble metal sensitizing agents, such as, potassium chloroaurate, aurous thiosulfate and potassium chloro-palladate; and reduction sensitizing agents, such as, stannous chloride, phenylhydrazine and reductone.
The tricarbocyanine dyes and the dicarbocyanine dyes which contain a 4-quinoline nucleus are hereafter referred to as the infrared sensitizing dyes of the present invention.
Among the tricarbocyanines which can be used in the present invention, those represented by general formulae (Ia) and (Ib) indicated below are especially preferred.
In formulae (Ia) and (Ib), R₁ and R₂ may be the same or different, each representing an alkyl group which preferably has from 1 to 8 carbon atoms (for example, methyl, ethyl, propyl, butyl, pentyl, heptyl) or a substituted alkyl group of which the alkyl moiety has not more than 6 carbon atoms. Examples of the substituent for the substituted alkyl group include, for example, a carboxyl group, a sulfo group, a cyano group, a halogen atom (for example, fluorine, chlorine, bromine), a hydroxyl group, an alkoxycarbonyl group (which has not more than 8 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl), an alkoxy group (which has not more than 7 carbon atoms, for example, methoxy, ethoxy, propoxy, butoxy, benzyloxy), an aryloxy group (for example, phenoxy, p-tolyloxy), an acyloxy group (which has not more than 3 carbon atoms, for example, acetyloxy, propionyloxy), an acyl group (which has not more than 8 carbon atoms, for example, acetyl, propionyl, benzoyl, mesyl), a carbamoyl group (for example, carbamoyl, N,N-dimethylcarbamoyl, morpholinocarbamoyl, piperidinocarbamoyl), a sulfamoyl group (for example, sulfamoyl, N,N-dimethylsulfamoyl, morpholinosulfonyl) or an aryl group (for example, phenyl, p-hydroxyphenyl, p-carboxyphenyl, p-sulfophenyl, α-naphthyl), and two or more of these substituent groups may be combined and substituted onto the alkyl group.
R represents a hydrogen atom, a methyl group, a methoxy group or an ethoxy group.
R₃ and R₄ each represents a hydrogen atom, a lower alkyl group, (for example, methyl, ethyl, propyl), a lower alkoxy group (for example, methoxy, ethoxy, propoxy, butoxy), a phenyl group or a benzyl group.
R₅ represents a hydrogen atom, a lower alkyl group (for example, methyl, ethyl, propyl), a lower alkoxy group (for example, methoxy, ethoxy, propoxy, butoxy), a phenyl group, a benzyl group or

W₁ and W₂ each represents a substituted or unsubstituted alkyl group (of which the alkyl moiety has from 1 to 18 carbon atoms, and preferably from 1 to 4 carbon atoms (for example, methyl, ethyl, propyl, butyl, benzyl, phenethyl)) or an aryl group (for example, phenyl, naphthyl, tolyl, p-chlorophenyl), and W₁ and W₂ may be joined together to form a five or six membered nitrogen containing heterocyclic ring.
D represents a group of atoms which is required to complete a divalent ethylene bond, for example, ethylene or triethylene. This ethylene bond may be substituted with one, two or more than two appropriate groups, for example, alkyl groups which have from 1 to 4 carbon atoms (for example, methyl, ethyl, propyl, isopropyl, butyl), halogen atoms (for example, chlorine, bromine) or alkoxy groups (which have from 1 to 4 carbon atoms, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy).
D₁ and D₂ each represents a hydrogen atom. However, D₁ and D₂ together may form a divalent ethylene bond having the same significance as D described above.
Z and Z₁ each represents a group of non-metal atoms which is required to complete a five or six membered nitrogen containing heterocyclic group, such as, for example, a thiazole nucleus (for example, benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 5-iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-ethoxybenzothiazole, 5-carboxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5-phenethylbenzothiazole, 5-fluorobenzothiazole, 5-trifluoromethylbenzothiazole, 5,6-dimethylbenzothiazole, 5-hydroxy-6-methylbenzothiazole, tetrahydrobenzothiazole, 4-phenylbenzothiazole, naphtho[2,1-d]thiazole, naphtho[1,2-d]thiazole, naphtho[2,3-d]thiazole, 5-methoxynaphtho[1,2-d]thiazole, 7-ethoxynaphtho[2,1-d]thiazole, 8-methoxynaphtho[2,1-d]thiazole, 5-methoxynaphtho[2,3-d]thiazole), a selenazole nucleus (for example, benzoselenazole, 5-chlorobenzoselenazole, 5-methoxybenzoselenazole, 5-methylbenzoselenazole, 5-hydroxybenzoselenazole, naphtho[2,1-d]selenazole, naphtho[1,2-d]selenazole), an oxazole nucleus (for example, benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-bromobenzoxazole, 5-fluorobenzoxazole, 5-phenylbenzoxazole, 5-methoxybenzoxazole, 5-trifluorobenzoxazole, 5-hydroxybenzoxazole, 5-carboxybenzoxazole, 6-methylbenzoxazole, 6-chlorobenzoxazole, 6-methoxybenzoxazole, 6-hydroxybenzoxazole, 4,6-dimethylbenzoxazole, 5-ethoxybenzoxazole, naphtho[2,1-d]oxazole, naphtho[1,2-d]oxazole, naphtho[2,3-d]oxazole), a quinoline nucleus (for example, 2-quinoline, 3-methyl-2-quinoline, 5-ethyl-2-quinoline, 6-methyl-2-quinoline, 8-fluoro-2-quinoline, 6-methoxy-2-quinoline, 6-hydroxy-2-quinoline, 8-chloro-2-quinoline, 8-fluoro-4-quinoline), a 3,3-dialkylindolenine nucleus (for example, 3,3-dimethylindolenine, 3,3-diethylindolenine, 3,3-dimethyl-5-cyanoindolenine, 3,3-dimethyl-5-methoxyindolenine, 3,3-dimethyl-5-methylindolenine, 3,3-dimethyl-5-chloroindolenine), an imidazole nucleus (for example, 1-methylbenzimidazole, 1-ethylbenzimidazole, 1-methyl-5-chlorobenzimidazole, 1-ethyl-5-chlorobenzimidazole, 1-methyl-5,6-dichlorobenzimidazole, 1-ethyl-5,6-dichlorobenzimidazole, 1-alkyl-5-methoxybenzimidazole, 1-methyl-5-cyanobenzimidazole, 1-ethyl-5-cyanobenzimidazole, 1-methyl-5-fluorobenzimidazole, 1-ethyl-5-fluorobenzimidazole, 1-phenyl-5,6-dichlorobenzimidazole, 1-allyl-5,6-dichlorobenzimidazole, 1-allyl-5-chlorobenzimidazole, 1-phenylbenzimidazole, 1-phenyl-5-chlorobenzimidazole, 1-methyl-5-trifluoromethylbenzimidazole, 1-ethyl-5-trifluoromethylbenzimidazole, 1-ethylnaphtho[1,2-d]imidazole) or a pyridine nucleus (for example, pyridine, 5-methyl-2-pyridine, 3-methyl-4-pyridine). Of these, the thiazole and oxazole nuclei are preferred. The use of a benzothiazole nucleus, a naphthothiazole nucleus, a naphthoxazole nucleus or a benzoxazole nucleus is most preferable.
X represents an acid anion.
Moreover, n represents 1 or 2.
Especially useful 4-quinoline nucleus containing dicarbocyanine dyes which can be used in the present invention are represented by general formula (II) below.
In formula (II), R₆ and R₇ have the same significance, respectively, as R₁ and R₂ in the above general formulae (Ia) and (Ib).
R₈ in formula (II) has the same significance as R₃ and R₄ in the above general formulae (Ia) and (Ib). However, R₈ is preferably a lower alkyl group or a benzyl group.
V in formula (II) represents a hydrogen atom, a lower alkyl group (for example, methyl, ethyl, propyl), an alkoxy group (for example, methoxy, ethoxy, butoxy), a halogen atom (for example, fluorine, chlorine) or a substituted alkyl group (for example, trifluoromethyl, carboxymethyl).
Z₂ in formula (II) has the same significance as Z and Z₁ in the above general formulae (Ia) and (Ib).
X₁ in formula (II) has the same significance as X in the above general formulae (Ia) and (Ib).
Moreover, m, n₁ and p each represents 1 or 2.
Actual examples of sensitizing dyes which can be used in the present invention are indicated below, but the invention is not limited to just these sensitizing dyes.
The above mentioned infrared sensitizing dyes which can be used in the present invention are included in the silver halide photographic emulsion in an amount of from 5 X 10⁻⁷ to 5 X 10⁻³ mol, preferably of from 1 x 10⁻⁶ to 1 x 10⁻³ mol, and most preferably of from 2 x 10⁻⁶ to 5 X 10⁻⁴ mol, per mol of silver halide.
The aforementioned infrared sensitizing dyes which are used in the present invention can be dispersed directly in the emulsion. Furthermore, they can be dissolved in a suitable solvent (for example, methyl alcohol, ethyl alcohol, methylcellosolve, acetone, water, pyridine or a mixture of these solvents) and added to the emulsion in the form of a solution. In addition, ultrasonics can be employed to achieve dissolution.
Other methods which can be used for the addition of the aforementioned infrared sensitizing dyes include: the method in which the dye is dissolved in a volatile organic solvent, the resulting solution is then dispersed in a hydrophilic colloid, and the dispersion is added to the emulsion as disclosed, for example, in U.S. Patent 3,469,987; the method in which a water insoluble dye is dispersed in a water soluble solvent in which it does not dissolve, and then the dispersion is added to the emulsion as disclosed, for example, in JP-B-46-24185; the method in which the dye is dissolved in a surfactant and the resulting solution is added to the emulsion, as disclosed in U.S. Patent 3,822,135; the method in which dissolution is achieved using a red-shifted compound, and the solution is added to the emulsion, as disclosed in JP-A-51-74624; and the method in which the dye is dissolved in substantially water free acid and the resulting solution is then added to the emulsion, as disclosed in JP-A-50-80826. The methods disclosed, for example, in U.S. Patents 2,912,343, 3,342,605, 2,996,287 and 3,429,835 can also be used for making the addition to the emulsion. Furthermore, the above mentioned infrared sensitizing dyes of general formulae (I) and (II) may be dispersed uniformly in the silver halide emulsion prior to coating on an appropriate support, and, of course, they may be dispersed at any stage during the preparation of the silver halide emulsion.
Moreover, combinations of other sensitizing dyes can be used with the above-mentioned infrared sensitizing dyes in accordance with the present invention. For example, use can be made of the sensitizing dyes disclosed, for example, in U.S. Patents 3,703,377, 2,688,545, 3,397,060, 3,615,635 and 3,628,964, British Patents 1,242,588 and 1,293,862, JP-B-43-4936, JP-B-44-14030, JP-B-43-10773, U.S. Patent 3,416,927, JP-B-43-4930, and U.S. Patents 3,615,613, 3,615,632, 3,617,295 and 3,635,721.
Compounds represented by general formula (III) below can be used in the present invention in order to further increase the supersensitizing effect and/or further improve storage properties.
In formula (III), -A- represents a divalent aromatic residual group that may contain an -SO₃M group (where M represents a hydrogen atom or a cation, for example, sodium, or potassium, which provides water solubility).
-A- may be selected from among the groups -A₁-or -A₂- indicated below. -A- is selected from group -A₁-when no -SO₃M group is included in R₉, R₁₀, R₁₁ or R₁₂ of formula (III). -A₁- represents, for example, the following groups:
In the above -A₁- groups, M represents a hydrogen atom or a cation which provides water solubility. -A₂- represents, for example, the following groups:
R₉, R₁₀, R₁₁ and R₁₂ each represents a hydrogen atom, a hydroxyl group, a lower alkyl group (which preferably has from 1 to 8 carbon atoms, for example, methyl, ethyl, n-propyl, n-butyl), an alkoxy group (which preferably has from 1 to 8 carbon atoms, for example, methoxy, ethoxy, propoxy, butoxy), an aryloxy group (for example, phenoxy, naphthoxy, o-toloxy, P-sulfophenoxy), a halogen atom (for example, chlorine, bromine), a heterocyclic nucleus (for example, morpholinyl, piperidyl), an alkylthio group (for example, methylthio, ethylthio), a heterocyclylthio group (for example, benzothiazolylthio, benzimidazolylthio, phenyltetrazolylthio), an arylthio group (for example, phenylthio, tolylthio), an amino group, a substituted or unsubstituted alkylamino group (for example, methylamino, ethylamino, propylamino, dimethylamino, diethylamino, dodecylamino, cyclohexylamino, β-hydroxyethylamino, di-(β-hydroxyethyl)amino, β-sulfoethylamino), a substituted or unsubstituted arylamino group (for example, anilino, o-sulfoanilino, m-sulfoanilino, p-sulfoanilino, o-toluidino, m-toluidino, p-toluidino, o-carboxyanilino, m-carboxyanilino, p-carboxyanilino, o-chloroanilino, m-chloroanilino, p-chloroanilino, p-aminoanilino, o-anisidino, m-anisidino, p-anisidino, o-acetaminoanilino, hydroxyanilino, disulfophenylamino, naphthylamino, sulfonaphthylamino), a heterocyclylamino group (for example, 2-benzothiazolylamino, 2-pyridylamino), a substituted or unsubstituted aralkylamino group (for example, benzylamino, o-anisylamino, m-anisylamino, p-anisylamino), an aryl group (for example, phenyl), or a mercapto group. R₉, R₁₀, R₁₁ and R₁₂ may be the same or different. In those cases where -A- is selected from the -A₂- group, at least one of R₉, R₁₀, R₁₁ and R₁₂ must have at least one sulfo group, which may be a free sulfo group or in the form of a salt. W represents -CH= or -N=, and preferably -CH=.
Actual examples of compounds represented by general formula (III) which can be used in the present invention are indicated below, but the invention is not limited to just these compounds.

(III-1): Disodium 4,4'-bis[4,6-di(benzothiazolyl-2-thio)pyrimidin-2-ylamino]stilbene-2,2'-disulfonate
(III-2): Disodium 4,4'-bis[4,6-di(benzothiazolyl-2-amino)pyrimidin-2-ylamino]stilbene-2,2'-disulfonate
(III-3): Disodium 4,4'-bis[4,6-di(naphthyl-2-oxy)pyrimidin-2-ylamino]stilbene-2,2'-disulfonate
(III-4): Disodium 4,4'-bis[4,6-di(naphthyl-2-oxy)pyrimidin-2-ylamino]bibenzyl-2,2'-disulfonate
(III-5): Disodium 4,4'-bis(4,6-dianilinopyrimidin-2-ylamino)stilbene-2, 2'-disulfonate
(III-6): Disodium 4,4'-bis[4-chloro-6-(2-naphthyloxy)pyrimidin-2-ylamino]biphenyl-2,2'-disulfonate.
(III-7): Disodium 4,4'-bis[4,6-di(1-phenyltetrazolyl-5-thio)pyrimidin-2-ylamino]stilbene-2,2'-disulfonate
(III-8): Disodium 4,4'-bis[4,6-di(benzimidazolyl-2-thio)pyrimidin-2-ylamino]stilbene-2,2'-disulfonate
(III-9): Disodium 4,4'-bis(4,6-diphenoxypyrimidin-2-ylamino)stilbene-2,2'-disulfonate
(III-10): Disodium 4,4'-bis(4,6-diphenylthiopyrimidin-2-ylamino)stilbene-2,2'-disulfonate.
(III-11): Disodium 4,4'-bis(4,6-dimercaptopyrimidin-2-ylamino)biphenyl-2, 2'-disulfonate
(III-12): Disodium 4,4'-bis(4,6-dianilinotriazin-2-ylamino)stilbene-2,2'-disulfonate
(III-13): Disodium 4,4'-bis(4-anilino-6-hydroxytriazin-2-ylamino)stilbene-2,2'-disulfonate
(III-14): Disodium 4,4'-bis(4-naphthylamino-6-anilinotriazin-2-ylamino)stilbene-2,2'-disulfonate

From among these actual examples, Compounds (III-1) to (III-12) are preferred, and Compounds (III-1), (III-2), (III-3), (III-4), (III-5) and (III-7) are especially preferred.
The compounds of general formula (III) are used in amounts of from about 0.01 gram to 5 grams per mol of silver halide in the emulsion.
The proportions by weight of the infrared sensitizing dyes of the present invention described earlier and the compounds represented by general formula (III) are such that the value of the ratio (all the infrared sensitizing dyes of the present invention/compound represented by general formula (III)) is from 1/1 to 1/100, and preferably from 1/2 to 1/50.
The compounds represented by general formula (III) which can be used in the present invention can be dispersed directly in the emulsion, or they can be added to the emulsion after dissolution in a suitable solvent (for example, methyl alcohol, ethyl alcohol, methyl-cellosolve or water) or in a mixture of such solvents. They can also be added to the emulsion as a solution or in the form of a dispersion in a colloid in accordance with the methods for the addition of other sensitizing dyes. Furthermore, they can be dispersed and added to the emulsion using the method disclosed in JP-A-50-80119.
Moreover, combinations of the infrared sensitizing dyes of the present invention with compounds which can be represented by the general formula (IV) indicated below can be used in the present invention.
In formula (IV), Z₃ represents a group of non-metal atoms which is required to complete a five or six membered nitrogen containing heterocyclic ring, such as, a thiazolium (for example, thiazolium, 4-methylthiazolium, benzothiazolium, 5-methylbenzothiazolium, 5-chlorobenzothiazolium, 5-methoxybenzothiazolium, 6-methylbenzothiazolium, 6-methoxybenzothiazolium, naphtho[1,2-d]thiazolium, naphtho[2,1-d]thiazolium), an oxazolium (for example, oxazolium, 4-methyloxazolium, benzoxazolium, 5-chlorobenzoxazolium, 5-phenylbenzoxazolium, 5-methylbenzoxazolium, naphtho[1,2-d]oxazolium), an imidazolium (for example, 1-methylbenzimidazolium, 1-propyl-5-chlorobenzimidazolium, 1-ethyl-5,6-dichlorobenzimidazolium, 1-allyl-5-trichloromethyl-6-chlorobenzimidazolium) and a selenazolium (for example, benzoselenazolium, 5-chlorobenzoselenazolium, 5-methylbenzothiazolium, 5-methoxybenzoselenazolium, naphtho[1,2-d]selenazolium). R₁₃ represents a hydrogen atom, an alkyl group which has not more than 8 carbon atom (for example, methyl, ethyl, propyl, butyl, pentyl), or an alkenyl group (for example, allyl). R₁₄ represents a hydrogen atom or a lower alkyl group (for example, methyl, ethyl). X₂ represents an acid anion (for example, Cl⁻, Br⁻, ClO₄⁻, p-toluenesulfonate). Among the groups represented by z₃, the use of a thiazolium is preferred. The use of a substituted or unsubstituted benzothiazolium or naphthothiazolium is preferred.
Actual examples of compounds represented by general formula (IV) are indicated below. However, the invention is not limited to just these compounds.
The compounds represented by the above mentioned general formula (IV) are preferably used in amounts of from about 0.01 gram to 5 grams per mol of silver halide in the emulsion.
The proportions in terms of the ratio by weight of the above infrared sensitizing dyes of the present invention and the compounds represented by general formula (IV) (which is to say the ratio by weight of all the infrared sensitizing dyes of the present invention/compound represented by general formula (IV)) is suitably from 1/1 to 1/300, and preferably from 1/2 to 1/50.
The compounds represented by general formula (IV) which are used in the present invention can be dispersed directly in the emulsion, and they can also be dissolved in an appropriate solvent (for example, water, methyl alcohol, ethyl alcohol, propanol, methyl-cellosolve or acetone), or in a mixture of these solvents, and added to the emulsion. They can also be added to the emulsion in solution, or in the form of a dispersion in a colloid, in accordance with methods for the addition of sensitizing dyes, such as the methods for adding the infrared sensitizing dyes of the present invention.
The compounds represented by general formula (IV) may be added to the emulsion before or after the addition of the infrared sensitizing dyes of the present invention described earlier. Furthermore, the compounds of general formula (IV) and the infrared sensitizing dyes of the present invention can be dissolved separately and added separately to the emulsion at the same time, or they can be added to the emulsion after mixing.
The dyes represented by general formula (F-I) are described in greater detail below.
The alkyl groups represented by R¹, R², R³, R⁴, R⁵ and R⁶ are preferably lower alkyl groups which have from 1 to 5 carbon atoms (for example, methyl, ethyl, n-propyl, n-butyl, iso-propyl, n-pentyl), and they may have substituent groups, for example, a sulfonic acid group, a carboxylic acid group, OPO₃M₂ (where M is H, Na, K or Li for example), a hydrophilic non-ionic group (for example, CN, CONH₂, COCH₃, NHCOCH₃, SO₂HN₂), a cyclic imido group
and a hydroxyl group. Preferably, R¹ and R⁴ represent lower alkyl groups which have from 1 to 5 carbon atoms which have sulfonic acid substituent groups or carboxylic acid substituent groups (for example, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, 3-sulfobutyl, carboxymethyl, sulfomethyl, 2-carboxyethyl).
A sulfonic acid group, a carboxylic acid group, a hydroxyl group, a halogen atom (for example, F, Cl, Br), a cyano group, a substituted amino group (for example, dimethylamino, diethylamino, ethyl-4-sulfobutylamino, di(3-sulfopropyl)amino), a carbamoyl group, a sulfamoyl group, an acetamido group, a methanesulfonamido group, a cyclic imido group, or a substituted or unsubstituted alkyl group which has from 1 to 5 carbon atoms {for example, methyl, ethyl, propyl, butyl, (preferably with, for example, a sulfonic acid group, a carboxylic acid group, a hydroxyl group, a cyano group, a sulfamoyl group, or a carbamoyl group as substituent groups)} which is bonded directly or via a divalent linking group (preferably, for example, -O-, -NHCO-, -NHSO₂-, -NHCOO-, -NHCONH-, -COO-, -CO- or -SO₂-) to the ring is an example of substituent group for the benzo-condensed rings and naphtho-condensed rings which are formed by the groups of non-metal atoms represented by z¹ and Z².
A pyridine ring, a thiophene ring, a furan ring and a pyrrole ring are examples of heterocyclic rings which can be formed by the groups of non-metal atoms represented by Z¹ and Z².
Lower alkyl groups which have from 1 to 5 carbon atoms (for example, methyl, ethyl, sulfoethyl, benzyl) and halogen atoms (for example, F, Cl, Br), for example, are the preferred substituent groups for the methine groups represented by L¹, L² and L³. Furthermore, a five membered ring (for example, a cyclopentene ring, a 1-chlorocyclopentene ring, a 1-morpholinocyclopentene ring, a 1-(4-ethoxycarbonylpiperazin-1-yl)cyclopentene ring or 1,1-dimethylaminocyclopentene ring) or a six membered ring (for example, a 4,4-dimethylcyclohexene ring, a cyclohexene ring or a 1-chlorocyclohexene ring) which contains three methine groups may be formed by the bonding together of the substituent groups of the methine groups represented by L¹, L² and L³.
At least three acid groups, and preferably from four to six acid groups, which the groups represented by R¹ to R⁶, Z¹ and Z² have are preferably sulfonic acid groups, carboxylic acid groups or

where Y represents O, S or an amino group, R represents H, an alkyl group (for example, methyl, ethyl), an alkoxy group (for example, methoxy, ethoxy) or OM (where M represents a cation such as H, Na, K, Li), and m represents 1 or 2. Most preferably, R¹ to R⁶, Z¹ and Z² are groups such that the dye molecule has four to six sulfonic acid groups.
In the present invention, the acid groups may be free acid groups or they may take the form of a salt (for example, the salt of an alkali metal such as Li, Na, K, an ammonium salt, or an organic ammonium salts such as a triethylamine salt, a tributylamine salt or pyridine salt).
The anion represented by X may be, for example, a halogen ion (Cl, Br), a p-toluenesulfonate ion or an ethyl sulfate ion.
Actual examples of dye compounds represented by the aforementioned general formula (F-I) which can be used in this present invention are indicated below, but the scope of the invention is not limited by these examples.
Dyes represented by general formula (F-I) can be prepared using the methods disclosed in JP-A-62-123454, JP-A-63-55544, JP-A-1-287559, JP-A-1-280750 and JP-A-1-239548, or in accordance with the methods disclosed in these specifications.
General formula (F-II) is described in detail below.
The aliphatic groups represented by R₂₁, R₂₂, R₂₃, R₂₄, R₂₅, R₂₆, R₂₇, R₂₈ and R₂₉ are preferably linear chain, branched or cyclic alkyl groups which have from 1 to 8 carbon atoms, aralkyl groups which have from 6 to 12 carbon atoms or alkenyl groups which have from 3 to 7 carbon atoms. Actual examples of such groups include methyl, ethyl, n-butyl, benzyl, 2-sulfoethyl, 4-sulfobutyl, 2-sulfobenzyl, 2,4-disulfobenzyl, 2-carboxyethyl, carboxymethyl, 2-hydroxyethyl, dimethylaminoethyl and trifluoromethyl.
The aromatic groups represented by R₂₁, R₂₂, R₂₃, R₂₄, R₂₅, R₂₆, R₂₇, R₂₈ and R₂₉ are preferably aryl groups which have from 6 to 10 carbon atoms. Actual examples include phenyl, naphthyl, 4-sulfophenyl, 3-sulfophenyl, 2-sulfophenyl, 2,5-disulfophenyl, 2,4-disulfophenyl, 3,5-disulfophenyl, 4-carboxyphenyl, 5,7-disulfo-3-naphthyl, 4-methoxyphenyl and p-tolyl.
The heterocyclic groups represented by R₂₁, R₂₂, R₂₄ and R₂₅ are five or six membered nitrogen containing heterocyclic groups (including benzo-condensed rings), and examples include 5-sulfopyridin-2-yl and 5-sulfobenzothiazol-2-yl.
The methine groups represented by L₄, L₅, L₆, L₇ and L₈ may have substituent groups (for example, methyl, ethyl, phenyl, chlorine, sulfoethyl, carboxyethyl, dimethylamino, cyano), and the substituent groups may be joined together to form a five or six membered ring (for example, cyclohexene, cyclopentene, 5,5-dimethylcyclohexene).
The single cation other than hydrogen represented by M^⊕ may be, for example, Na^⊕, K^⊕, HN^⊕(C₂H₅)₃,
or Li^⊕.
Actual examples of dyes represented by general formula (F-II) which can be used in the present invention are indicated below, but the invention is not limited by these examples. (Actual examples of the substituent groups in the general formula (F-II) are shown in the following table.)
The dyes represented by general formula (F-II) can be prepared using the methods disclosed in JP-A-63-316853 and JP-B-58-35544, or on the basis of these methods, or on the basis of the method outlined below.

Synthesis Example 1 (Preparation of F-II-8)

Compound (A) indicated below was obtained by reacting 1-(4-sulfophenyl)-3-amino-2-pyrazoline-5-one and ethyl acetoacetate in acetic acid solution for 5 hours at a temperature of 85°C to 90°C using triethylamine as a base. Eight grams of Compound (A) and 10 ml of 1,1,3,3-tetramethoxypropane were added to a mixed solvent comprised of 20 ml of pyridine and 10 ml of acetic acid and the mixture was heated and stirred for 2 hours at a temperature of 95°C to 100°C. The crystals which formed were removed by filtration. The black powder so obtained (3 grams) was dissolved in 9 ml of distilled water and a salt was formed by adding 10 ml of a methanolic solution which contained 2 grams of potassium acetate. The crystals which formed were removed by filtration, washed with methanol and dried, whereupon 2 grams of (F-II-8) were obtained. Compound (F-II-8) was tested and found to have the following properties:

λmax =: 645 nm (molar extinction coefficient:
ε= 8.2 x 10⁴) (Distilled water)

Melting Point: above 300°C
The dyes represented by general formulae (F-I) and (F-II) described above can be dissolved in an appropriate solvent (for example, water, methanol, ethanol, N,N-dimethylformamide or a mixture of such solvents) and added to the coating liquid which is to be used for a hydrophilic colloid layer of the present invention. Furthermore, when the dyes are sparingly soluble in water they may be added as dispersions of solid, finely divided particles.
In those cases where dyes of general formula (F-I) and/or (F-II) are used in the form of a solid, finely divided particle dispersion, both the dyes of general formula (F-I) and (F-II) may be used as dispersions of solid, finely divided particles or just one may be used in the form of a dispersion of solid, finely divided particles.
Fine particle dispersions of dyes of general formula (F-I) or (F-II) of the present invention can be formed using the method in which the dyes of formula (F-I) and/or (F-II) of the present invention are precipitated in the form of a dispersion and/or the methods in which the dispersion is formed using a known means of pulverization, for example, ball milling (for example, with a ball mill, vibrating ball mill or satellite ball mill), sand milling, colloid milling, jet milling or roller milling, in the presence of a dispersing agent (in this case, a solvent (for example, water or alcohol) may also be present).
Alternatively, a fine crystalline powder can be precipitated by dissolving the dye of formula (F-I) and/or (F-II) of the present invention in an appropriate solvent and then adding a poor solvent for the dye, and in this case a surfactant for dispersion purposes may be used. Alternatively, the dyes of formula (F-I) and/or (F-II) of the present invention may be first dissolved by controlling the pH and then precipitated as fine crystals by changing the pH.
The solid, finely divided particles of dye of formula (F-I) and/or (F-II) of the present invention in the dispersion are of average particle size not more than 10 µm, preferably not more than 2 µm and more preferably not more than 0.5 µm and, depending on the particular case, fine particles of not more than 0.1 µm are most preferable.
The dyes of general formula (F-I) or (F-II) of the present invention can be used in an emulsion layer or in any other hydrophilic colloid layer, and the respective dyes can be used in the same layer and/or in different layers. These dyes may be used in combinations of two or more types.
The amount of the dyes of general formulae (F-I) and (F-II) of the present invention can be selected according to the intended purpose. Preferably the dye of general formula (F-I) and the dye of general formula (F-II) each is used in amounts of from 10⁻⁴ g/m² to 1 g/m², and more preferably in amounts within the range from 10⁻³ g/m² to 0.5 g/m².
Various compounds can be added to the photographic emulsions of the present invention to prevent any loss of sensitivity or fogging during the manufacturing processes, storage or processing of the light-sensitive material. Many of these compounds, including heterocyclic compounds, mercury containing compounds, mercapto compounds and metal salts for example, such as nitrobenzimidazole, ammonium chloroplatinate, 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene and 1-phenyl-5-mercaptotetrazole, have been known for a very long time. Examples of compounds which can be used include those disclosed in the literature on pages 344 - 349 of K. Mees, The Theory of the Photographic Process (third ed., 1966) and other compounds including, for example, the thiazolium salts disclosed, for example, in U.S. Patents 2,131,038 and 2,694,716, the azaindenes disclosed, for example, in U.S. Patents 2,886,437 and 2,444,605, the urazoles disclosed, for example, in U.S Patent 3,287,135, the sulfocatechols disclosed, for example, in U.S. Patent 3,236,652, the oximes disclosed, for example, in British Patent 623,448, the mercaptotetrazoles, nitron and nitroindazoles disclosed, for example, in U.S. Patents 2,403,927, 3,266,897 and 3,397,987, the polyvalent metal salts disclosed, for example, in U.S. Patent 2,839,405, the thiouronium salts disclosed, for example, in U.S. Patent 3,220,839, and the palladium, platinum and gold salts disclosed, for example, in U.S. Patents 2,566,263 and 2,597,915.
The silver halide photographic emulsions may contain developing agents, for example hydroquinones, catechols, aminophenols, 3-pyrazolidones, ascorbic acid and derivatives thereof, reductones and phenylenediamines, or combinations of developing agents. The developing agents can be introduced into the silver halide emulsion layer and/or other photographic layers (for example, protective layers, intermediate layers, filter layers, anti-halation layers and backing layers). The developing agents can be dissolved in an appropriate solvent for addition, or they can be added in the form of a dispersion as disclosed in U.S. Patent 2,592,368 or French Patent 1,505,778.
The development accelerators disclosed, for example, in U.S. Patents 3,288,612, 3,333,959, 3,345,175 and 3,708,303, British Patent 1,098,748, and West German Patents 1,141,531 and 1,183,784 can be used in the present invention.
Inorganic or organic hardening agents may be included in the photographic emulsions of the present invention. For example, use can be made of chromium salts (for example, chrome alum, chromium acetate), aldehydes (for example, formaldehyde, glyoxal, glutaraldehyde), N-methylol compounds (for example, dimethylolurea, methyloldimethylhydantoin), dioxane derivatives (for example, 2,3-dihydroxydioxane), active vinyl compounds (for example, 1,3,5-triacryloyl-hexahydro-s-triazine, bis(vinylsulfonyl)methyl ether, N,N'-methylenebis[β-(vinylsulfonyl)propionamide]), active halogen compounds (for example, 2,4-dichloro-6-hydroxy-s-triazine), mucohalogenic acids (for example, mucochloric acid, mucophenoxychloric acid), isooxazoles, dialdehyde starch, and 2-chloro-6-hydroxytriazinylated gelatin, these being used either individually or in combinations. Examples of hardening agents are disclosed, for example, in U.S. Patents 1,870,354, 2,080,019, 2,726,162, 2,870,013, 2,983,611, 2,992,109, 3,047,394, 3,057,723, 3,103,437, 3,321,313, 3,325,287, 3,362,827, 3,539,644 and 3,543,29-2, British Patents 676,628, 825,544 and 1,270,578, German Patents 872,153 and 1,090,427, JP-B-34-7133 and JP-B-46-1872.
Various surfactants may be included for various purposes in the photographic emulsion layers or other hydrophilic colloid layers of the light-sensitive material of the present invention, for example as coating aids, for anti-static purposes, for improving slip properties, for emulsification and dispersion purposes, for preventing sticking or for improving photographic performance (for example, for accelerating development, increasing contrast or for sensitization).
For example, use can be made of non-ionic surfactants, such as saponin (steroid based), alkylene oxide derivatives (for example, polyethylene glycol, polyethylene glycol/polypropylene glycol condensate, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkyl amines or amides and poly(ethylene oxide) adducts of silicones), glycidol derivatives (for example, alkenyl succinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols and the alkyl esters of sugars; anionic surfactants such as those which contain an acidic group such as a carboxyl group, sulfo group, phospho group, sulfate ester group or phosphate ester group, for example alkylcarboxylates, alklysulfonates, alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkylsulfate esters, alkylphosphate esters, N-acyl-N-alkyltaurines, sulfosuccinate esters, sulfoalkylpolyoxyethylene alkylphenyl ethers and polyoxyethylene alkyl phosphate esters; amphoteric surfactants, such as amino acids, aminoalkylsulfonic acids, aminoalkylsulfate or phosphate esters, alkylbetaines and amine oxides; and cationic surfactants such as alkylamine salts, aliphatic and aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium salts and imidazolium salts, and phosphonium or sulfonium salts which contain aliphatic or heterocyclic rings.
In those cases where a mordant is used, the conjoint use of an anionic surfactant and an amphoteric surfactant is preferred for facilitating coating and improving the mordanting properties. These surfactants may be added to a light-insensitive hydrophilic colloid layer coating liquid or to an emulsion layer coating liquid. The amount used and the ratio of the two types of surfactant are optional and can be determined easily by experiment.
The anionic group of the anionic surfactants which can be used in the present invention can be, for example, a sulfonic acid group, a carboxylic acid group or a phosphoric acid group, and the hydrophobic portion is, for example, a hydrocarbon or a partially or fully fluorinated hydrocarbon.
Typical examples of the anionic surfactants which are preferably used in the present invention are indicated below by formula (A-1) to (A-9), but the invention is not limited by these examples.
In formula (A-1), R₆₀ is a saturated or unsaturated hydrocarbyl group or fluorinated derivative thereof which has from 3 to 20 carbon atoms, and R₆₁ is a hydrogen atom, a methyl group, an ethyl group or a propyl group. Moreover, n₆₀ is an integer from 1 to 20, and preferably from 1 to 8. M is a univalent alkali metal, and preferably Na or K.
In general formulae (A-2) and (A-3), R₆₀, M and n₆₀ have the same significanceas in general formula (A-1), and a represents 0, 1 or 2. Moreover, m₆₀ is an integer from 1 to 6, and preferably from 2 to 4.
R₆₀ and M in general formulae (A-4), (A-5) and (A-6) have the same significance as those in general formula (A-1).
R₆₁ and M in general formula (A-7) have the same significance as in general formula (A-1), and m₆₀ has the same significance as in general formula (A-2).
In general formulae (A-8) and (A-9), R₆₂ is a saturated or unsaturated hydrocarbon of which the hydrogen part has been fluorinated and which has from 3 to 22, and preferably from 7 to 18, carbon atoms. R₆₁ and M have the same significance as in general formula (A-1) and m₆₀ has the same significance as in general formula (A-2).
Actual examples of the anionic surfactants which are particularly preferably used are indicated below.
The amphoteric surfactants which can be used in the present invention have both an anionic group and a cationic group in a single molecule, and are surfactants which form intramolecular salts. These surfactants can be represented by general formula (B).
In general formula (B), A^⊖ is an anion radical which contains an anionic group such as a sulfonic acid group, carboxylic acid group or phosphoric acid group for example, and C^⊕ is an organic cation radical.
Actual examples of amphoteric surfactants which are particularly preferably used in the present invention are indicated below.

B-1: (10-Carboxydecyl)dimethyldodecylammonium hydroxide
B-2: (2-Carboxyethyl)dimethyldodecylammonium hydroxide
B-3: (3-Sulfopropyl)dimethyldodecylammonium hydroxide
B-4: (4-Sulfobutyl)diethyldodecylammonium hydroxide
B-5: (2-Carboxyethyl)dimethyloctadecylammonium hydroxide
B-6: (3-Sulfopropyl)dimethyloctadecylammonium hydroxide
B-7: (Carboxymethyl)dimethyloctadecylammonium hydroxide
B-8: (Carboxymethyl)dimethylundecylcarbamoylpropylammonium hydroxide
B-9: (3-Sulfobutyl)dimethylundecylcarbamoylpropylammonium hydroxide
B-10: 1-(10-Carboxydecyl)pyridium hydroxide
B-11: 1-(10-Sulfodecyl)pyridium hydroxide
B-12: 3-Carboxy-1-dodecylpyridinium hydroxide
B-13: 1-(1-Carboxytridecylpyridinium hydroxide

The use of polyalkylene oxide compounds (for example, polyalkylene oxides comprised of at least 10 units of an alkylene oxide which has from 2 to 4 carbon atoms, such as ethylene oxide, propylene-1,2-oxide, butylene-1,2-oxide, and preferably ethylene oxide, condensates with compounds which have at least one active hydrogen atom, such as water, aliphatic alcohols, aromatic alcohols, fatty acids, organic amines and hexytol derivatives, or block copolymers of two or more types of polyalkylene oxide) is preferable for improving the cut off at the toe of the characteristic curve and for obtaining halftone dot and line works of improved quality. In practice, the following compounds can be used as the polyalkylene oxide compounds:
Polyalkylene glycols
Polyalkylene glycol alkyl ethers
Polyalkylene glycol aryl ethers
Polyalkylene glycol (alkyl aryl) ethers
Polyalkylene glycol esters
Polyalkylene glycol fatty acid amides
Polyalkylene glycol amines
Polyalkylene glycol block copolymers
Polyalkylene glycol graft polymers
The molecular weight must be at least 600.
The molecules are not limited to having just one polyalkylene oxide chain, and the molecule may contain two or more such chains. In such cases the individual polyalkylene oxide chains may be comprised of not more than 10 alkylene oxide units, but the total number of alkylene oxide units within the molecule must be at least 10. In those cases where there are two or more polyalkylene oxide chains in the molecule, these chains may each be comprised of different alkylene oxide units, for example they may be comprised of ethylene oxide and propylene oxide. The polyalkylene oxide compounds which can be used in the present invention preferably have from 14 to 100 alkylene oxide units.
The polyalkylene oxide compounds disclosed in JP-A-50-156423, JP-A-52-108130 and JP-A-53-3217 can be used as the polyalkylene oxide compound. Just one of these polyalkylene oxide compounds can be used, or two or more types can be used conjointly.
In those cases where these polyalkylene oxide compounds are added to a silver halide emulsion, they can be added as an aqueous solution of the appropriate concentration or after dissolution in a low boiling point organic solvent which is miscible with water to the emulsion at an appropriate time before coating, and preferably after chemical ripening.
These polyalkylene oxide compounds are preferably used in amounts of from 1 x 10⁻⁵ mol to 1 x 10⁻² mol per mol of silver halide.
The above mentioned polyalkylene oxide compounds may also be added to light-insensitive hydrophilic colloid layers, such as intermediate layers, protective layers and filter layers, for example, rather than being added to the emulsion.
Gelatin is useful as a binding agent or protective colloid for the photographic emulsion, but other hydrophilic colloids can also be used for this purpose. For example, use can be made of proteins such as gelatin derivatives, graft polymers of gelatin and other macromolecules, albumin and casein, sugar derivatives such as cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfate esters, sodium alginate and starch derivatives, and various synthetic hydrophilic macromolecular materials including homopolymers such as poly(vinyl alcohol), partially acetalated poly(vinyl alcohol), poly(N-vinylpyrrolidone), poly(acrylic acid), poly(methacrylic acid), polyacrylamlde, polyvinylimidazole and polyvinylpyrazole, and copolymers of these materials.
Acid-processed gelatins as well as lime-processed gelatins can be used as the gelatin. Gelatin hydrolyzates and enzyme degradation products of gelatin can also be used. Use can be made of the gelatin derivatives obtained by reacting gelatin with various compounds, such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkanesultones, vinylsulfonamides, maleimide compounds, polyalkylene oxides and epoxy compounds for example. Actual examples have been disclosed, for example, in U.S. Patents 2,614,928, 3,132,945, 3,186,846 and 3,312,553, British Patents 861,414, 1,033,189 and 1,005,784, and JP-B-42-26845.
Graft polymers obtained by grafting homopolymers or copolymers of vinyl based monomers, such as acrylic acid, methacrylic acid, the ester and amide derivatives of these acids, acrylonitrile and styrene, for example, onto gelatin can be used as the aforementioned gelatin graft polymers. In such a case, the use of graft polymers with polymers such as acrylic acid, methacrylic acid, acrylamide, methacrylamide and hydroxyalkyl methacrylates, for example, which have a certain compatibility with gelatin is preferred. Examples of these have been disclosed, for example, in U.S. Patents 2,763,625, 2,831,767 and 2,956,884. Typical synthetic hydrophilic macromolecular materials have been disclosed, for example, in West German Patent Application (OLS) 2,312,708, U.S. Patents 3,620,751 and 3,879,205, and JP-B-43-7561.
Dispersions of water insoluble or sparingly soluble synthetic polymers can be included in the photographic emulsion of the present invention to improve dimensional stability. For example, use can be made of polymers derived from alkyl (meth)acrylates, alkoxyacryl (meth)acrylates, glycidyl (meth)acrylates, (meth)acrylamides, vinyl esters (for example, vinyl acetate), acrylonitrile, olefins, styrene or combinations of these materials, or polymers in which these are combined with monomer components such as acrylic acid, methacrylic acid, α,β-unsaturated dicarboxylic acids, hydroxyalkyl (meth)acrylates, sulfoalkyl (meth)acrylates or styrenesulfonic acid for example. For example, the materials disclosed in U.S. Patents 2,376,005, 2,739,137, 2,853,457, 3,062,674, 3,411,911, 3,488,708, 3,525,620, 3,607,290, 3,635,715 and 3,645,740, and British Patents 1,186,699 and 1,307,373 can be used.
Any method of photographic development may be applied to the light-sensitive materials of the present invention. Dihydroxybenzene based developing agents, 1-phenyl-3-pyrazolidone based developing agents and p-aminophenol based developing agents, for example, can be used as developing agents in the developer, and these developing agents may be used individually, or combinations of these developing agents (for example, 1-phenyl-3-pyrazolidones and dihydroxybenzenes or p-aminophenols and dihydroxybenzenes) can be used. Furthermore, the light-sensitive materials of the present invention may be processed in an infectious developer in which a sulfite ion buffer such as a carbonyl bisulfite and hydroquinone are used.
In the above description, the dihydroxybenzene based developing agents include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone and 2,5-dimethylhydroquinone, for example; the 1-phenyl-3-pyrazolidone based developing agents include 1-phenyl-3-pyrazolidone, 4,4-dimethyl-1-phenyl-3-pyrazolidone, 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone and 4,4-dihydroxymethyl-1-phenyl-3-pyrazolidone, for example; and the p-aminophenol based developing agents include p-aminophenol and N-methyl-p-aminophenol, for example.
Compounds which provide free sulfite ions, such as sodium sulfite, potassium sulfite, potassium metabisulfite, and sodium bisulfite, for example, can be added to the developer as a preservative. Formaldehyde sodium bisulfite which provides hardly any free sulfite ion in a developer may be used with an infectious developer.
Potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, sodium acetate, potassium triphosphate, diethanolamine and triethanolamine, for example, can be used as the alkali agent for the developer used in the present invention. The pH of the developer is generally set to at least 9, and preferably to at least 9.7.
Known organic compounds may be included in the developer as anti-foggants or development inhibitors. Examples of such compounds include azoles (for example, benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles and mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole)), mercaptopyrimidines, mercaptotriazines, thioketo compounds such as oxazolinethione, azaindenes (for example, triazaindene, tetraazaindene (especially 4-hydroxy substituted (1,3,3a,7)tetraazaindenes) and pentaazaindenes), benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonamido and sodium 2-mercaptobenzimidazole-5-sulfonate.
The same polyalkylene oxides as described earlier may be included as development inhibitors in the developers which can be used in the present invention. For example, polyethylene oxide of molecular weight from 1000 to 10000 can be included at concentrations within the range from 0.1 to 10 grams per liter.
Nitrilotriacetic acid, ethylenediaminetetraacetic acid, triethylenetetraminehexaacetic acid and diethylenetetramine pentaacetic acid, for example, are preferably added as hard water softening agents to the developers which can be used in the present invention.
Any generally used fixer composition can be employed in the present invention.
Organic sulfur compounds which are known to be effective as fixing agents can be used as well as thiosulfate, and thiocyanate for the fixing agent.
Water soluble aluminum compounds can also be included in the fixer as hardening agents.
A complex of ethylenediamine tetraacetic acid and trivalent iron ion can also be included in the fixer as an oxidizing agent.
The processing time and the processing temperature are established according to the intended application, but in general, a processing temperature of from 18°C to 50°C is suitable, and a rapid processing time of from 15 to 120 seconds is preferably carried out using an automatic processor.
The present invention will now be illustrated in greater detail by way of the following Examples, but it should be understood that the present invention is not deemed to be limited thereto.

EXAMPLE 1

Silver halide grains were precipitated using the double jet method and physically ripened and desalted, after which the grains were chemically ripened and cubic silver chlorobromide grains of average grain size 0.28 µm which contained 70 mol% silver chloride were obtained (variation coefficient 10%). One kilogram of this emulsion contained 0.60 mol of silver halide.

Preparation of Coated Samples

The infrared sensitizing dye represented by formula I-6 (30 mg), 70 ml of a 0.5% methanolic solution of Compound (III-3) and 90 ml of a 0.5% methanolic solution of Compound (IV-6) were added to 1 Kg of the emulsion described above.
Moreover, 100 mg/m² of hydroquinone, poly(ethyl acrylate) latex in an amount of 25% with respect to the gelatin binder as a plasticizer and 86.2 mg/m² of 2-bis(vinylsulfonylacetamido)ethane as a hardening agent were added and the mixture was coated onto a polyester support in such a way as to provide a coated silver weight of 3.7 g/m². The coated weight of gelatin was 2.5 g/m².
A protective layer to which 0.6 g/m² of gelatin, 60 mg/m² of poly(methyl methacrylate) of particle size 3 to 4 µm and 70 mg/m² of colloidal silica of particle size 10 to 20 mµ as matting agents, and 100 mg/m² of silicone oil had been added and to which sodium dodecylbenzenesulfonate and the fluorine based surfactant of structural formula (1) indicated below had been added, and a lower protective layer to which 0.7 g/m² of gelatin, 225 mg/m² of poly(ethyl acrylate) latex, 20 mg/m² of the comparative dye of structural formula (2) indicated below, 10 mg/m² of the dye (F-I-11) of the present invention, and sodium dodecylbenzenesulfonate as coating aid had been added were coated simultaneously over the top to provide Sample 1.
Moreover, the support used for this example had a backing layer and a backing protective layer of which the compositions are indicated below. (The swelling factor of the backing layer was 110%.)
Sample 2 was obtained by replacing dye (2) in Sample 1 with dye (3) indicated below disclosed in JP-A-2-1837.
Furthermore, Samples 3 to 8 were prepared by replacing dyes (2) and (F-I-11) in Sample 1 with the various dyes indicated in Table 1 below.
Furthermore, Sample 9 was prepared by omitting the dyes (2) and F-I-11 from Sample 1.

Evaluation of Photographic Performance

The samples obtained were exposed using a xenon flash light with a flash duration of 10⁻⁶ second through an interference filter which had a peak at 780 nm and a continuous wedge, developed at 38°C for 20 seconds using developer having a formulation described below, fixed using fixer having a formulation described below, washed and dried in an FG-360F automatic processor manufactured by Fuji Photo Film Co., Ltd. (washing tank capacity 6 liters) and then subjected to sensitometry.
Sensitivity was taken as the reciprocal of the exposure amount required to provide a density of 3.0 and the relative sensitivities on taking the sensitivity of Sample 9 to be 100 are shown in Table 1.
Fogging after safelight illumination is the fogging observed on development processing after illumination for 20 minutes at a distance of 2 meters using a 10W tungsten lamp with a paraffin paper over a safelight filter No. 4 LD manufactured by Fuji Photo Film Co., Ltd., and the results obtained are shown in Table 1.
Moreover, dye F-II-25 was added as a solid, finely divided particle dispersion (average particle size 0.45 µm) in Sample 6.
It is clear from Table 1 that in Samples 3 to 8 in which dyes of the present invention had been used, not only was the fogging after safelight illumination greatly suppressed when compared with Sample 9 in which no dye had been used, but there was also less fogging than observed in Samples 1 and 2 in which known combinations of dyes had been used.
Furthermore, Samples 3 to 8 of this present invention, like comparative Samples 1 and 2, had excellent sharpness and they were also excellent in terms of residual coloration after processing.

EXAMPLE 2

(1) Preparation of Silver Halide Emulsion

After adding an appropriate amount of ammonia to a vessel containing gelatin, sodium chloride and water which had been heated to 55°C, an aqueous solution of silver nitrate and a mixed aqueous solution of potassium bromide and sodium chloride were added using the double jet method while maintaining a pAg value in the reaction vessel at 7.00 and a monodisperse silver chlorobromide emulsion of average grain size 0.55 µm (silver chloride content 60 mol%) was obtained. This emulsion was such that 98% of all the grains were of a size within the average grain size ±40%. The emulsion was then desalted, after which it was gold-sulfur sensitized using sodium thiosulfate and chloroauric acid after adjustment to pH 6.2, pAg 7.30, and the prescribed photographic emulsion was obtained.
The (100) plane/(111) plane ratio of this emulsion measured using the Kubelka-Munk method was 98/2. This was called Emulsion A.

(2) Preparation of the Emulsion Coating Liquid

One kilogram of Emulsion A was weighed out and heated to 40°C and dissolved, after which 70 ml of a methanolic solution of a near infrared region sensitizing dye (structural formula I-12) described earlier (9 x 10⁻⁴ M/1), an aqueous solution of 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene, an aqueous solution of dodecylbenzenesulfonate as a coating aid, and an aqueous solution of a poly(potassium p-vinylbenzenesulfonate) compound as a thickening agent were added and an emulsion coating liquid was obtained.

(3) Preparation of a Surface Protective Layer Coating Liquid for the Light-sensitive Layer

An aqueous solution of poly(sodium ethylenesulfonate) as a thickening agent, fine poly(methyl methacrylate) particles (average particle size 3.0 µm) as a matting agent, N,N'-ethylenebis(vinylsulfonylacetamide) as a hardening agent, an aqueous solution of sodium t-octylphenoxyethoxyethanesulfonate as a coating aid, an aqueous solution of polyethylene based surfactant as an anti-static agent and an aqueous solution of the fluorine based compounds of which the structural formulae (c) and (d) are shown below were added to a 10 wt% aqueous gelatin solution which had been heated to 40°C and a coating liquid was obtained.

(c) C₈F₁₇SO₂N(C₃H₇)CH₂COOK

4. Preparation of Back Coating Liquid 1

An aqueous solution of poly(sodium ethylenesulfonate) as a thickening agent, the dye (F-I-32) of the present invention, an aqueous solution of N,N'-ethylenebis(vinylsulfonylacetamide) as a hardening agent and an aqueous solution of sodium tert-octylphenoxyethoxyethanesulfonate as a coating aid were added to 1 kg of a 10 wt% aqueous gelatin solution which had been heated to 40°C to thereby obtain Back Coating Liquid 1.

(5) Preparation of a Surface Protective Layer Coating Liquid for the Backing Layer

An aqueous solution of poly(sodium ethylenesulfonate) as a thickening agent, fine particles of poly(methyl methacrylate) (average particle size 3.0 µm) as a matting agent, an aqueous solution of sodium tert-octylphenoxyethoxyethanesulfonate as a coating aid, an aqueous solution of a polyethylene based surfactant as an anti-static agent and an aqueous solution containing the fluorine based compounds (c) and (d) described in section (3) above were added to a 10 wt% aqueous gelatin solution which had been heated to 40°C and a coating liquid was obtained.

(6) Preparation of Coated Samples

The above mentioned Back Coating Liquid 1 was coated along with the surface protective layer coating liquid for the backing layer onto one side of a poly(ethylene terephthalate) support in such a way that the coated weight of gelatin was 4 g/m². Furthermore, the dye (F-I-32) of the present invention was coated at a rate of 0.01 g/m². Next, the emulsion coating liquid with Emulsion A into which the near infrared sensitizing dye had been incorporated and the surface protective layer coating liquid for the light-sensitive emulsion layer were coated onto the opposite side of the support in such a way as to provide a coated weight of gelatin of 2.8 g/m², and Sample 201 was thus obtained.
Sample 202 was obtained by adding the dye (F-II-8) of the present invention as a dye for improving the safelight fogging properties in such a way as to provide a coated weight of 0.005 g/m² to the surface protective layer coating liquid for the light-sensitive emulsion layer used in Sample 201.
Furthermore, Samples 203 to 206 were prepared by changing the combination of F-I-32 and F-II-8 in Sample 202 in the ways indicated in Table 2 below.
Furthermore, Sample 207 was prepared in the same way as Sample 201, except that the dye F-I-32 in Sample 201 was omitted.
Samples 201 to 207 were exposed in the way indicated below, developed, fixed, washed and dried using an imagewise exposure and automatic developing apparatus.
The exposure made was a 10⁻⁷ second scanning exposure using a semiconductor laser of wavelength 830 nm.
The post exposure developing and fixing were carried out using the developer and fixer described below. The standard development temperature was 35°C and processing, including fixing, washing and drying, was completed in 70 seconds.
The relative sensitivity and the fogging after safelight illumination shown in Table 2 were obtained in the same way as in Example 1.
It is clear from Table 2 that Samples 202 to 206 in which dyes of the present invention had been used exhibited less fogging after safelight illumination than comparative Samples 201 and 207, and they were excellent light-sensitive materials.
Furthermore, Samples 202 to 206 had excellent sharpness and no residual coloration after processing.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

Claims

A silver halide photographic light-sensitive material having a silver halide emulsion layer comprised of silver halide grains which contain at least silver chloride and which have been spectrally sensitized to infrared using at least one tricarbocyanine dye and/or dicarbocyanine dye which contains a 4-quinoline nucleus, wherein there is at least one hydrophilic colloid layer which contains at least one dye which is represented by general formula (F-I) indicated below and at least one hydrophilic colloid layer which contains at least one dye which is represented by general formula (F-II) indicated below,
wherein R¹, R², R³, R⁴, R⁵ and R⁶ may be the same or different, each being a substituted or unsubstituted alkyl group; Z¹ and Z² each represents a group of non-metal atoms which is required to form a substituted or unsubstituted benzo-condensed ring, naphtho-condensed ring or five or six membered heterocyclic condensed ring; provided that R¹, R², R³, R⁴, R⁵, R⁶, Z¹ and Z² are groups such that the dye molecule has at least three acid groups; L¹, L² and L³ represent substituted or unsubstituted methine groups; X represents an anion; and n is 1 or 2, and n is 1 when the dye forms an intramolecular salt,
wherein R₂₁ and R₂₄ each represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group; R₂₂ and R₂₅ each represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, COR₂₉ or SO₂R₂₉; R₂₃ and R₂₆ each represents a hydrogen atom, a cyano group, an alkyl group, an aryl group, -COOR₂₇, -OR₂₇, -NR₂₇R₂₈, -N(R₂₈)COR₂₉, -N(R₂₈)SO₂R₂₉, -CONR₂₇R₂₈ or -N(R₂₇)CONR₂₇R₂₈ (where R₂₉ represents an aliphatic group or an aromatic group and R₂₇ and R₂₈ each represents a hydrogen atom, an aliphatic group or an aromatic group); L₄, L₅, L₆, L₇ and L₈ represent methine groups; n₁ and n₂ each represents 0 or 1; and M^⊕ represents hydrogen or some other univalent cation; provided that at least one of R₂₁, R₂₂, R₂₃, R₂₄, R₂₅, R₂₆, L₄, L₅, L₆, L₇ or L₈ represents a group which has at least one carboxylic acid group or sulfonic acid group.
The silver halide photographic light-sensitive material as in claim 1, wherein the tricarbocyanine dye is represented by the following general formula (Ia) or (Ib):
wherein R₁ and R₂ which may be the same or different, each represents an alkyl group or a substituted alkyl group; R represents a hydrogen atom, a methyl group, a methoxy group or an ethoxy group; R₃ and R₄ each represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group or a benzyl group; R₅ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group, a benzyl group or
in which W₁ and W₂ each represents a substituted or unsubstituted alkyl group, or an aryl group and W₁ and W₂ may be joined together to form a five or six membered nitrogen containing heterocyclic ring; D represents a group of atoms which is required to complete a divalent ethylene bond; D₁ and D₂ each represents a hydrogen atom or D₁ and D₂ together may form a divalent ethylene bond; Z and Z₁ each represents a group of non-metal atoms which is required to complete a five or six membered nitrogen containing heterocyclic group; X represents an acid anion; and n represents 1 or 2.
The silver halide photographic light-sensitive material as in claim 1, wherein the dicarbocyanine dye which contains a 4-quinoline nucleus is represented by General Formula (II):
wherein R₆ and R₇ may be the same or different, each represents an alkyl group or a substituted alkyl group; R₈ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group or a benzyl group; V represents a hydrogen atom, a lower alkyl group, an alkoxy group, a halogen atom or a substituted alkyl group; Z₂ represents a group of non-metal atoms which is required to complete a five or six membered nitrogen containing heterocyclic group; X₁ represents an acid anion; and m, n₁ and p each represents 1 or 2.
The silver halide photographic light-sensitive material as in claim 1, wherein the dye of general formula (F-I) and the dye of general formula (F-II) each is present in an amount of from 10⁻⁵ g/m² to 1 g/m².
The silver halide photographic light-sensitive material as in claim 4, wherein the dye of general formula (F-I) and the dye of general formula (F-II) each is present in an amount of from 10⁻³ g/m² to 0.5 g/m².
The silver halide photographic light-sensitive material as in claim 1, wherein the infrared sensitizing dyes are present in the silver halide photographic emulsion in an amount of from 5 X 10⁻⁷ to 5 x 10⁻³ mol, per mol of silver halide.
The silver halide photographic light-sensitive material as in claim 6, wherein the infrared sensitizing dyes are present in the silver halide photographic emulsion in an amount of from 1 x 10⁻⁶ to 1 x 10⁻³ mol, per mol of silver halide.
The silver halide photographic light-sensitive material as in claim 7, wherein the infrared sensitizing dyes are present in the silver halide photographic emulsion in an amount of from 2 x 10⁻⁶ to 5 x 10⁻⁴ mol, per mol of silver halide.
The silver halide photographic light-sensitive material as in claim 1, wherein a compound represented by General Formula (III) is included in the emulsion:
wherein A represents a divalent aromatic residual group; R₉, R₁₀, R₁₁ and R₁₂ each represents a hydrogen atom, a hydroxyl group, a lower alkyl group, an alkoxy group, an aryloxy group, a halogen atom, a heterocyclic nucleus, an alkylthio group, a heterocyclylthio group, an arylthio group, an amino group, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted arylamino group, a heterocyclylamino group, a substituted or unsubstituted aralkylamino group, an aryl group or a mercapto group; and W represents -CH= or -N=.
The silver halide photographic light-sensitive material as in claim 9, wherein the compound of General Formula (III) is present in an amount of from 0.01 g to 5 g per mol of silver halide emulsion.
The silver halide photographic light-sensitive material as in claim 1, wherein a compound represented by General Formula (IV) is present in the emulsion:
wherein Z₃ represents a group of non-metal atoms which is required to complete a five or six membered nitrogen containing heterocyclic ring; R₁₃ represents a hydrogen atom, an alkyl group or an alkenyl group; R₁₄ represents a hydrogen atom or a lower alkyl group; X₂ represents an acid anion.
The silver halide photographic light-sensitive material as in claim 11, wherein the compound represented by General Formula (IV) is present in an amount of from 0.01 g to 5 g per mol of silver halide in the emulsion.
The silver halide photographic light-sensitive material as in claim 1, wherein the silver chloride content of the emulsion is from 25 to 100 mol%.
The silver halide photographic light-sensitive material as in claim 1, wherein the silver halide emulsion is a monodisperse silver halide emulsion having an average grain size of from 0.04 µm to 0.7 µm.