DE69121941T2 - Silver halide photographic light-sensitive materials - Google Patents

Description

The present invention relates to a silver halide photographic light-sensitive material which is spectrally sensitized to the infrared region and, in particular, to a silver halide photographic light-sensitive material with improved sensitivity in the infrared region and with improved protection under darkroom illumination.

Photographic emulsion layers and other layers in silver halide photographic light-sensitive materials are sometimes colored to absorb light of a specific wavelength band.

The colored layer is provided on the side farther 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 incident on the photographic emulsion layer. A layer colored in this way is called a filter layer. When there are a plurality of photographic emulsion layers, as in multilayer color light-sensitive materials, layers can also be provided between these layers.

Colored layers have been formed between the photographic emulsion layer and the support or on the side of the support opposite to that on which the photographic emulsion layer is arranged in order to prevent image blurring (halation) caused by stray light which is generated during the passage through the photographic emulsion layer or after the passage at the interface between the emulsion layer and the support or which is reflected at the surface of the photosensitive material on the opposite side of the emulsion layer and is redirected into the photographic emulsion layer. Colored layers of this type are called antihalation layers. In the case of multilayer color photosensitive materials, a Antihalation layer can also be arranged between the different layers.

The photographic emulsion layers may also be colored to prevent the loss of image sharpness caused by stray light within the photographic emulsion layer. This phenomenon is generally referred to as irradiation.

In many cases, the layer to be colored is composed of hydrophilic colloid and therefore water-soluble dyes are generally used in these layers. These dyes must meet three requirements listed below:

(1) They must have a suitable spectral absorptivity for the intended application.

(2) They must be photochemically inert. Thus, they must not have any adverse effect in the chemical sense on the performance of the photographic silver halide emulsion layer. Such adverse effects include, for example, a reduction in sensitivity leading to the absence of the latent image or the formation of fog.

(3) They must be decoloured or removed by dissolution during the photographic processing and no unwanted colouring must remain after processing of the photographic light-sensitive material.

Many dyes that absorb in the visible and ultraviolet regions and that satisfy these requirements are known. However, there are currently some dyes that have an absorbance in the infrared region of the spectrum that satisfy the three requirements mentioned above.

For example, cyanine dyes having various heterocyclic rings have been disclosed in US-A-2 895 955 and 4 263 397, JP-A-58-179266, JP-A-59-191032 and JP-A-59-192242; however, when these dyes are used for anti-irradiation purposes in the emulsion layers of the silver halide light-sensitive materials which have been spectrally sensitized to the infrared region, problems arise in that they sometimes cause spectral sensitization in areas where it is not required or they may cause desorption of the sensitizing dyes, resulting in loss of sensitivity. (The term "JP-A" used herein means "unexamined published Japanese patent application.") In addition, there are problems with residual coloration after processing, although favorable results are obtained when these dyes are used in antihalation layers and filter layers.

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 of preventing halo and irradiation when added to a silver halide photographic light-sensitive material which has been spectrally sensitized to the infrared region. However, since the absorption waveform is sharp, fogging occurs when the materials are handled under bright saferoom lighting, known as daylight illumination. It is therefore necessary to use dyes that have a shorter wavelength than these dyes combined.

A dye having an absorbency in the safelight wavelength range may be added to the photosensitive material to reduce the degree of fogging due to the safelight. The dyes known to date, for example oxonol dyes, which have a pyrazolone nucleus or a barbituric acid nucleus, for example disclosed in GB-A-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-48-8513C, 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 US-A-3 247 127, 3 469 985 and 4 078 933 and other oxonol dyes, for example disclosed in US-A-2 533 472 and 3 379 533 and GB-A-1 278 621, the azo dyes, for example disclosed in GB-A-575 691, 680 631, 599 623, 786 907, 907 125 and 1 045 609, US-A- 4 255 326 and JP-A-59-211043, the azomethine dyes, for example disclosed in JP-A-50-100116, JP-A-54-118247 and GB-A-2 014 598 and 750 031, the anthraquinone dyes disclosed in GB-A-2 865 752, the arylidene dyes disclosed for example in US-A-2 538 009, 2 688 541 and 2 538 008, GB-A-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 GB-A-446 583 and 1 335 422 and JP-A-59-228250, the merocyanine dyes disclosed, for example, in GB-A-1 075 653, 1 153 341, 1 284 730, 1 475 228 and 1 542 807 and the cyanine dyes disclosed, for example, in US-A-2 843 486 and 3 294 539, actually had no effect in reducing the degree of fogging due to safelight when applied to silver halide photographic light-sensitive materials spectrally sensitized to the infrared region, and even if they did not show such an effect, they are added in large amounts to achieve this effect. (The term "JP-B" used here means "Examined Japanese Patent Publication.") In general, if dye is added to the light-sensitive material in large amounts, some dye inevitably remains in the light-sensitive material after photographic processing and discoloration occurs, which reduces the commercial value of the light-sensitive material. Proposals addressing these problems have been made in JP-A-61-174540 and JP-A-2-1837, but satisfactory results have not yet been achieved.

A first object of the present invention is to provide a silver halide photographic light-sensitive material having a hydrophilic colloidal layer colored with a water-soluble dye which has no adverse effect on the photographic properties of the photographic emulsion and which can be easily decolored by photographic processing.

A second object of the present invention is to provide a silver halide photographic light-sensitive material which provides good images and which has sufficiently low sensitivity to visible light and high sensitivity to infrared light.

The above and other objects of the present invention have been achieved by providing a silver halide photographic light-sensitive material having a silver halide emulsion layer comprising silver halide grains containing at least silver chloride and which have been spectrally sensitized in the infrared region using at least one tricarbocyanine dye and/or dicarbocyanine dye containing a 4-quinoline nucleus, characterized in that the material comprises at least one hydrophilic colloid layer containing at least one dye represented by the general formula (FI) given below and at least one hydrophilic colloid layer containing at least one dye represented by the general formula (F-II) given below.

wherein R¹, R², R³, R⁴, R⁵ and R⁶ may be the same or different and each represents a substituted or unsubstituted alkyl group; Z¹ and Z² each represents a group of non-metal atoms required to form a substituted or unsubstituted benzo-fused ring, naphtho-fused ring or five- or six-membered heterocyclic fused ring; with the proviso that R¹, R², R³, R⁴, R⁵, R⁵, Z¹ and Z² are selected 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 if the dye forms an intramolecular salt,

wherein R₂₁ and R₂₄ each represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group; R₂₂ and R₂₅ each represent a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, COR₂₠ or SO₂R₂₠; R₂₃ and R₂₆ each represent a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, COR₂₠ or SO₂R₂₠; each represents a hydrogen atom, a cyano group, an alkyl group, an aryl group, -COOR₂₇, -OR₂₇, -NR₂₇₇R₂₈, -N(R₂₈)COR₂₠, -N(R₂₈)SO₂R₂₇, -CONR₂₇R₂₈, or -N(R₂₇)CONR₂₇R₂₈ (wherein R₂₇ represents an aliphatic group or an aromatic group, and R₂₇ and R₂₈ each represent a hydrogen atom, an aliphatic group or an aromatic group); L₄, L₅, L₆, L₇ and L₈ represent methine groups; n₁ and n₂ each represent 0 or 1; and M⁺ represents hydrogen or another monovalent cation; with the proviso that at least one of R₂₁, R₂₂, R₂₃, R₂₄, R₂₅, R₂₆, L₄, L₅, L₆, L₇ or L₈ represents a group having at least one carboxylic acid group or one sulfonic acid group.

Silver halide containing silver chloride such as silver chloride, silver chlorobromide, silver chloroiodide or silver chloroiodobromide can be used as the silver halide in the present invention, for example. The silver iodide content of the silver halide should preferably be 0 to 2 mol%, most preferably 0 to 1 mol%. The silver chloride content of the silver halide is preferably at least 1 mol%, more preferably at least 10 mol%, most preferably 25 to 100 mol%.

These emulsions 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 0.04 µm to 4 µm and in particular not more than 0.7 µm are preferred.

The crystal structure of the silver halide grains may also be uniform in 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 GB-A-635 841 and US-A-3 622 318. The grains may also be of the type in which the latent image is mainly formed on the grain surface or of the internal latent image type in which the latent image is mainly formed inside the grains.

Ammonia, potassium thiocyanate, ammonium thiocyanate, thioether compounds (such as disclosed in US-A-3,271,157, 3,574,628, 3,704,130, 4,297,439, 4,276,374), thione compounds (such as disclosed in JP-A-53-144319, JP-A-53-82408 and JP-A-55-77737) and amine compounds (such as disclosed in JP-A-54-100717) can be used as silver halide solvents for controlling grain growth during the formation of these silver halide grains.

Water-soluble rhodium and/or water-soluble indium may also 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 chemical sensitization processes known in the art. For example, gold sensitization (for example disclosed in US-A- 2 540 085, 2 597 876, 2 597 915 and 2 399 083), sensitization with Group VIII metal ions (for example disclosed in US-A- 2 448 060, 2 540 086, 2 566 245, 2 566 263 and 2 598 079), sulfur sensitization (for example disclosed in US-A- 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 disclosed in US-A-2,518,698, 2,419,974, 2,983,610, Research Disclosure, Volume 176 (December 1978) RD-17643, Section III), Sensitization with thioether compounds (for example disclosed in US-A-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 sensitization methods may be used.

Other examples of specific chemical sensitizers used include sulfur sensitizers such as allylthiocarbamide, thiourea, thiosulfate, thioether and cysteine; noble metal sensitizers such as potassium chloroaurate, gold(I) thiosulfate and potassium chloropalladate and reduction sensitizers such as stannous chloride, phenylhydrazine and reductone.

The tricarbocyanine dyes and the dicarbocyanine dyes containing a 4-quinoline nucleus are hereinafter referred to as infrared sensitizing dyes used in the present invention.

Among the tricarbocyanines which can be used in the present invention, those of the general formula (Ia) and (Ib) shown below are particularly preferred.

In formulas (Ia) and (Ib), R₁ and R₂, identical or different, may each represent an alkyl group, preferably having 1 to 8 carbon atoms (for example methyl, ethyl, propyl, butyl, pentyl, heptyl) or a substituted alkyl group whose alkyl radical does not represent 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 (e.g., fluorine, chlorine, bromine), a hydroxyl group, an alkoxycarbonyl group (having not more than 8 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl), an alkoxy group (having not more than 7 carbon atoms, for example, methoxy, ethoxy, propoxy, butoxy, benzyloxy), an aryloxy group (e.g., phenoxy, p-tolyloxy), an acyloxy group (having not more than 3 carbon atoms, for example, acetyloxy, propionyloxy), an acyl group (having not more than 8 carbon atoms, for example, acetyl, propionyl, benzoyl, mesyl), a carbamoyl group (e.g., carbamoyl, N,N-dimethylcarbamoyl, morpholinocarbamoyl, piperidinocarbamoyl), a sulfamoyl group (e.g. sulfamoyl, N,N-dimethylsulfamoyl, morpholinosulfonyl) or an aryl group (e.g. phenyl, p-hydroxyphenyl, p-carboxyphenyl, p-sulfophenyl, α-naphthyl) one and two or more of these substituent groups can be combined and substituted on the alkyl group.

R represents a hydrogen atom, a methyl group, a methoxy group or an ethoxy group.

R₃ and R₄ each represent a hydrogen atom, a lower alkyl group (e.g. methyl, ethyl, propyl), a lower alkoxy group (e.g. methoxy, ethoxy, propoxy, butoxy), a phenyl group or a benzyl group.

R₅ represents a hydrogen atom, a lower alkyl group (e.g. methyl, ethyl, propyl), a lower alkoxy group (e.g. methoxy, ethoxy, propoxy, butoxy), a phenyl group, a benzyl group or

W₁ and W₂ each represent a substituted or unsubstituted alkyl group (the alkyl group having 1 to 18 carbon atoms and preferably 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 taken together to form a five- or six-membered nitrogen-containing heterocyclic ring.

D represents a group of atoms 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 suitable groups, for example alkyl groups having 1 to 4 carbon atoms (for example methyl, ethyl, propyl, isopropyl, butyl), halogen atoms (for example chlorine, bromine) or alkoxy groups (having 1 to 4 carbon atoms, for example methoxy, ethoxy, propoxy, isopropoxy, butoxy).

D₁ and D₂ each represent a hydrogen atom. However, D₁ and D₂ may form a divalent ethylene bond as defined for D above.

Z and Z1; each represent a group of non-metal atoms required to complete a five- or six-membered, nitrogen-containing heterocyclic residue, for example a thiazole nucleus (such as 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 (e.g. benzoselenazole, 5-chlorobenzoselenazole, 5-methoxybenzoselenazole, 5-methylbenzoselenazole, 5-hydroxybenzoselenazole, naphtho[2,1-d]selenazole, naphtho[1,2-d]selenazole), an oxazole nucleus (e.g. 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 (e.g. 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 (e.g. 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 (e.g., pyridine, 5-methyl-2-pyridine, 3-methyl-4-pyridine). Of these, thiazole and oxazole nuclei are preferred. The use of a benzothiazole nucleus, a naphthothiazole nucleus, a naphthoxazole nucleus or a benzoxazole nucleus is most preferred.

X represents an acid anion.

Furthermore, n represents 1 or 2.

Particularly useful in the present invention are 4-quinoline nuclei-containing dicarbocyanine dyes having the general formula below.

In formula (II), R₆ and R₇ have the same meaning as R₁ and R₂, respectively, in the above general formulas (Ia) and (Ib).

R₈ in formula (II) has the same meaning as R₃ and R₄ in the above-mentioned general formulas (Ia) and (Ib). However, R₈ preferably has a lower alkyl group or a benzyl group.

V in formula (II) represents a hydrogen atom, a lower alkyl group (e.g. methyl, ethyl, propyl), an alkoxy group (e.g. methoxy, ethoxy, butoxy), a halogen atom (e.g. fluorine, chlorine) or a substituted alkyl group (e.g. trifluoromethyl, carboxymethyl).

Z₂ in formula (II) has the same meaning as Z and Z₁ in the above general formulas (Ia) and (Ib).

X₁ in formula (II) has the same meaning as X in the above general formulas (Ia) and (Ib).

m, n₁ and p also represent 1 or 2, respectively.

Concrete examples of sensitizing dyes that can be used in the present invention are shown below.

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 moles, preferably from 1 x 10⁻⁷ to 1 x 10⁻³ moles, most preferably from 2 x 10⁻⁷ to 5 x 10⁻⁴ moles per mole of silver halide.

The above-mentioned infrared sensitizing dyes which can be used in the present invention can be directly dispersed in the emulsion. In addition, they can be dissolved in an appropriate solvent (for example, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine or a mixture of these solvents) and added to the emulsion in the form of a solution. In addition, ultrasound can be used to achieve dissolution.

Other methods that can be used for adding the above-mentioned infrared sensitized 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 in, for example, US-A-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 in, for example, 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 US-A-3,822,135; the method in which the dissolution is achieved using a red-shifting compound and the solution is added to the emulsion as disclosed in JP-A-51-74624; and the method in which the dye is substantially dissolved in anhydrous acid and the resulting solution is then added to the emulsion as disclosed in JP-A-50-80826. The methods disclosed in, for example, US-A-2,912,343, 3,342,605, 2,996,287 and 3,429,835 can also be used to carry out the addition to the emulsion. The above-mentioned infrared sensitizing dyes of the general formulae (I) and (II) may also be uniformly dispersed in the silver halide emulsion before coating on a suitable support, and they may of course be added at any stage during the preparation of the silver halide emulsion.

Combinations of other sensitizing dyes can also be used with the above-mentioned infrared sensitizing dyes used in accordance with the present invention. For example, use can be made of the sensitizing dyes as disclosed in US-A-3,703,377, 2,688,545, 3,397,060, 3,615,635 and 3,628,964, GB-A-1,242,588 and 1,293,862, JP-B-43-4936, JP-B-44-14030, JP-B-43-10773, US-A-3,416,927, JP-B-43-4930 and US-A-3,615,613, 3,615,632, 3,617,295 and 3,635,721.

Compounds represented by the general formula (III) below can be used in the invention to increase the supersensitizing effect and/or further improve the storage properties.

In formula (III), -A- represents a divalent aromatic group which may contain a group -SO₃M (wherein M represents a hydrogen atom or a cation, e.g. sodium or potassium, which provide water solubility).

-A- can be selected from the groups -A₁- or -A₂- identified below. -A- is selected from the group -A₁- when no group -SO₃M is present in R₉, R₁₀, R₁₁ or R₁₂ of the formula (III).

For example, -A�1;- represents the following groups:

In the above groups -A₁-, M represents a hydrogen atom or a cation which imparts water solubility.

For example, -A2- represents the following groups:

R�9;, R₁₀, R₁₁ and R₁₂ each represent a hydrogen atom, a hydroxyl group, a lower alkyl group (preferably having 1 to 8 carbon atoms, such as methyl, ethyl, n-propyl, n-butyl), an alkoxy group (preferably having 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 (e.g. benzothiazolylthio, benzimidazolylthio, phenyltetrazolylthio), an arylthio group (e.g. phenylthio, tolylthio), an amino group, a substituted or unsubstituted alkylamino group (e.g. methylamino, ethylamino, propylamino, dimethylamino, Diethylamino, dodecylamino, cyclohexylamino, β-hydroxyethylamino, di-(β-hydroxyethyl)amino, β-sulfoethylamino), a substituted or unsubstituted arylamino group (e.g. anilino, o-sulfoanilino, m-sulfoanilino, p- Sulfoanilino, o-Toluidino, m-Toluidino, p-Toluidino, o-Carboxyanilino, m-Carboxyanilino, p-Carboxyanilino, o-Chloranilino, m-Chloranilino, p-Chloranilino, 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 (e.g. phenyl) or a mercapto group. R₉, R₁₀, R₁₁ and R₁₂ may be the same or different. In any case, when -A- is selected from the group -A₂-, at least one R₉, R₁ and R₁₂ must be hydrogen. R 0 , R 11 and R 12 have at least one sulpho group which may be a free sulpho group or in the form of a salt. W represents -CH= or -N= and preferably -CH=.

Concrete examples of the compounds represented by the general formula (III) that can be used in the present invention are shown below.

(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]dibenzyl-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 .

Among these concrete 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 particularly preferred.

The compounds of the general formula (III) can be used in amounts of 0.01 to 5 g per mole of silver halide in the emulsion.

The ratios by weight of the infrared sensitizing dye used in the present invention and described above and the compounds represented by general formula (III) are designed such that the value of the ratio (all infrared sensitizing dyes used in the present invention / compound represented by general formula (III)) is 1/1 to 1/100, and preferably 1/2 to 1/50.

The compounds represented by general formula (III) used in the present invention may be directly dispersed in the emulsion or they may be added to the emulsion after dissolving in a suitable solvent (e.g., methyl alcohol, ethyl alcohol, methyl cellosolve or water) or in a mixture of such solvents. They may also be added to the emulsion as a solution or in the form of a dispersion in a colloid according to the methods for adding other sensitizing dyes. In addition, they may be dispersed and added to the emulsion using the method disclosed in JP-A-50-80119.

Combinations of the infrared sensitizing dyes used in the present invention with compounds represented by the general formula (IV) shown below can be used in the present invention.

In formula (IV), Z&sub3; a group of non-metal atoms required to complete a five- or six-membered nitrogen-containing heterocyclic ring, such as thiazolium (for example thiazolium, 4-methylthiazolium, benzthiazolium, 5-methylbenzthiazolium, 5-chlorobenzthiazolium, 5-methoxybenzthiazolium, 6-methylbenzthiazolium, 6-methoxybenzthiazolium, 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, not more than 8 carbon atoms (e.g. methyl, ethyl, propyl, butyl, pentyl) or represents an alkenyl group (e.g. allyl). R₁₄ represents a hydrogen atom or a lower alkyl group (e.g. methyl, ethyl). X₂ represents an acid anion (e.g. Cl⁻, Br⁻, ClO₄⁻, p-toluenesulfonate). Among the groups represented by Z₃, the use of thiazolium is preferred. The use of a substituted or an unsubstituted benzothiazolium or naphthothiazolium is preferred.

Concrete examples of the compounds represented by the general formula (IV) are shown below.

The compounds represented by the above general formula (IV) can preferably be used in amounts of 0.01 g to 5 g per mole of silver halide in the emulsion.

The weight ratios of the above-mentioned infrared sensitizing dyes used in the present invention and the compounds represented by general formula (IV) (that is, the weight ratio of all the infrared sensitizing dyes used in the present invention/the compound represented by general formula (IV)) are suitably 1/1 to 1/300, and preferably 1/2 to 1/50.

The compounds represented by the general formula (IV) used in the present invention can be directly dispersed in the emulsion, and they can also be dissolved in a suitable 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 according to methods for adding a sensitizing dye as in the methods for adding the infrared sensitizing dye used in the invention.

The compounds represented by the general formula (IV) may be added to the emulsion before or after the addition of the above-described infrared sensitizing dyes used in the present invention. The compounds represented by the general formula (IV) and the infrared sensitizing dyes used in the present invention may be dissolved separately and then added simultaneously to the emulsion separately, or they may be added to the emulsion after mixing.

The dyes represented by the general formula (F-I) are described in more detail below.

The alkyl groups represented by R¹, R², R³, R⁴, R⁵ and R⁶ are preferably lower alkyl groups having 1 to 5 carbon atoms (for example, methyl, ethyl, n-propyl, n-butyl, isopropyl, n-pentyl), and they may have substituent groups such as a sulfonic acid group, a carboxylic acid group, OPO₃M₂ (wherein M is, for example, H, Na, K or Li), a hydrophilic nonionic group (for example, CN, CONH₂, COCH₃, NHCOCH₃, SO₂HN₂), a cyclic imido group (for example,

and a hydroxyl group.

Preferably, R¹ and R⁴ represent lower alkyl groups having 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 (e.g. F, Cl, Br), a cyano group, a substituted amino group (e.g. 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 having 1 to 5 carbon atoms {for example, methyl, ethyl, propyl, butyl (preferably having, 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)} bonded to the ring directly or via a divalent linking group (for example, -O-, -NHCO-, -NHSO₂-, -NHCOO-, -NHCONH-, -COO-, -CO- or -SO₂-) is an example of the substituent group for the benzo-condensed rings and naphtho-condensed rings represented by the groups of the groups represented by Z¹ and Z². Non-metal atoms are formed.

A pyridine ring, a thiophene ring, a furan ring and a pyrrole ring are examples of heterocyclic rings that can be formed by the groups of non-metal atoms represented by Z¹ and Z².

Lower alkyl groups having 1 to 5 carbon atoms (e.g. methyl, ethyl, sulfoethyl, benzyl) and halogen atoms (e.g. F, Cl, Br) are, for example, preferred substituent groups for the methine groups, represented by L¹, L² and L³. In addition, a five-membered ring (e.g., a cyclopentene ring, a 1-chlorocyclopentene ring, a 1-morpholinocyclopentene ring, a 1-(4-ethoxycarbonylpiperazin-1-yl)cyclopentene ring, or a 1,1-dimethylaminocyclopentene ring) or a six-membered ring (e.g., a 4,4-dimethylcyclohexene ring, a cyclohexene ring, or a 1-chlorocyclohexene ring) containing three methine groups can be formed by bonding together with the substituent groups of the methine groups represented by L¹, L², and L³.

At least three acid groups and preferably four to six acid groups, the groups being represented by R¹ to R⁶, Z¹ and Z², preferably have sulfonic acid groups, carboxylic acid groups or the group

where Y represents O-, S- or an amino group, R represents H, an alkyl group (e.g. methyl, ethyl) an alkoxy group (e.g. 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 designed 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, a salt of an alkali metal such as Li, Na, K, an ammonium salt or an organic ammonium salt such as triethylamine salt, tributylamine salt or pyridine salt).

The anion represented by X can be, for example, a halogen ion (Cl, Br), a p-toluenesulfonate ion or an ethyl sulfate ion.

Concrete examples of dye compounds represented by the above general formula (F-I) which can be used in the present invention are shown below.

Dyes represented by the general formula (F-I) can be prepared using methods disclosed in JP-A-62-123454, JP-A-63-55544, JP-A-1-287559, JP-A-1-280750 and JP-A-1-239548, based on the methods disclosed in these specifications.

The general formula (F-II) is described in more detail below.

The aliphatic groups represented by R₂₁, R₂₂, R₂₃, R₂₄, R₂₅, R₂₆, R₂₆, R₂₇, R₂₃, and R₂₇ are preferably linear chain, branched or cyclic alkyl groups having 1 to 8 carbon atoms, aralkyl groups having 6 to 12 carbon atoms or alkenyl groups having 3 to 7 carbon atoms. Specific 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, R₂₆, R₂₇, R₂₃, R₂₆, R₂₇, and R₂₇ are preferably aryl groups having 6 to 10 carbon atoms. Concrete 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-fused rings) and examples include 5-sulfopyridin-2-yl and 5-sulfobenzothiazol-2-yl.

The methine groups represented by L4, L5, L6, L7 and L8 have substituent groups (e.g., methyl, ethyl, phenyl, chloro, sulfoethyl, carboxyethyl, dimethylamino, cyano) and the substituent groups may taken together form a five- or six-membered ring (e.g., 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+.

Concrete examples of dyes represented by the general formula (F-II) which can be used in the present invention are shown below. (Concrete examples of the substituent groups in the general formula (F-II) are shown in the table below.)

The dyes represented by the 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 methods indicated below.

Synthesis example 1 (preparation of F-II-8)

Compound (A) shown below was prepared by reacting 1-(4-sulfophenyl)-3-amino-2-pyrazolin-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. 8 g of compound (A) and 10 ml of 1,1,3,3-tetramethoxypropane were added to a mixed solvent containing 20 ml of pyridine and 10 ml of acetic acid, and the mixture was heated and stirred at a temperature of 95°C to 100°C for 2 hours. The crystals formed were removed by filtration. The black powder thus obtained (3 g) was dissolved in 9 ml of distilled water, and a salt was formed by adding 10 ml of methanolic solution containing 2 g of potassium acetate. The crystals formed were removed by filtration, washed with methanol and dried to obtain 2 g of (F-II-8). Compound (F-II-8) was examined and showed the following properties:

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

Melting point: above 300ºC Connection (A)

Dyes represented by general formulas (F-I) and (F-II) described above can be dissolved in a suitable solvent (for example, water, methanol, ethanol, N,N-dimethylformamide or a mixture of such solvents) and added to the coating liquid to be used for a hydrophilic colloid layer used in the present invention. Furthermore, when the dyes are hardly soluble in water, they can be added as dispersions of solid finely divided particles.

In those cases where the dyes of the general formula (FI) and/or (F-II) are used in the form of a solid, finely divided, particulate dispersion mixture, both dyes of the general formula (FI) and (F-II) can be used as a dispersion of solid, finely divided particles or only one can be used in the form of a Dispersion of solid, finely divided particles.

Fine particulate dispersions of dyes of the general formula (F-I) or (F-II) used in the present invention can be prepared using the method in which the dyes of the formula (F-I) and/or (F-II) used in the present invention are precipitated in the form of a dispersion and/or the method in which the dispersion is formed using known means for pulverizing, for example, ball mill (for example, with a ball mill, vibrating ball mill or a satellite ball mill), sand mill, colloid mill, impact mill or roller mill, in the presence of a dispersant (in the case of a solvent (for example, water or alcohol) may also be present).

Alternatively, a fine crystalline powder may be precipitated by dissolving the dye of formula (F-I) and/or (F-II) used in the present invention in a suitable solvent and then adding a poorer solvent for the dye, and in this case a surfactant may be used for dispersion purposes. Alternatively, the dyes of formula (F-I) and/or (F-II) used in the present invention may be dissolved first by adjusting the pH and then precipitated as fine crystals to change the pH.

The solid, finely divided particles of the dye of formula (F-I) and/or (F-II) used in the present invention in the dispersion are of a particle size of 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 preferred.

The dyes of the general formula (FI) or (F-II) used in the present invention can be used in an emulsion layer or in another hydrophilic colloid layer and the respective Dyes can be used in the same layer and/or in different layers. These dyes can be used in combinations of two or more types.

The amount of the dyes of the general formulas (F-I) and (F-II) used in the present invention can be selected according to the intended purpose. Preferably, the dye of the general formula (F-I) and the dye of the general formula (F-II) are each used in amounts of 10-4 g/m2 to 1 g/m2, and more preferably in amounts within the range of 10-3 g/m2 to 0.5 g/m2.

Various compounds can be added to the photographic emulsion used in the present invention in order to prevent 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, nitrobenzimidazole, ammonium chloroplatinate, 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene and 1-phenyl-5-mercaptotetrazole, have long been known. Examples of such compounds which may be used include those disclosed in the literature on pages 344-349 of K. Mees, The Theory of the Photographic Process (third edition, 1966) and further compounds include, for example, the thiazolium salts disclosed, for example, in US-A-2,131,038 and 2,694,716, the azaindenes disclosed, for example, in US-A-2,886,437 and 2,444,605, the urazoles disclosed, for example, in US-A-3,287,135, the sulfocatechins disclosed, for example, in US-A-3,236,652, the oximes disclosed, for example, in GB-A-623,448, the mercaptotetrazoles, nitrone and nitroindazoles disclosed, for example, in US-A-2,403,927, 3,266,897 and 3,397,987, the polyvalent metal salts disclosed for example in US-A-2,839,405, the thiouronium salts disclosed for example in US-A-3,220,839 and the palladium, platinum and gold salts disclosed for example in US-A-2,566,263 and 2,597,915.

The photographic silver halide emulsions may contain developing agents, for example hydroquinones, Catechins, aminophenols, 3-pyrazolidones, ascorbic acid and derivatives thereof, reductones and phenylenediamines or combinations of developing agents. The developing agents can be incorporated into the silver halide emulsion layer and/or other photographic layers (e.g. protective layers, interlayers, filter layers, antihalation layers and backing layers). The developing agents can be dissolved in a suitable solvent for addition or they can be added in the form of a dispersion as disclosed in US-A-2 592 368 or FR-A-1 505 778.

The development accelerators disclosed, for example, in US-A-3,288,612, 3,333,959, 3,345,175 and 3,708,303, GB-A-1,098,748 and DE-A-1141,531 and 1183,784 can be used in the present invention.

Inorganic or organic hardeners can be used in the photographic emulsions used in the present invention. For example, use can be made of chromium salts (e.g., chrome alum, chromium acetate), aldehydes (e.g., formaldehyde, glyoxal, glutaraldehyde), N-methylol compounds (e.g., dimethylol urea, methyloldimethylhydantoin), dioxane derivatives (e.g., 2,3-dihydroxydioxane), active vinyl compounds (e.g., 1,3,5-triacryloylhexahydro-s-triazine, bis(vinylsulfonyl)methyl ether, N,N'-methylenebis[β-(vinylsulfonyl)propionamide]), active halogen compounds (e.g., 2,4-dichloro-6-hydroxy-s-triazine), mucohalogen compounds (e.g., mucochloric acid, mucophenoxychloric acid), isooxazoles, dialdehyde starch, and 2-chloro-6-hydroxytriazinylated gelatin, used individually or in combination. Examples of hardeners are given in US-A-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 3 543 292, GB-A-676 628, 825 544 and 1 270 578, DE-A-8 72 153 and 10 90 427, JP-B-34- 7133 and JP-B-46-1872 disclosed.

Different surfactants can be incorporated for different purposes into the photographic emulsion layers or other hydrophilic colloid layers of the light-sensitive material of the present invention, for example as casting aids, for antistatic purposes, to improve slip properties, for emulsification and dispersion purposes, to prevent sticking or to improve photographic performance (for example, to accelerate development, increase contrast or for sensitization).

For example, 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 alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol amines or amides and poly(ethylene oxide) adducts of silicones), glycidyl derivatives (for example alkenyl succinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols and alkyl esters of sugars; anionic surfactants such as those containing an acidic group such as a carboxylic acid group, a sulfo group, a phospho group, a sulfate ester group or phosphate ester group, for example alkyl carboxylate, alkyl sulfonate, alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkyl sulfate esters, alkyl phosphate esters, N-acyl-N-alkyltaurines, sulfosuccinate esters, sulfoalkylpolyoxyethylenealkylphenyl ethers and polyoxyethylenealkylphosphate esters; amphoteric surfactants such as amino acids, aminoalkylsulfonic acids, aminoalkyl sulfate 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 containing aliphatic and heterocyclic rings.

In those cases where a mordant is used, simultaneous use of an anionic surfactant and an amphoteric surfactant may be preferred to accelerate casting and improve the mordant properties. These surfactants may be added to a light-insensitive hydrophilic colloid layer casting liquid or to an emulsion layer casting liquid. The amount used and the Ratios of the two types of surfactants are optional and can be easily determined by experiment.

The anionic group of the anionic surfactants that 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 part is, for example, a hydrocarbon residue or a partially or fully fluorinated hydrocarbon residue.

Typical examples of the anionic surfactants which can be preferably used in the present invention are shown below by formulas (A-1) to (A-9).

In formula (A-1), R 60 is a saturated or unsaturated hydrocarbon group or a fluorinated derivative thereof having 3 to 20 carbon atoms, and R 61 is a hydrogen atom, a methyl group, an ethyl group or a propyl group. Furthermore, n 60 is an integer of 1 to 20, preferably 1 to 8. M is a monovalent alkali metal, and preferably Na or K.

In the general formulas (A-2) and (A-3), R₆₀, M and n₆₀ have the same meanings as in the general Formula (A-1) and a represents 0, 1 or 2. In addition, m60 is an integer of 1 to 6, and preferably 2 to 4.

R₆₀ and M in the general formulas (A-4), (A-5) and (A-6) have the same meanings as those in the general formula (A-1).

R₆₁ and M in the general formula (A-7) have the same meaning as in the general formula (A-1), and m₆₀ has the same meaning as in the general formula (A-2).

In the general formulas (A-8) and (A-9), R₆₂ is a saturated or unsaturated hydrocarbon of which the hydrogen portion has been fluorinated and which has 3 to 22 and preferably 7 to 18 carbon atoms. R₆₁ and M have has the same meaning as in the general formula (A-1) and m₆₀ has the same meaning as in the general formula (A-2).

Specific examples of the anionic surfactants that can be preferably used are shown below.

A-1

C₁₁₁H₂₃CONHCH₂SO₃Na

A-2

C₇F₁₅CONH(CH₂)₂SO₃Na

A-10

C₇H₁₅-O-SO₃K

A-11

C₁₂H₂₅O-SO₃Na A-12

A-13

C₈F₁₇-SO₂NH(CH₂)₃COONa

A-14

C₁₇F₃₃SO₂NH(CH₂)₄COONa

A-15

C₁₃F₂₇SO₂NH(CH₂)₃OPO(OH)₂ A-16

The amphoteric surfactants that can be used in the present invention have both an anionic group and a cationic group in a single molecule and are surfactants that form intramolecular salts. These surfactants can be represented by the general formula (B).

(B) A⊃min; - C⊃plus;

In the general formula (B), A is an anionic residue containing an anionic group such as a sulfonic acid group, a carboxylic acid group or a phosphoric acid group, for example, and C+ is an organic cationic residue.

Specific examples of amphoteric surfactants which can be particularly preferably used in the present invention are shown 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-Carboxytridecyl)pyridinium hydroxide

The use of polyalkylene oxide compounds (for example, polyalkylene oxides comprising at least 10 units of an alkylene oxide having 2 to 4 carbon atoms such as ethylene oxide, propylene-1,2-oxide, butylene-1,2-oxide and preferably ethylene oxide, condensates with compounds containing at least one active hydrogen atom such as water, aliphatic alcohols; aromatic alcohols, fatty acids, organic amines and hexitol derivatives or block copolymers of two or more kinds of polyalkylene oxide) is preferred for improving the cut-off at the peak of the characteristic curve to obtain dot-matrix and linework with improved quality. In practice, the following compounds can be used as polyalkylene oxide compounds:

Polyalkylene glycols

Polyalkylene glycol alkyl ether

Polyalkylene glycol aryl ether

Polyalkylene glycol (alkylaryl) ether

Polyalkylene glycol esters

Polyalkylene glycol fatty acid amides

Polyalkylene glycolamines

Polyalkylene glycol block copolymers

Polyalkylene glycol graft polymers

The molecular weight must be at least 600.

The molecules are not limited to having only one polyalkylene oxide chain and the molecule may contain two or more such chains. In such a case, the individual polyalkylene oxide chains must not have more than 10 alkylene oxide units, but the total number of alkylene oxide units within the molecule must be at least 10. In such cases, when two or more polyalkylene oxide chains are present in the molecule, these chains may each comprise different alkylene oxide units, for example, they may comprise 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. Only one of these polyalkylene oxide compounds may be used, or two or more forms may be used together.

In such cases, when these polyalkylene oxide compounds are added to a silver halide emulsion, they may be added to the emulsion as an aqueous solution of appropriate concentration or after dissolving in a low boiling point organic solvent miscible with water at an appropriate time before casting and preferably after chemical ripening.

These polyalkylene oxide compounds are preferably used in amounts of 1 x 10⁻⁵ to 1 x 10⁻² moles per mole of silver halide.

The above-mentioned polyalkylene oxide compounds can also be used as light-insensitive hydrophilic colloid layers, such as intermediate layers, protective layers and filter layers, for example instead of adding to the emulsion.

Gelatin is suitable as a binding agent or as a 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 hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfate esters, sodium alginate and starch derivatives, and various synthetic hydrophilic macromolecular materials including homopolymers of poly(vinyl alcohol), partially acetalized poly(vinyl alcohol), poly(N-vinylpyrrolidone), poly(acrylic acid), poly(methacrylic acid), polyacrylamide, polyvinylimidazole and polyvinylpyrazole and copolymers of these materials.

Acid-processed gelatin and lime-processed gelatin can be used as gelatin. Gelatin hydrolysates and enzyme degradation products of gelatin can also be used. 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 can be used. Specific examples have been disclosed in, for example, US-A-2,614,928, 3,132,945, 3,186,846 and 3,312,553, GB-A-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 esters and amide derivatives of these acids, acrylonitrile and styrene, for example, onto gelatin can be used as the above-mentioned 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, having a certain compatibility with gelatin, is preferred. Examples of these have been disclosed in US-A-2,763,625, 2,831,767 and 2,956,884. Typical synthetic hydrophilic macromolecular materials have been for example in DE-A-(OLS)-23 12 708, US-A-3 620 751 and 3 879 205 and JP-B-43-7561.

Dispersions of water-insoluble or sparingly soluble synthetic polymers can be used in the photographic emulsions of the 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 (e.g. vinyl acetate), acrylonitrile, olefins, styrene or combinations of these materials or polymers in which they 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, the materials disclosed in US-A-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 GB-A-1 186 699 and 1 307 373 can be used.

Any method of photographic development can be applied to the light-sensitive material of the present invention. For example, dihydroxybenzene-based, 1-phenyl-3-pyrazolidone-based and p-aminophenol-based developers can be used as developing agents in the developer, and these developing agents can be used singly or in combination of these developing agents (for example, 1-phenyl-3-pyrazolidones and dihydroxybenzenes or p-aminophenols and dihydroxybenzenes). In addition, the light-sensitive materials of the present invention can be processed with an infectious developer in which a sulfite ion buffer such as carbonyl bisulfite and hydroquinone is used.

In the present invention, the dihydroxybenzene-based developing agents include, for example, hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone and 2,5-dimethylhydroquinone; the 1-phenyl-3-pyrazolidone-based developing agents include, for example, 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; and the p-aminophenol-based developing agents include p-aminophenol and N-methyl-p-aminophenol.

For example, compounds that provide free sulfite ions, such as sodium sulfite, potassium sulfite, potassium metabisulfite and sodium bisulfite, can be added to the developer as a preservative. Formaldehyde sodium bisulfite, which hardly provides a free sulfite ion in a developer, can 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 alkaline agent for the developer. The pH of the developer is generally adjusted to at least 9 and preferably to at least 9.7.

Known organic compounds can be used in the developer as antifogging agents or development inhibitors. Examples of such compounds include azoles (e.g. benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles and mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole)), mercaptopyrimidines, mercaptotriazines, thioketo compounds such as oxazolinethione, azaindenes (e.g. triazaindene, tetraazaindene (e.g. 4-hydroxy-substituted (1,3,3a,7)-tetraazaindenes and pentaazaindenes), benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfoamido and Sodium 2-mercaptobenzimidazole-5-sulfonate, a.

The same polyalkylene oxides described earlier can be used in the developer as development inhibitors. For example, polyethylene oxide with a molecular weight of 1000 to 10,000 can be used in concentrations in the range of 0.1 to 10 g per liter.

For example, nitrilotriacetic acid, ethylenediaminetetraacetic acid, triethylenetetraminehexaacetic acid and diethylenetetraminepentaacetic acid are suitable as softeners for hard water for developers.

Any commonly used fixing compositions may be used.

Organic sulfur compounds, which are known to be effective as fixatives, as well as thiosulfate and thiocyanates, can be used as fixatives.

Water-soluble aluminum compounds can also be used as hardeners in the fixative.

A complex of ethylenediaminetetraacetic acid and trivalent iron ions can also be used in the fixative as an oxidizing agent.

The processing time and processing temperature are made according to the intended application, but generally a processing temperature of 18ºC to 50ºC is suitable and a rapid processing time of 15 to 120 seconds is preferably carried out using an automatic processor.

The present invention will now be explained in more detail by the following examples.

example 1

Silver halide grains were precipitated using the double jet method and physically ripened and desalted, after which the grains were chemically ripened to obtain cubic silver chlorobromide grains with an average grain size of 0.28 µm containing 70 mol% silver chloride (coefficient of variation 10%). 1 kg of this emulsion contained 0.60 mol of silver halide.

Production of cast 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) was added to 1 kg of the emulsion described above.

Further, 100 mg/m² of hydroquinone, poly(ethyl acrylate) latex in an amount of 25% with respect to gelatin binder as a plasticizer and 86.2 mg/m² of 2-bis(vinylsulfonylacetamido)ethane as a hardener were added and the mixture was cast on a polyester support in a manner to give a cast silver weight of 3.7 g/m². The cast 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 µm as matting agent and 100 mg/m² of silicone oil were added and to which sodium dodecylbenzenesulfonate and a fluorine-based surfactant of the structural formula (1) shown below were 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 the structural formula (2) shown below, 10 mg/m² of the dye (FI-11) used in the present invention and sodium dodecylbenzenesulfonate as a casting aid were added were simultaneously coated over the upper poured to provide Sample 1.

In addition, the support used in this example has a backing layer and a backing protective layer of the compositions shown below. (The swelling factor of the backing layer was 110%).

Backing layer

Gelatin 3.0 g/m²

Sodium dodecylbenzenesulfonate 80 mg

Colorant (a) 80 mg

Colorant (b) 30 mg

F-I-11 100 mg

1,3-Divinylsulfonyl-2-propanol 60 mg/m²

Poly(potassium vinylbenzenesulfonate) 30 mg/m²

Back protective layer

Gelatin 0.75 g/m²

Poly(methyl methacrylate) (particle size 4.7 µm) 30 mg/m²

Sodium dodecylbenzenesulfonate 20 mg/m²

Fluorine-based surfactant (compound (1) mentioned above) 2 mg/m²

Silicone oil 100 mg/m²

Example 2 was obtained by replacing dye (2) in sample 1 with dye (3) as shown below and disclosed in JP-A-2-1837.

In addition, samples 3 to 8 were prepared by replacing dyes (2) and (F-I-11) in sample 1 with different dyes as shown in Table 1 below.

In addition, sample 9 was prepared by omitting dyes (2) and F-I-11 from sample 1.

Evaluation of photographic performance

The obtained samples were exposed using a xenon flash lamp with a flash duration of 10-6 s through an interference filter having a peak at 780 nm and a continuous wedge, developed at 38°C for 20 s using a developer having a formulation described below, fixed using a fixer having the formulation described below, washed and dried in an FG-360F automatic processor, manufactured by Fuji Photo Film Co., Ltd., (wash tank had a capacity of 6 L), and then subjected to sensitometry.

The sensitivity was calculated as the reciprocal of the amount of exposure required to provide a density of 3.0 and the relative sensitivities with respect to the sensitivity of Sample 9, which was set at 100, are shown in Table 1.

Fogging after safelighting is the fogging observed after development treatment after 20 minutes of illumination at a distance of 2 m using a 10 W tungsten lamp with a paraffin paper over a darkroom filter No.4 LD manufactured by Fuji Photo Ltd., and the results obtained are shown in Table 1.

Developer formulation

Water 720ml

Disodium ethylenediaminetetraacetate 4 g

Sodium hydroxide 44 g

Sodium sulphite 45 g

2-Methylimidazole 2 g

Sodium carbonate 26.4 g

Boric acid 1.6 g

Potassium bromide 1g

Hydroquinone 36 g

Diethylene glycol 39 g

5-Methylbenzotriazole 0.2 g

Pyrazone 0.7 g

Water for refilling 1 l

Fixative formulation

Ammonium thiosulfate 170 g

Sodium sulphite (anhydrous) 15 g

Boric acid 7 g

Glacial acetic acid 15 ml

Potassium alum 20 g

Ethylenediaminetetraacetic acid 0.1 g

Tartaric acid 3.5 g

Water for refilling 1 l Table 1

In addition, dye F-II-25 was added as a solid, finely divided particle dispersion (average particle size 0.45 µm) in sample 6.

From Table 1, it is clear that in Samples 3 to 8, in which the dye of the present invention was used, not only was fogging after darkroom illumination largely suppressed compared with Sample 9 in which no dye was added, but also little fogging was observed in Samples 1 and 2 in which known combinations of dyes were used.

In addition, Samples 3 to 8 of the present invention were excellent in sharpness like Comparative Samples 1 and 2, and were also excellent in residual color 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 heated to 55°C, an aqueous solution of silver nitrate and a mixed aqueous solution of potassium bromide and sodium chloride were added thereto by a double jet method while maintaining the pAg value of the reaction in the vessel at 7.00 to obtain a monodisperse silver chlorobromide emulsion having an average grain size of 0.55 µm (silver chloride content 60 mol%). This emulsion was designed such that 98% of all grains were of a size within an average particle size range ± 40%. The emulsion was then desalted, after which it was gold-sulfur sensitized using sodium thiosulfate and chloroauric acid after adjusting to pH 6.2, pAg 7.30 and the prescribed photographic emulsion was obtained.

The (100) plane/(111) plane ratio of this emulsion by the Kubelka-Munk method was 98/2. This was called Emulsion A.

(2) Preparation of the emulsion casting liquid

1 kg of emulsion A was weighed and heated to 40°C and dissolved, after which 70 ml of a methanolic solution of a near infrared sensitizing dye (structural formula I-12) described above (9 x M/L), an aqueous solution of 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene, an aqueous solution of dodecylbenzenesulfonate as a casting aid and an aqueous solution of poly(potassium p-vinylbenzenesulfonate) compound as a thickener were added and an emulsion casting solution was obtained.

(3) Preparation of a surface protective layer liquid for the photosensitive layer

An aqueous solution of poly(sodium ethylene sulfonate) as a thickener, fine poly(methyl methacrylate) particles (average particle size 3.0 µm) as a matting agent, N,N'-ethylenebis(vinylsulfonylacetamide) as a hardener, a Aqueous solution of sodium t-octylphenoxyethoxyethanesulfonate as a casting aid, an aqueous solution of polyethylene-based surfactant as an antistatic agent and an aqueous solution of fluorine-based compounds of which the structural formulas (c) and (d) are shown below were added to 10 wt% aqueous gelatin solution heated to 40°C and a casting liquid was obtained.

(c) C₈F₁₇SO₂N(C₃H₇)CH₂COOK

(d) C₈F₁₇SO₂N(C₃H₇)(CH₂CH₂-O)₁₅H

(4) Preparation of pour-back liquid 1

An aqueous solution of poly(sodium ethylenesulfonate) as a thickener, dye (F-I-32) used in the present invention, an aqueous solution of N,N'-ethylenebis(vinylsulfonylacetamide) as a hardener and an aqueous solution of sodium tert-octylphenoxyethoxyethanesulfonate as a casting aid were added to 1 kg of 10 wt% aqueous gelatin solution heated to 40°C, thereby obtaining a recasting liquid 1.

(5) Preparation of a surface protection layer casting liquid for the backing layer

An aqueous solution of poly(sodium ethylenesulfonate) as a thickener, 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 casting aid, an aqueous solution of polyethylene-based surfactant as an antistatic agent and an aqueous solution containing fluorine-based compounds (c) and (d) described in section (3) above were added to a 10 wt% aqueous gelatin solution heated to 40°C and a casting liquid was obtained.

(6) Preparation of cast samples

The above-mentioned backcasting liquid 1 was cast with the surface protective layer casting liquid for the backing layer on one side of a poly(ethylene terephthalate) support in such a manner that the casting weight of gelatin was 4 g/m². Further, the dye (FI-32) used in the present invention was coated at a rate of 0.01 g/m². Then, the emulsion coating liquid containing Emulsion A in which a near infrared sensitizing dye was mixed and the surface protective layer coating solution for the light-sensitive emulsion were coated on the opposite side of the support in a manner to provide a coating coating weight of gelatin of 2.8 g/m², and Sample 201 was obtained.

Sample 202 was prepared by adding the dye (F-II-8) used in the present invention as a dye for improving the darkroom light-fogging properties in a manner such that a coating weight of 0.005 g/m² was provided on the surface of the protective layer coating liquid for the photosensitive emulsion layer used in Sample 201.

In addition, Samples 203 to 206 were prepared by changing the combination of F-I-32 and F-II-8 in Sample 202 in a manner shown in Table 2 below.

In addition, sample 207 was prepared in a manner as for sample 201, except that dye F-I-32 was omitted from sample 201.

Samples 201 to 207 were developed, fixed, washed and dried in a manner indicated below using an image-wise exposure and automatic development device.

The exposure was carried out with a 10⁻⁷ s raster exposure using a semiconductor laser with a wavelength of 830 nm.

Post-exposure development and fixing were carried out by changing the developer and the fixer described below. The usual development temperature was 35ºC and processing, including fixing, washing and drying, was completed in 70 s.

developer

Potassium hydroxide 16.98 g

Glacial acetic acid 1.8 g

Sodium sulphite 60 g

Potassium carbonate 5.0 g

Boric acid 3 g

Diethylene glycol 12 g

Diethylenetriaminepentaacetic acid 2.0 g

5-Methylbenzotriazole 0.6 g

Hydroquinone 25.0 g

4-Hydroxymethyl-4-methyl-1-phenyl- 3-pyrazolidone 1.65 g

Potassium bromide 2.0 g

Water for refilling 1 l

(pH adjusted to 10.50)

fixer

Ammonium thiosulfate 140 g

Sodium sulphite (anhydrous) 15 g

Disodium ethylenediaminetetraacetate dihydrate 0.025 g

pH adjusted to 5.1 with glacial acetic acid.

Water for refilling 1 l

The results obtained are presented in Table 2. Table 2

The relative sensitivity and fogging after darkroom illumination shown in Table 2 were obtained in the same manner as in Example 1.

From Table 2, it is clear that Samples 202 to 206, in which the dyes used in the present invention were used, had less fogging after darkroom illumination than Comparative Examples 201 and 207, and were excellent photosensitive materials.

In addition, samples 202 and 206 had excellent sharpness and no residual coloration after processing.

Claims (14)

1. A silver halide photographic light-sensitive material having a silver halide emulsion layer comprising silver halide grains containing at least silver chloride which have been spectrally sensitized in the infrared region using at least one tricarbocyanine dye and/or dicarbocyanine dye containing a 4-quinoline nucleus, characterized in that the material comprises at least one hydrophilic colloid layer containing at least one dye represented by the general formula (FI) given below and at least one hydrophilic colloid layer containing at least one dye represented by the general formula (F-II) given below, wherein R¹, R², R³, R⁴, R⁵ and R⁶ may be the same or different and each represents a substituted or unsubstituted alkyl group; Z¹ and Z² each represents a group of non-metal atoms required to form a substituted or unsubstituted benzo-fused ring, naphtho-fused ring or 5- or 6-membered heterocyclic fused ring; with the proviso that R¹, R², R³, R⁴, R⁵, R⁵, Z¹ and Z² are selected such that the dye molecule contains 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 if the dye forms an intramolecular salt, wherein R₂₁ and R₂₄ each represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group; R₂₂ and R₂₅ each represent a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, COR₂₠ or SO₂R₂₠; R₂₃ and R₂₆ each represent a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, COR₂₠ or SO₂R₂₠; each represents a hydrogen atom, a cyano group, an alkyl group, an aryl group, -COOR₂₇, -OR₂₇, -NR₂₇R₂₈, -N(R₂₈)COR₂₠, -N(R₂₈)SO₂R₂₈, -CONR₂₇R₂₈ or -N(R₂₇)CONR₂₇R₂₈ (wherein R₂₇ represents an aliphatic group or an aromatic group, and R₂₇ and R₂₈ each represent a hydrogen atom, an aliphatic group or an aromatic group); L₄, L₅, L₆, L₇ and L₈ represent methine groups; n₁ and n₂ each represent 0 or 1; and M represents hydrogen or another monovalent cation; with the proviso that at least one of the groups R₂₁, R₂₂, R₂₃, R₂₄, R₂₅, R₂₆, L₄, L₅, L₆, L₇ or L₈ represents a group having at least one carboxylic acid group or sulfonic acid group. 2. A silver halide photographic light-sensitive material as claimed in claim 1, wherein the tricarbocyanine dye is represented by the following general formula (Ia) or (Ib): General formula (Ia) General formula (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; R₆ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group, a benzyl group or wherein W₁ and W₂ each represent a substituted or unsubstituted alkyl group or an aryl group, and W₁ W₂ and W₂ may be joined together to form a 5- or 6-membered nitrogen-containing heterocyclic ring; D represents a group of atoms required to complete a divalent ethylene bond; D₁ and D₂ each represent a hydrogen atom, or D₁ and D₂ may together form a divalent ethylene bond; Z and Z₁ each represent a group of non-metal atoms required to complete a 5- or 6-membered nitrogen-containing heterocyclic group; X represents an acid anion; and n represents 1 or 2. 3. A silver halide photographic light-sensitive material as claimed in claim 1, wherein the dicarbocyanine dye containing a 4-quinoline nucleus is represented by the general formula (II): General formula (II) wherein R6 and R7, which may be the same or different, each represent 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 required to complete a 5- or 6-membered nitrogen-containing heterocyclic group; X1 represents an acid anion; and m, n1 and p each represent 1 or 2. 4. The silver halide photographic light-sensitive material as claimed in claim 1, wherein the dye of the general formula (F-I) and the dye of the general formula (F-II) are each present in an amount of 10-4 g/m² to 1 g/m². 5. A silver halide photographic light-sensitive material as claimed in claim 4, wherein the dye of the general formula (F-I) and the dye of the general formula (F-II) are each present in an amount of 10⁻³ g/m² to 0.5 g/m². 6. A silver halide photographic light-sensitive material as claimed in claim 1, wherein the infrared sensitizing dyes are present in the silver halide photographic emulsion in an amount of 5 x 10⁻⁷ to 5 x 10⁻³ mol, per mol of the silver halide. 7. A silver halide photographic light-sensitive material as claimed in claim 6, wherein the infrared sensitizing dyes are present in the silver halide photographic emulsion in an amount of 1 x 10⁻⁶ to 1 x 10⁻³ mol per mol of the silver halide. 8. A silver halide photographic light-sensitive material as claimed in claim 7, wherein the infrared sensitizing dyes are present in the silver halide photographic emulsion in an amount of 2 x 10⁻⁶ to 5 x 10⁻⁴ mol, per mol of the silver halide. 9. The silver halide photographic light-sensitive material of claim 1, wherein a compound represented by the general formula (III) is incorporated in the emulsion: General formula (III) wherein A represents a divalent aromatic residual group; R9, R10, R11 and R12 each represent 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 heterocyclic thio group, an arylthio group, an amino group, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted arylamino group, a heterocyclic amino group, a substituted or unsubstituted aralkylamino group, an aryl group or a mercapto group; and W represents -CH= or -N=. 10. A silver halide photographic light-sensitive material as claimed in claim 9, wherein the compound of the general formula (III) is present in an amount of 0.01 g to 5 g per mole of the silver halide emulsion. 11. The silver halide photographic light-sensitive material of claim 1, wherein a compound represented by the general formula (IV) is present in the emulsion: General formula (IV) wherein Z₃ represents a group of non-metal atoms required to complete a 5- or 6-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. 12. The silver halide photographic light-sensitive material as claimed in claim 11, wherein the compound represented by the general formula (IV) is present in an amount of 0.01 g to 5 g per mol of the silver halide in the emulsion. 13. A silver halide photographic light-sensitive material as claimed in claim 1, wherein the silver chloride content of the emulsion is 25 to 100 mol%. 14. The silver halide photographic light-sensitive material as claimed in claim 1, wherein the silver halide emulsion is a monodisperse silver halide emulsion having an average grain size of 0.04 µm to 0.7 µm.