JP2663192B2 - Silver halide photographic material - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an infrared spectrally sensitized high silver chloride light-sensitive material having improved storage stability with time of a light-sensitive material. More specifically, aimed at obtaining an image by scanning exposure using high density light such as a laser or light emitting diode,
The present invention relates to an infrared spectrally sensitized high silver chloride photographic material having improved storage stability.

(Prior Art) In recent years, technology for transmitting and storing image information in the form of an electric signal and reproducing it on a CRT has been extremely developed. Accordingly, demands for hard copies from this image information have increased, and various hard copy means have been proposed. However, many of these have poor image quality and are incomparable to current prints using color paper. To provide high-quality hard copy, there are two types of thermal developing dye diffusion method of silver halide and LE.
Although there is Pictrography (trade name) manufactured by FUJIFILM Corporation using the D-scanning exposure method, there is still dissatisfaction with the cost of photosensitive materials, processing stability, and the like.

On the other hand, with the progress of silver halide photographic materials and compact simple rapid development systems (for example, minilab systems), extremely high-quality printed photographs are relatively easily supplied in a short time and at low cost. Therefore, there is an extremely high demand for a hard copy material which can provide high speed, low cost, quick and always stable performance as a hard copy of image information.

As a method of obtaining a hard copy from an electric signal, generally, a scanning exposure method in which image information is sequentially taken out and exposed is generally used, and a light-sensitive material suitable for this method is required.

As a method of forming an image by scanning exposure, there is an image forming method by a so-called scanner method. There are various types of recording apparatuses that have practically used the scanner method, and a glow lamp, a xenon lamp, a mercury lamp, a tungsten lamp, a light emitting diode, and the like have been used as a recording light source of the scanner method recording apparatus. However, each of these light sources has a practical disadvantage that the output is weak and the life is short. To compensate for these disadvantages, there is a scanner using a coherent laser light source such as a gas laser such as a He-Ne laser, an argon laser, or a He-Cd laser, or a semiconductor laser as a light source of a scanner system.

A gas laser can provide high output, but has disadvantages such as a large device, high cost, and a need for a modulator.

On the other hand, semiconductor lasers have advantages such as small size, low cost, easy modulation, and a longer life than gas lasers. The emission wavelength of these semiconductor lasers is mainly in the infrared region, and thus a photosensitive material having high sensitivity in the infrared region is required. However, conventional infrared-sensitive light-sensitive materials have poor storage properties due to the instability of infrared sensitizing dyes, require refrigeration or frozen storage, and have only very poor handling properties. .

For these reasons, a method has been considered in which an image is formed by exposing a silver halide photosensitive material spectrally sensitized with a sensitizing dye in the visible region having good storage stability while maintaining the advantages of a semiconductor laser. I have. That is, as disclosed in JP-A-63-113534, JP-A-63-18343, and EP-03350047, a semiconductor laser and a nonlinear optical material are combined, and the second harmonic of the semiconductor laser is taken out as visible light. Is what you are going to use. However, the production stability of this nonlinear optical material, cost, conversion efficiency to the second harmonic,
Considering the service life and the like, practical use still has considerable problems.

Therefore, it is considered that it is most preferable to solve the problem of the storage stability of the infrared sensitized material and use it as a scanning exposure material in combination with a semiconductor laser from the viewpoint of the total cost, size, life, etc. of the system. Can be

Further, when color paper is considered as an output by scanning exposure of an image, simplification and speeding up of processing are very important. Thus, as described in W087-04534,
It is useful to use a method of rapidly processing a silver chloride color photographic light-sensitive material with a color developer substantially free of sulfite ions and benzyl alcohol. It is important to be suitable for speeding up. However, if silver halide grains having a high silver chloride content are spectrally sensitized by infrared spectroscopy, the storage stability of the photographic material over time will be further deteriorated. Sex gets worse.

Based on the above, we have developed a high silver chloride color photosensitive material that has a spectral sensitivity suitable for scanning exposure with a semiconductor laser in the infrared region, is simple and quick to process, and has excellent storage stability. Is very much awaited.

With the aim of obtaining a full-color hard copy inexpensively and quickly with a silver halide photosensitive material, JP-A-61-13
No. 7,149 discloses that a support is provided with three kinds of silver halide emulsion layers each containing a normal color coupler which develops cyan, magenta or yellow, and at least two of the layers are exposed to visible light. In addition, it discloses a color photographic light-sensitive material that has been spectrally sensitized so as to be sensitive to laser light in the infrared region, and basic conditions thereof. JP-A-63-197,947 discloses that a support is provided with three types of photosensitive layers each containing three types of color couplers capable of developing cyan, magenta and yellow, at least one of which has a spectral sensitivity maximum. Full-color recording materials, which are spectrally sensitized to wavelengths longer than about 670 nm and are exposed to LEDs and semiconductor laser light, and obtain color images by optical scanning exposure and subsequent color development, are particularly high Sensitive and stable spectral sensitization methods and methods of using dyes are disclosed. Furthermore, JP-A-55-13,505
Discloses a color image recording method for a photographic material that obtains full color by controlling the color development of yellow, magenta, and cyan with three types of light beams having different wavelengths, for example, green, red, and infrared light beams. Have been.

However, the above-mentioned JP-A-61-137,149 and JP-A-63-197,947 disclose the basic constitution of the color photographic material, but the object of the present invention is to obtain an infrared spectrally sensitized chloride. There is no specific description about means for improving the storability of a light-sensitive material using a silver halide emulsion having a high silver content.

As a method for improving the preservability of a silver halide sensitized material subjected to infrared spectral sensitization, JP-A-59-191032 discloses that a benzothiazole compound is used together with an infrared sensitizing dye to preserve the photographic material. It is disclosed that the property is improved. However, the high silver chloride content (80
In the case of silver halide emulsions, satisfactory storage performance could not be obtained even when these compounds were used.

JP-A-2-20853 discloses that high sensitivity can be attained by doping a high silver chloride emulsion with a six-coordinate complex of Re, Ru or Os having at least four cyanogen ligands. . However, only the emulsion using the spectral sensitizing dye for the visible region is specifically described, but there is no specific description of the infrared-sensitized light-sensitive material. There is no description of the preservability of the sensitized material thus prepared, especially the desensitization caused by the thermal instability of the sensitizing dye.

EP-242,190 discloses that a photosensitive material containing silver halide emulsion grains, which have been spectrally sensitized by infrared rays and doped with an Rh complex having three or more cyanide ligands, is used for scanning exposure with a laser to obtain high illuminance. It is disclosed that reciprocity failure is improved and a high-sensitivity and high-sensitivity photographic material can be obtained. However, this patent specifically describes the Rh complex having a cyan ligand (Ir complex as a comparative example), but does not describe other metal complexes having an an ligand. Storage quality of the photosensitive material,
In particular, there is no description about desensitization caused by the thermal instability of the sensitizing dye. Further, even when the Rh or Ir complex having the cyan ligand is used, no improvement in the storage stability of the light-sensitive material is observed.

EP-350,046 contains a silver halide emulsion layer having a silver chloride content of 95 mol% or more and containing a metal ion of Group VIII and a transition metal ion of Group II in the periodic table. It is disclosed that the fluctuation of photographic properties due to the fluctuation of the processing solution can be improved by performing scanning exposure and development processing of the color sensitized material subjected to external spectral sensitization. The metal complexes specifically used are iridium chloride, potassium hexachlororhodate and potassium ferrocyanide, and the description of the metal complex having a cyanide ligand is only potassium ferrocyanide. Moreover, there is no description about the storage stability of the sensitized material subjected to infrared spectral sensitization, particularly the desensitization caused by the thermal instability of the sensitizing dye.

[Problems to be Solved by the Invention] Accordingly, an object of the present invention is to provide a high silver chloride photosensitive material having a spectral sensitivity suitable for scanning exposure by a semiconductor laser in the infrared region and having a simple and quick processing. Another object of the present invention is to develop a photosensitive material having excellent storage stability.

[Means for Achieving the Object] An object of the present invention is to provide a silver halide photographic material having at least one photosensitive emulsion layer containing a silver halide emulsion on a support, wherein at least one of the photosensitive emulsion layers is provided. Co, Ni having a spectral sensitivity maximum at 730 nm or more and having at least two cyanogen ligands in the photosensitive emulsion layer.
A silver halide photographic light-sensitive material comprising silver halide grains containing at least one selected from metal complexes of Ru, Re, Os, Pt and Au and having a silver chloride content of 80 mol% or more. Have been found to be achievable using.

The metal complex of Co, Ni, Ru, Re, Os, Pt or Au having at least two cyanide ligands used in the present invention is preferably represented by the following general formula [CI] or [C-II]. .

[M ₁ (CN) _6-a L _a ] ⁿ [C-I] [M ₂ (CN) _4-b L _b ] ^m [C-II] M ₁ ; Co, Ru, Re, Os, or Pt M ₂ ; Ni, Pt or Au L; ligands other than CN a; 0, 1 or 2 b; 0, 1 or 2 n; -2, -3 or -4 m; -1 or -2 The metal complex represented by the general formula [CI] is more preferably used. Further, in the general formula [C-I]
The M _1, Ru, Re, Os is the most preferable.

Specific examples of the metal complex having at least two cyan ligands used in the present invention are shown below. As counter ions of these metal complexes, ammonium and alkali metal ions such as sodium and potassium are preferably used.

^{_{[Co (CN) 6] -3}} [Ni (CN) 4] -2 [Ru (CN) 6] -4 [Ru (CN) 5 F] -4 [Ru (CN) 4 F 2] -4 [Ru (CN) ₅ Cl] ^-4 [Ru (CN) ₄ Cl ₂ ] ^-4 [Ru (CN) ₅ Br] ^-4 [Ru (CN) ₄ Br ₂ ] ^-4 [Ru (CN) ₆ I] ^-4 _{[Ru (CN) 4 I 2} ] -4 [Ru (CN) 5 (OCN)] -4 [Ru (CN) 5 (SCN)] -4 [Ru (CN) 5 (N 3)] -4 [Ru (CN) ₅ (H ₂ O)] ^-3 [Re (CN) ₆ ] ^-4 [Re (CN) ₅ F] ^-4 [Re (CN) ₄ F ₂ ] ^-4 [Re (CN) ₅ Cl] ^-4 [Re (CN) ₄ Cl ₂ ] ^-4 [Re (CN) ₅ Br] ^-4 [Re (CN) ₄ Br ₂ ] ^-4 [Re (CN) ₅ I] ^-4 [Re (CN) ₄ I ₂ ] ^-4 [Os (CN) ₆ ] ^-4 [Os (CN) ₅ F] ^-4 [Os (CN) ₄ F ₂ ] ^-4 [Os (CN) ₅ Cl] ^-4 [Os (CN) ₄ Cl ₂ ] ^-4 [Os (CN) ₅ Br] ^-4 [Os (CN) ₄ Br ₂ ] ^-4 [Os (CN) ₅ I] ^-4 [Os (CN) ₄ I ₂ ] ^-4 [Os (CN) ₅ (OCN)] ^-4 [Os (CN) ₅ (SCN)] ^-4 [Os (CN) ₅ (N ₃ )] ^-4 [Os (C _{N) 5 (H 2 O)} ] -3 [Pt (CN) 4] -2 [Pt (CN) 4 Cl 2] -2 [Pt (CN) 4 Br 2] -2 [Pt (CN) 4 I 2 ] ^-2 [Au (CN) ₄ ] ^-1 [Au (CN) ₂ Cl ₂ ] ^-1 The content of at least one metal complex selected from the metal complexes having at least two cyanogen ligands used in the present invention is as follows:
It is preferably from 10 ^{-6 to} 10 ^-3 per mol of silver halide, and more preferably from 5 × 10 ^{-6 to} 5 × 10 ^-4 mol per mol of silver halide.

At least one selected from metal complexes having at least two cyanide ligands used in the present invention is added and contained at any stage before and after preparation of silver halide grains, that is, nucleation, growth, physical ripening, and chemical sensitization. May be. Further, it may be added and contained by dividing it several times. However, at least two silver halide grains are contained in the silver halide grains.
It is preferable that 50% or more of the total content of at least one selected from metal complexes having two cyan ligands is contained in a surface layer of 50% or less of the particle volume. Here, the surface layer of 50% or less of the particle volume refers to a surface portion corresponding to a volume of 50% or less of the volume of one particle. The volume of this surface layer is preferably 40% or less, more preferably 20% or less. Further, a layer not containing a metal complex may be provided further outside the surface layer containing a metal complex defined herein.

These metal complexes are dissolved in water or a suitable solvent,
When forming silver halide grains, add them directly to the reaction solution, or add them to an aqueous halide solution for forming silver halide grains, an aqueous silver salt solution, or other solutions to form grains. Is preferably contained. Further, it is also preferable to add and dissolve silver halide fine particles containing a metal complex in advance and to deposit on a separate silver halide particle to contain these metal complexes.

The halogen composition of the silver halide grains of the present invention may be a silver chlorobromide containing substantially no silver iodide wherein 80 mol% or more of the total silver halide constituting the silver halide grains is silver chloride, or silver chloride. Must consist of Here, "contains substantially no silver iodide" means that the silver iodide content is 1.0 mol% or less. Preferred halogen composition of silver halide grains,
95 mol% of all silver halide constituting silver halide grains
The above is silver chlorobromide or silver chloride substantially free of silver iodide which is silver chloride. The most preferred halogen composition of the silver halide grains is silver chlorobromide or silver chloride containing substantially no silver iodide wherein 98 mol% or more of the total silver halide constituting the silver halide grains is silver chloride. .

The silver halide grains of the present invention preferably have a localized phase exceeding at least 10 mol% in silver bromide content. The arrangement of the localized phase having a high silver bromide content is as follows.
In order to exhibit the effects of the present invention, it is preferable that the particles are located near the particle surface, from the viewpoints of pressure characteristics, treatment solution composition dependency, and the like. Here, “near the grain surface” means a position within 1/5 of the grain size of the silver halide grains used, measured from the outermost surface. The position is preferably within 1/10 of the grain size of the silver halide grains to be used, as measured from the outermost surface. The most preferred configuration of the localized phase having a high silver bromide content is:
A localized phase having a silver bromide content of at least more than 10 mol% is epitaxially grown at the corners of cubic or tetradecahedral silver chloride grains.

Localized phase with high silver bromide content has a silver bromide content of 10 mol%
However, if the silver bromide content is too high, desensitization may occur when pressure is applied to the photosensitive material,
Variations in the composition of the processing solution may impart undesired characteristics to the photographic material, such as a significant change in sensitivity and gradation. Taking these points into consideration, the silver bromide content of the localized phase having a high silver bromide content is 10
Is preferably in the range of from 20 to 60 mol%, most preferably in the range of from 20 to 50 mol%. The silver bromide content of the localized phase having a high silver bromide content can be determined by an X-ray diffraction method (for example, described in “Chemical Society of Japan, New Experimental Chemistry Course 6, Structural Analysis” Maruzen) and the like. Can be used to analyze. The localized phase having a high silver bromide content is 0.1% of the total silver constituting the silver halide grains of the present invention.
Preferably comprised of 1 to 20% silver, 0.5
More preferably, it is composed of silver of from 7 to 7%.

The interface between the localized phase having a high silver bromide content and other phases may have a clear phase boundary, or may have a transition region in which the halogen composition changes gradually. Good.

Various methods can be used to form such a localized phase having a high silver bromide content. For example, a localized phase can be formed by reacting a soluble silver salt and a soluble halogen salt by a one-side mixing method or a simultaneous mixing method. Further, a localized phase can be formed by using a conversion method for converting already formed silver halide grains into silver halide having a lower solubility product. The silver bromide content is obtained by mixing cubic or tetradecahedral silver halide host grains with silver halide fine grains having a smaller average grain size than the silver halide host grains and having a high silver bromide content, followed by ripening. It is most preferable to form a localized phase having a high ratio in order to exhibit the effects of the present invention.

It is also preferable that the localized phase having a high silver bromide content contains at least one selected from metal complexes having at least two cyanogen ligands, that is, the formation of the localized phase is preferably performed in the presence of these metal complexes. Done. Here, performing the formation of the localized phase in the presence of the metal complex means that the supply of silver ions or halogen ions for forming the localized phase is performed simultaneously.
This refers to supplying the metal complex immediately before or immediately after the supply. After mixing silver halide fine grains having a smaller average grain size than silver halide host grains and having a high silver bromide content and then ripening to form a localized phase having a high silver bromide content, It is preferred that the silver halide fine particles having a high silver bromide content contain a metal complex in advance.

The silver halide grains of the present invention are preferably gold sensitized. Examples of the gold sensitizer include chloroaurate, auric trichloride, potassium auric thiocyanate, and potassium iodooleate. The preferable addition amount of the gold sensitizer is 5 × 10 ^-7 to 1 mol per mol of silver halide.
The amount is 1 × 10 ⁻³ mol, and the more preferable addition amount is 1 × 10 ⁻⁶ to
1 × 10 ^-4 mol. The timing of adding the gold sensitizer may be at any stage of the production process of the silver halide emulsion, but is preferably after the completion of the formation of silver halide grains.

The silver halide grains of the present invention are sulfur sensitized, selenium sensitized,
It is preferable to perform reduction sensitization or chemical sensitization other than gold sensitization such as noble metal sensitization in combination. Among these chemical sensitizations, it is particularly preferable to carry out sulfur sensitization in combination.

The chemical sensitization with sulfur used in the present invention is performed using a compound containing sulfur which can react with active gelatin or silver (for example, thiosulfate, thioureas, mercapto compounds, rhodanines). These examples are described in U.S. Pat.
No. 574,944, No. 2,278,947, No. 2,410,689, No.
Nos. 2,728,668 and 3,656,955.

The silver halide grains of the present invention may have a (100) face, an (111) face, or both of them on the outer surface. May include higher-order planes, but are preferably cubes mainly composed of (100) planes or tetradecahedrons.

The size of the silver halide grains of the present invention may be within the range usually used, but the average grain size is 0.1 μm to 1.5 μm.
m is preferred. The particle size distribution may be polydisperse or monodisperse, but is preferably monodisperse. The particle size distribution, which represents the degree of monodispersion, is the ratio (s / d) between the statistical standard deviation (s) and the average particle size (d).
Is preferably 0.2 or less, more preferably 0.15 or less. It is also preferable to use a mixture of two or more monodisperse emulsions.

In the silver halide grains of the present invention, in addition to a metal complex having at least two cyanogen ligands, a metal complex or a metal salt as described below is used for the purpose of, for example, reducing sensitivity and variation in gradation due to a change in exposure illuminance. It is also preferred to contain

Hexachloroiridium (III) or (IV) acid salt,
Hexaamine iridium (III) or (IV), trioxalatoiridium (III) or (IV), hexacyanoferrate (II) or (III), ferrous thiocyanate or thiocyanate Iron salt, potassium hexachlororhodium (III).

The addition amount of the above iridium ion is preferably in the range of 10 ^-9 mol to 10 ^-6 mol per mol of silver halide, and most preferably in the range of 10 ^-8 mol to 10 ^-6 mol per mol of silver halide. The amount of iron ion added is 1 silver halide.
The range is preferably from 10 ^-8 mol to 10 ^-4 mol per mol, and most preferably from 10 ^-7 mol to 10 ^-4 mol per mol of silver halide. The addition amount of the above rhodium ion is preferably in the range of 10 ^-9 mol to 10 ^-6 mol per mol of silver halide, and most preferably in the range of 10 ^-8 mol to 10 ^-6 mol per mol of silver halide.

To the silver halide emulsion used in the present invention, various compounds or their precursors are added for the purpose of preventing fogging during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. be able to. As specific examples of these compounds, those described on pages 39 to 72 of JP-A-62-215272 are preferably used.

The structure of the light-sensitive material of the present invention will be described. The light-sensitive material of the present invention has at least one silver halide emulsion layer on a support, and at least one layer has a spectral sensitivity maximum at 730 nm or more. In order to use the light-sensitive material of the present invention as a color hard copy material, it is necessary to contain at least one kind of coupler which forms a color by a coupling reaction with an oxidized aromatic amine compound. For a full-color hard copy, the support has at least three kinds of silver halide photosensitive layers having different color sensitivities on a support, and each of the layers is formed by a coupling reaction with an oxidized form of an aromatic amine compound. It is preferable to contain either a coupler that develops magenta or cyan. These three different spectral sensitivities can be arbitrarily selected depending on the wavelength of the light source used for the scanning exposure. However, it is preferable that the closest spectral sensitivities are at least 30 nm apart from the viewpoint of color separation. There is no particular limitation on the correspondence with the color couplers (Y, M, C) contained in the photosensitive layers (λ1, λ2, λ3) having at least three different spectral sensitivity maxima. That is, 3 × 2 = 6 combinations are possible. There is no particular limitation on the order of application of the photosensitive layers having at least three different spectral sensitivity maxima from the support side. Therefore, there are 36 possible combinations of the three different spectral sensitivities, the three color couplers, and the layer order. The present invention can be effectively used for all of these 36 types of photosensitive materials.

By using the silver halide emulsion of the present invention in a layer using a sensitizing dye having a spectral sensitivity maximum at 730 nm or more, desensitization of a light-sensitive material over time can be improved. A more preferable use method is to use a layer having a spectral sensitivity maximum at 780 nm or more.

In the present invention, it is particularly preferable to use a semiconductor laser as the light source for scanning exposure. In order to obtain a full-color hard copy, it is preferable that at least two of the silver halide photosensitive layers having different color sensitivity have a spectral sensitivity maximum in a long wavelength region of 670 nm or more, more preferably Is that all three types of silver halide photosensitive layers having different color sensitivity have a spectral sensitivity maximum in a long wavelength region of 650 nm or more.

Table 1 shows specific examples of the scanning exposure light source, the spectral sensitivity maximum, and the color coupler, but the present invention is not limited thereto.

Spectral sensitization is performed for the purpose of imparting spectral sensitivity to a desired light wavelength range to the emulsion of each layer in the light-sensitive material of the present invention. In the present invention, it is preferable to add a dye that absorbs light in a wavelength range corresponding to the intended spectral sensitivity—a spectral sensitizing dye. Examples of spectral sensitizing dyes used at this time include, for example, Heterocyclic compo by FM Harmer.
unds-Cyanine dyes and related compounds (John Wil
ey '& Sons [New York, London], 1964. As specific examples of the compounds, those described in the above-mentioned JP-A-62-215272, page 22, upper right column to page 38, are preferably used.

In the present invention, the following general formulas (QI), (Q-II), and (Q-
It can be used by selecting from the sensitizing dyes represented by III).

The general formulas (QI), (Q-II), and (Q-
The sensitizing dye represented by III) will be described in detail.

General formula (QI) In the formula, Z ₆₁ and Z ₆₂ each represent an atomic group necessary for forming a heterocyclic nucleus.

As the heterocyclic nucleus, a 5- or 6-membered ring nucleus containing a nitrogen atom and other optionally a sulfur atom, an oxygen atom, a selenium atom or a molull atom (condensed rings are further bonded to these rings. And a substituent may be further bonded).

Specific examples of the heterocyclic nucleus include thiazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, selenazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus, oxazole nucleus, benzoxazole nucleus, naphthoxazole nucleus, imidazole nucleus, benzozine Imidazole nucleus, naphthoimidazole nucleus, 4-quinoline nucleus, pyrroline nucleus, pyridine nucleus, tetrazole nucleus, indolenine nucleus, benzindolenine nucleus, indole nucleus, tellurazole nucleus, benzotellurazole nucleus, naphthotellurazole nucleus and the like. it can.

R ₆₁ and R ₆₂ each represent an alkyl group, an alkenyl group, an alkynyl group or an aralkyl group. These groups and the groups described below are used in the meaning including their respective substituents. Taking an alkyl group as an example, it includes unsubstituted and substituted alkyl groups, and these groups may be linear, branched or cyclic. The alkyl group preferably has 1 to 8 carbon atoms.

Specific examples of the substituent of the substituted alkyl group include a halogen atom (chlorine, bromine, fluorine, etc.), a cyano group, an alkoxy group, a substituted or unsubstituted amino group, a carboxylic acid group,
Examples thereof include a sulfonic acid group and a hydroxyl group, and one or a combination of these may be substituted.

Specific examples of the alkenyl group include a vinylmethyl group.

Specific examples of the aralkyl group include a benzyl group and a phenethyl group.

m ₆₁ represents a positive number of 1, 2, or 3.

R ₆₃ represents a hydrogen atom, R ₆₄ represents a hydrogen atom, a lower alkyl group or an aralkyl group, and can be linked to R ₆₂ to form a 5- or 6-membered ring. When R ₆₄ represents a hydrogen atom, R ₆₃ may be linked to another R ₆₃ to form a hydrocarbon ring or a heterocyclic ring. These rings are preferably 5- or 6-membered rings. j ₆₁ and k ₆₁ represent 0 or 1, X ₆₁ represents an acid anion, and n ₆₁ represents 0 or 1.

General formula (Q-II) In the formula, Z ₇₁ and Z ₇₇ have the same meanings as Z ₆₁ or Z ₆₂ described above. R
₇₁ and R ₇₂ have the same meaning as R ₆₁ or R ₆₂ , and R ₇₃ is alkyl,
Represents an alkenyl, alkynyl or aryl group (for example, a substituted or unsubstituted phenyl group). m ₇₁ represents 2 or 3. R ₇₄ is a hydrogen atom, a lower alkyl group, in addition to an aryl group, it may form a hydrocarbon ring or a heterocyclic ring linked and the R ₇₄ and the other R _74. These rings are preferably 5- or 6-membered rings.

 Q₇₁Is a sulfur atom, oxygen atom, selenium atom or NR
₇₅And R₇₅Is R₇₃Is synonymous with j₇₁,R₇₁, ▲ X ₇₁▼ and n₇₁Is j₆₁, K₆₁, ▲ X ₆₁You
And n₆₁Is synonymous with

General formula (Q-III) In the formula, Z ₈₁ represents an atomic group necessary for forming a heterocyclic ring. As the heterocyclic ring, those described for Z ₆₁ and Z ₆₂ and specific examples thereof include other thiazolidine, thiazoline, benzothiazoline, naphthothiazoline, selenazolidine, selenazoline, benzoselenazoline, naphthoselenazoline, benzoxazoline, naphthooxazoline,
Examples include nuclei such as dihydropyridine, dihydroquinoline, benzimidazoline and naphthoimidazoline.

Q ₈₁ has the same meaning as that of Q _71. R ₈₁ is R ₆₁ or R ₆₂ and R ₈₂ is
Synonymous with R ₇₃ . m ₈₁ represents 2 or 3.
R ₈₃ Other synonymous with R _74, may form a hydrocarbon ring or a heterocyclic ring linked and the R ₈₃ and the other R _83. j ₈₁ has the same meaning as j _61.

In the general formula (QI), the heterocyclic nucleus of Z ₆₁ and / or Z ₆₂ is particularly preferably a naphthothiazole nucleus, a naphthoselenazole nucleus, a naphthoxazole nucleus, a naphthoimidazole nucleus,
Sensitizing dyes having a 4-quinoline nucleus are preferred. General formula (Q
Z ₇₁ and / or Z ₇₂ or the general formula in -II) (Q-
The same applies to III). Further, a ring-enhancing dye whose methine chain forms a hydrocarbon ring or a heterocyclic ring is preferable.

Infrared sensitization uses sensitization by the M band of a sensitizing dye, so that the spectral sensitivity distribution is generally broader than that by the J band. For this reason, it is preferable to correct the spectral sensitivity distribution by providing a coloring layer containing a dye in the colloid layer on the photosensitive surface side of the predetermined photosensitive layer. This colored layer is effective for preventing color mixing by a filter effect.

As a sensitizing dye for infrared sensitization, a reduction potential is particularly -1.
Compounds having a value of 05 (VvsSCE) or lower are preferred, and compounds having a reduction potential of −1.10 or lower are particularly preferred. A sensitizing dye having this property is advantageous for increasing sensitivity, particularly for stabilizing sensitivity and stabilizing latent increase.

The reduction potential can be measured by phase discrimination type second harmonic AC polarography. A mercury dropping electrode is used as a working electrode, a saturated calomel electrode is used as a reference electrode, and platinum is used as a counter electrode.

The measurement of the reduction potential by phase discrimination second harmonic AC voltammetry using platinum as the working electrode is described in "Journal of Ima
ging Science), Vol. 30, pages 27-35 (1986).

Specific examples of the sensitizing dyes represented by formulas (QI), (Q-II) and (Q-III) are shown below.

In order to incorporate these spectral sensitizing dyes into a silver halide emulsion, they may be directly dispersed in the emulsion,
Or water, methanol, ethanol, propanol,
A solvent such as methylcellosolve, 2,2,3,3-tetrafluoropropanol or the like may be dissolved alone or in a mixed solvent and added to the emulsion. In addition, JP-B-44-23389, JP-B-44
No. 27555, Japanese Patent Publication No. 57-22089, etc. to co-exist with an acid or a base to form an aqueous solution, and U.S. Pat.
As described in U.S. Pat. No. 4,060,525, an aqueous solution or colloidal dispersion in the presence of a surfactant may be added to the emulsion. After dissolving in a substantially water-immiscible solvent such as phenoxyethanol, a dispersion in water or a hydrophilic colloid may be added to the emulsion.
As described in JP-A-53-102733 and JP-A-58-105141, the dispersion may be directly dispersed in a hydrophilic colloid, and the dispersion may be added to the emulsion. The timing of addition to the emulsion may be at any stage in the preparation of the emulsion which has hitherto been known to be useful. In other words, before the formation of the silver halide emulsion grains, during the grain formation, immediately after the grain formation and before the washing step,
It can be selected from before the chemical sensitization, during the chemical sensitization, immediately after the chemical sensitization, until the emulsion is cooled and solidified, or during the preparation of the coating solution. Most commonly, after chemical sensitization is completed, it is performed before coating, but as described in U.S. Patent Nos. 3,628,969 and 4,225,666, it is added simultaneously with a chemical sensitizer and spectrally added. The sensitization can be performed simultaneously with the chemical sensitization, or can be performed prior to the chemical sensitization as described in JP-A-58-113828, and added before the completion of the formation of silver halide grains. Spectral sensitization can also be started. Furthermore, as taught in U.S. Pat.No. 4,225,666, spectral sensitizing dyes can be added separately, i.e., some added prior to chemical sensitization and the remainder added after chemical sensitization. It is possible at any time during silver halide grain formation, including the method taught in US Pat. No. 4,183,756. Among them, it is particularly preferable to add a sensitizing dye before the step of washing the emulsion or before the chemical sensitization.

The addition amount of these spectral sensitizing dyes may vary over a wide range depending on the case, but is 0.5 × 10 ^{−6 to} 1.0 × 10 ⁻⁶ per mol of silver halide.
A range of × 10 ^-2 is preferred. More preferably, 1.0 × 10
^{-6 to} 5.0 × 10 ^-3 .

In the red or infrared sensitization of the present invention, the M-band sensitization includes, in particular, the following general formulas [A], [B],
Supersensitization with the compound represented by [Ea], [Eb] or [Ec] is useful.

The supersensitizer represented by the general formula [A] is used in combination with the supersensitizer represented by the general formulas [B], [Ea], [Eb], and [Ec] to specifically enhance the supersensitizer. The color sensitizing effect can be increased.

General formula (A) In the formula, A ₉₁ represents a divalent aromatic residue. R ₉₁ , R ₉₂ , R
₉₃ and R ₉₄ are each a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, a heterocyclic nucleus, a heterocyclylthio group, an arylthio group, an amino group, an alkylamino group, an arylamino group, an aralkylamino group, Represents an aryl group or a mercapto group,
These groups may be substituted.

Provided that at least one of A ₉₁ , R ₉₁ , R ₉₂ , R ₉₃ and R ₉₄
One has a sulfo group. X ₉₁ and Y ₉₁ are each -CH =, - N = represents, at least one among X ₉₁ and Y ₉₁ represents -N =.

In the general formula [A], more specifically, -A _91- represents a divalent aromatic residue, and these are -SO ₃ M groups [where M is a hydrogen atom or a cation imparting water solubility (for example, sodium,
Potassium, etc.). ] May be included.

As -A _91- , for example, those selected from the following -A ₉₂ -or -A _93- are useful. However, R ₉₁ , R ₉₂ R ₉₃ or R ₉₄ −
When not included SO ₃ M ₉₁ group is, -A ₉₁ - is -A ₉₂ - it is selected from the group of.

−A ₉₂ −: Such. Here, M represents a hydrogen atom or a cation providing water solubility.

−A ₉₃ −: Such.

R ₉₁ , R ₉₂ , R ₉₃ and R ₉₄ each represent a hydrogen atom, a hydroxyl group or an alkyl group (preferably having 1 to 8 carbon atoms; for example, a methyl group, an ethyl group, an n-propyl group, an n-
Butyl group, etc.), alkoxy group (1 carbon atom
To 8 are preferred. For example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group and the like, an aryloxy group (for example, a phenoxy group, a naphthoxy group, an o-tolyloxy group, a p-type group)
-Sulfophenoxy group, etc.), halogen atom (eg, chlorine atom, bromine atom, etc.), heterocyclic nucleus (eg, morpholinyl group, piperidyl group, etc.), alkylthio group (eg, methylthio group, ethylthio group, etc.), heterocyclylthio group (eg, Benzothiazolylthio group, benzimidazolythio group, phenyltetrazolylthio group, etc.), arylthio group (for example, phenylthio group, tolylthio group),
Amino group, alkylamino group or substituted alkylamino group (for example, methylamino group, ethylamino group, propylamino group, dimethylamino group, diethylamino group, dodecylamino group, cyclohexylamino group, β-hydroxyethylamino group, di- ( β-hydroxyethyl) amino group, β-sulfoethylamino group), arylamino group, or substituted arylamino group (for example, anilino group,
o-sulfoanilino group, m-sulfoanilino group, p-sulfoanilino group, o-toluidino group, m-toluidino group, p-toluidino group, o-carboxyanilino group, m
-Carboxyanilino group, p-carboxyanilino group,
o-chloroanilino group, m-chloroanilino group, p-chloroanilino group, p-aminoanilino group, o-anisidino group, m-anisidino group, p-anisidino group, o-acetaminoanilino group, hydroxyanilino group, di A sulfophenylamino group, a naphthylamino group, a sulfonaphthylamino group, a heterocyclylamino group (eg, a 2-benzothiazolylamino group, a 2-pyridyl-amino group, etc.), a substituted or unsubstituted aralkylamino group (eg, benzyl group) Represents an amino group, an o-anisylamino group, an m-anisylamino group, a p-anisylamino group, an aryl group (eg, a phenyl group), or a mercapto group.

R ₉₁ , R ₉₂ , R ₉₃ and R ₉₄ may be the same or different from each other. When −A ₉₁ − is selected from the group of −A ₉₃ −,
At least one of R ₉₁ , R ₉₂ , R ₉₃ and R ₉₄ needs to have the above sulfo group (which may be a free acid group or may form a salt). X ₉₁ and Y ₉₁ are -CH = or -N
Wherein X ₉₁ is -CH = and Y ₉₁ is -N =.

Next, specific examples of the compound included in the general formula [A] used in the present invention will be described. However, the present invention is not limited only to these compounds.

(A-1) 4,4'-bis [2,6-di (2-naphthoxy) pyrimidine-
4-ylamino] stilbene-2,2'-disulfonic acid disodium salt (A-2) 4,4'-bis [2,6-di (2-naphthylamino) pyrimidin-4-ylamino] stilbene-2, Disodium salt of 2'-disulfonate (A-3) Disodium salt of 4,4'-bis (2,6-dianilinopyrimidin-4-ylamino) stilbene-2,2'-disulfonate (A-4) 4 , 4'-Bis [2- (2-naphthylamino) -6-anilinopyrimidin-4-ylamino] stilbene-2,2 '
Disodium disulfonate (A-5) 4,4'-bis (2,6-diphenoxypyrimidin-4-ylamino) stilbene-2,2'-disulfonic acid triethylammonium salt (A-6) 4,4 '-Bis [2,6-di (benzimidazolyl-2-thio) pyrimin-4-ylamino] stilbene-2,2'-
Disodium disulfonate (A-7) 4,4'-bis [4,6-di (benzothiazolyl-2-thio)
Pyrimidin-2-ylamino] stilbene-2,2'-disulfonic acid disodium salt (A-8) 4,4'-bis [4,6-di (benzothiazolyl-2-amino) pyrimidin-2-ylamino] stilbene- 2,2 ′
Disodium disulfonate (A-9) 4,4'-bis [4,6-di (naphthyl-2-oxy) pyrimidin-2-ylamino] stilbene-2,2'-disulfonate disodium salt (A -10) 4,4'-bis (4,6-diphenoxypyrimidin-2-ylamino) stilbene-2,2'-disulfonate disodium salt (A-11) 4,4'-bis (4,6- Diphenylthiopyrimidin-2-ylamino) stilbene-2,2'-disulfonate disodium salt (A-12) 4,4'-bis (4,6-dimercaptopyrimidin-2-ylamino) biphenyl-2,2 ' Disodium disulfonate (A-13) 4,4'-Bis (4,6-dianilino-triazin-2-ylamino) stilbene-2,2'-disulfonate disodium salt (A-14) 4,4 '-Bis (4-anilino-6-hydroxy-triazine-2- Ilamino) stilbene-2,2'-disulfonic acid disodium salt (A-15) 4,4'-bis [4,6-di (naphthyl-2-oxy) pyrimidin-2-ylamino] bibenzyl-2,2 ' Disodium disulfonate (A-16) 4,4'-bis (4,6-dianilinopyrimidin-2-ylamino) stilbene-2,2'-disulfonate disodium salt (A-17) 4,4 '-Bis (4-chloro-6- (2-naphthyloxy) pyrimidin-2-ylamino) biphenyl-2,2'
-Disulfonate disodium salt (A-18) 4,4'-bis [4,6-di (1-phenyltetrazolyl-5)
Thio) pyrimidin-2-ylamino] stilbene-2,
Disodium salt of 2'-disulfonate (A-19) 4,4'-bis [4,6-di (benzimidazolyl-2-thio) pyrimidin-2-ylamino] stilbene-2,2 '
Disodium disulfonate (A-20) 4,4'-bis (4-naphthylamino-6-anilino-triazin-2-ylamino) stilbene-2,2'-disulfonate disodium salt Among them, (A-1) to (A-6) are preferable, and in particular, (A-1), (A-2), (A-4),
(A-5), (A-9), (A-15) and (A-20) are preferred.

The compound represented by the general formula [A] is used in an amount of 0.01 to 5 g per mole of silver halide, and the weight ratio of the compound to the sensitizing dye is 5 to 2000 times, preferably 20 to 1500 times. There is an advantageous usage. Further, it is preferable to use the compound represented by the general formula [B] in combination.

Next, the compound represented by formula (B) will be described.

General formula (B) In the formula, Zo ₁ represents a group of nonmetallic atoms necessary for completing a 5- or 6-membered nitrogen-containing heterocyclic ring. This ring may be fused with a benzene or naphthalene ring. For example, thiazoliums {eg, thiazolium, 4-methylthiazolium, benzothiazolium, 5-methylbenzothiazolium, 5-chlorobenzothiazolium, 5-methoxybenzothiazolium, 6-methylbenzothiazolium , 6-
Methoxybenzothiazolium, naphtho [1,2-d] thiazolium, naphtho [2,1-d] thiazolium, etc., oxazoliums such as oxazolium, 4-methyloxazolium, benzoxazolium, 5-chlorobenzo Oxazolium, 5-phenylbenzoxazolium, 5-methylbenzoxazolium, naphtho [1,2-
d] oxazolium, etc.), imidazoliums [for example, 1-methylbenzimidazolium, 1-propyl-5-
Chlorobenzimidazolium, 1-ethyl-5,6-cyclorobenzimidazolium, -allyl-5-trifluoromethyl-6-chloro-benzimidazolium, etc.), selenazoliums {eg benzoselenazolium, 5-chloro Benzoselenazolium, 5-methylbenzoselenazolium, 5-methoxybenzoselenazolium, naphtho [1,2-d] selenazolium and the like]. R
_o1 represents a hydrogen atom, an alkyl group (preferably having 8 or less carbon atoms, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a ventil group and the like) or an alkenyl group (for example, an allyl group and the like). Ro ₂ represents a hydrogen atom or a lower alkyl group (eg, a methyl group, an ethyl group, etc.). Ro ₁ and Ro ₂
May be a substituted alkyl group. Xo ₁ represents an acid anion (eg, Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ^—, etc.). Preferably in zo ₁ is thiazolium compounds are advantageously used. More preferably, substituted or unsubstituted benzothiazolium or naphthothiazolium is advantageously used. In addition, these groups and the like include those substituted even if not specifically mentioned.

Specific examples of the compound represented by the general formula [B] are shown below. However, the present invention is not limited to only these compounds.

The compound represented by formula [B] used in the present invention is advantageously used in an amount of about 0.01 to 5 grams per mole of silver halide in the emulsion.

The ratio (weight ratio) of the infrared sensitizing dye to the compound represented by the general formula [B] is preferably in the range of dye / compound represented by the general formula [B] = 1/1 to 1/300. , Especially 1/2
A range of 1/1/200 is advantageously used.

The compound represented by the general formula [B] used in the present invention can be directly dispersed in the emulsion, or a suitable solvent (eg, water, methyl alcohol, ethyl alcohol, propanol, methyl cellosolve, acetone, etc.)
Alternatively, these solvents can be dissolved in a mixed solvent using a plurality of solvents and added to the emulsion. The sensitizing dye can be added to the emulsion in the form of a solution or a dispersion in a colloid according to the method of adding the sensitizing dye.

The compound represented by the general formula [B] may be added to the emulsion before the sensitizing dye is added, or may be added later. Further, the compound of the formula (B) and the sensitizing dye may be separately dissolved, and these may be separately and simultaneously added to the emulsion, or may be mixed and then added to the emulsion.

It is advantageously used when a combination of an infrared sensitizing dye and a compound represented by the general formula [B] is combined with a compound represented by the general formula [A].

In the infrared-sensitized high silver chloride emulsion, when a heterocyclic mercapto compound is used together with a supersensitizer represented by the general formula [A] or [B], in addition to sensitization and suppression of fog, latent And the dependence of gradation linearity on the development process is remarkably improved.

For example, the heterocyclic compound contains a thiazole ring, an oxazole ring, an oxazine ring, a thiazole ring, a thiazoline ring, a zelenazole ring, an imidazole ring, an indoline ring, a pyrrolidine ring, a tetrazole ring, a thiadiazole ring, a quinoline ring or an oxadiazole ring. It is a compound having a substituted mercapto group. Particularly, a compound into which a carboxyl group, a sulfo group, a carbamoyl group, a sulfamoyl group, or a hydroxyl group is introduced is preferable. JP-B-43-22883 discloses that a mercaptoheterocyclic compound is used as a supersensitizer. In the present invention, a remarkable antifogging effect and a supersensitizing effect are exhibited particularly when used in combination with the compound represented by the general formula [B].

Further, for the red or infrared sensitization according to the present invention, a substituted or unsubstituted polyhydroxybenzene represented by the following general formula [Ea], [Eb] or [Ec] is used as a supersensitizer, and formaldehyde. A condensate of 2 to 10 units of a condensation unit with is useful. In addition, there is an effect that the regression of the latent increase due to aging is prevented, and the gradation is prevented from lowering.

General formula (Ea) General formula (Eb) General formula (Ec) In the formula, R ₀₃ and R ₀₄ are OH, OM ₀₁ , OR ₀₆ , NH ₂ , and NHR, respectively.
_{06, -N (R 06) 2} , represent -NHNH ₂ or -NHNHR _06.
However, _R06 represents an alkyl group (1-8 carbon atoms), an allyl group or an aralkyl group.

M ₀₁ represents an alkali metal or an alkaline earth metal.

R ₀₅ represents OH or a halogen atom.

n ₀₁ and n ₀₂ represent 1, 2 or 3, respectively.

Next, specific examples of the substituted or unsubstituted polyhydroxybenzene, which is a condensation component of the aldehyde condensate used in the present invention, will be shown, but the present invention is not limited thereto.

(E-1) β-resorcinic acid (E-2) γ-resorcinic acid (E-3) 4-hydroxybenzoic acid hydrazide (E-4) 3,5-hydroxybenzoic acid hydrazide (E-5) p-chloro Phenol (E-6) Sodium hydroxybenzenesulfonate (E-7) p-hydroxybenzoic acid (E-8) o-hydroxybenzoic acid (E-9) m-hydroxybenzoic acid (E-10) p-dioxy Benzene (E-11) Gallic acid (E-12) Methyl p-hydroxybenzoate (E-13) O-hydroxybenzenesulfonic acid amide (E-14) N-ethyl-o-hydroxybenzoic acid amide (E-15) N-diethyl-o-hydroxybenzoic acid amide (E-16) o-hydroxybenzoic acid-2-methylhydrazide More specifically, it can be selected from derivatives of the compounds represented by formulas (IIa), (IIb) and (IIc) described in JP-B-49-49504.

The emulsion used in the present invention is any of a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface and a so-called internal latent image type emulsion in which a latent image is mainly formed inside the grain. Is also good.

When the present invention is applied to a color light-sensitive material, the color light-sensitive material is coupled with an oxidized form of an aromatic amine-based color developing agent to form a yellow coupler, a magenta coupler, and a cyan coupler which respectively form yellow, magenta, and cyan. Is usually used.

Cyan coupler preferably used in the present invention,
The magenta coupler and the yellow coupler are represented by the following formulas (C-I), (C-II), (M-I), (M-II) and (Y).

General formula (C-I) General formula (C-II) General formula (MI) General formula (M-II) General formula (Y) In the general formulas (C-1) and (C-II), R ₁ , R ₂
And R ₄ represents a substituted or unsubstituted aliphatic, aromatic or heterocyclic group; R ₃ , R ₅ and R ₆ represent a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group or an acylamino group; ₃ may represent a non-metallic atomic group forming a 5- or 6-membered nitrogen-containing ring together with R ₂ . Y ₁ and Y _{2 each} represent a hydrogen atom or a group capable of leaving during a coupling reaction with an oxidized form of a developing agent. n represents 0 or 1.

R ₅ in the general formula (C-II) is preferably an aliphatic group, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentadecyl group, a tert-butyl group, a cyclohexyl group, a cyclohexylmethyl group, Examples include a phenylthiomethyl group, a dodecyloxyphenylthiomethyl group, a butanamidomethyl group, a methoxymethyl group, and the like.

Preferred examples of the cyan coupler represented by the general formula (CI) or (C-II) are as follows.

In formula (CI), preferred R ₁ is an aryl group or a heterocyclic group, and is a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, an acyl group, a carbamoyl group, a sulfonamide group, or a sulfamoyl group. , A sulfonyl group, a sulfamide group, an oxycarbonyl group, and an aryl group substituted with a cyano group.

When R ₃ and R ₂ do not form a ring in formula (CI), R ₂ is preferably a substituted or unsubstituted alkyl group,
It is an aryl group, particularly preferably a substituted aryloxy-substituted alkyl group, and R ₃ is preferably a hydrogen atom.

In formula (C-II), R ₄ is preferably a substituted or unsubstituted alkyl group or aryl group, and particularly preferably a substituted aryloxy-substituted alkyl group.

In the general formula (C-II), preferred R ₅ has 2 to 15 carbon atoms.
And a methyl group having a substituent having 1 or more carbon atoms, and the substituent is preferably an arylthio group, an alkylthio group, an acylamino group, an aryloxy group, or an alkyloxy group.

In the general formula (C-II), R ₅ is more preferably an alkyl group having 2 to 15 carbon atoms, particularly preferably an alkyl group having 2 to 4 carbon atoms.

In the general formula (C-II), R ₆ is preferably a hydrogen atom or a halogen atom, and particularly preferably a carbon atom or a fluorine atom. Preferred Y ₁ and Y ₂ in the general formulas (CI) and (C-II) are a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, and a sulfonamide group, respectively.

In the general formula (MI), R ₇ and R ₉ represent an aryl group, R ₈ represents a hydrogen atom, an aliphatic or aromatic acyl group, an aliphatic or aromatic sulfonyl group, and Y ₃ represents hydrogen. Represents an atom or a leaving group. The substituents permitted for the aryl group (preferably a phenyl group) for R ₇ and R ₃ are the same as the substituents permitted for the substituent R ₁ , and when there are two or more substituents, they are the same. But they may be different. R ₈
Is preferably a hydrogen atom, an aliphatic acyl group or a sulfonyl group, and particularly preferably a hydrogen atom. Desirable Y ₃ is of a type capable of releasing at any of a sulfur, oxygen or nitrogen atom, and particularly preferred is a type of releasing at a sulfur atom as described in, for example, US Pat. No. 4,351,897 and International Publication WO88 / 04795.

In the general formula (M-II), R ₁₀ represents a hydrogen atom or a substituent. Y ₄ represents a hydrogen atom or a leaving group, particularly preferably a halogen atom or an arylthio group. Za, Zb and
Zc represents methine, substituted methine, = N- or -NH-,
One of the -Zb bond and the Zb-Zc bond is a double bond, and the other is a single bond. The case where the Zb-Zc bond is a carbon-carbon double bond includes the case where it is a part of an aromatic ring. When R ₁₀ or Y ₄ forms a dimer or more multimer, Za,
When Zb or Zc is a substituted methine, the case where the substituted methine forms a dimer or more multimer is included.

Among the pyrazoloazole couplers represented by the general formula (M-II), the imidazo [1,2-b] pyrazole described in U.S. Pat. No. 4,500,630 is advantageous in terms of low yellow side absorption and light fastness of a generated dye. Are preferred, US Pat.
The pyrazolo [1,5-b] [1,2,4] triazole described in 4,540,654 is particularly preferred.

In addition, a branched alkyl group as described in JP-A-61-65245 is directly linked to the 2-, 3- or 6-position of the pyrazolotriazole ring to form a pyrazolotriazole coupler.
Pyrazoloazole couplers containing a sulfonamide group in the molecule as described in 65246, JP-A-61-147254
Pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group as described in JP-A No. 226,849 and pyrazoloazole couplers having an alkoxy group or aryloxy group at the 6-position as described in EP-A-226,849 and EP 294,785. The use of zorotriazole couplers is preferred.

In the general formula (Y), R ₁₁ represents a halogen atom, an alkoxy group, a trifluoromethyl group or an aryl group, and R ₁₂ represents a hydrogen atom, a halogen atom or an alkoxy group. A is _{-NHCOR 13, -NHSO 2 -R 13,} -SO 2 NHR 13,
−COOR ₁₃ , Represents Here, R ₁₃ and R ₁₄ each represent an alkyl group, an aryl group or an acyl. Y ₅ represents a leaving group. R ₁₂ and R
₁₃ and R ₁₄ are the same as the substituents permitted for R ₁ and the leaving group Y ₅ is preferably of a type capable of leaving at either an oxygen atom or a nitrogen atom; Atomic desorption type is particularly preferred.

Formulas (C-I), (C-II), (M-I), and (M-
Specific examples of the couplers represented by II) and (Y) are listed below.

The couplers represented by the above general formulas (C-I) to (Y) are usually added in the silver halide emulsion layer constituting the photosensitive layer in an amount of 0.1 to 1.0 mol, preferably 0.1 to 1.0 mol per mol of silver halide.
0.50.5 mol.

In the present invention, various known techniques can be applied to add the coupler to the photosensitive layer. Usually, it can be added by an oil-in-water dispersion method known as an oil protection method, and after being dissolved in a solvent, it is emulsified and dispersed in a gelatin aqueous solution containing a surfactant. Alternatively, water or an aqueous gelatin solution may be added to a coupler solution containing a surfactant to form an oil-in-water dispersion with phase inversion. The alkali-soluble coupler can also be dispersed by a so-called Fisher dispersion method. After removing the low-boiling organic solvent from the coupler dispersion by a method such as distillation, noodle washing or ultrafiltration, it may be mixed with a photographic emulsion.

Dielectric constant (25 ° C) as a dispersion medium for such couplers
It is preferable to use a high-boiling organic solvent having a refractive index of 2 to 20 and a refractive index (25 ° C.) of 1.5 to 1.7 and / or a water-insoluble polymer compound.

As the high boiling point organic solvent, preferably, the following general formula (A)
The high-boiling organic solvent represented by (E) is used.

General formula (A) General formula (B) W ₁ -COO-W ₂ General formula (C) General formula (D) Formula (E) W ₁ —O—W ₂ (wherein W ₁ , W ₂ and W ₃ each represent a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aryl group or heterocyclic group; W ₄ is W ₁ , OW ₁ or SW
_And n is an integer of 1 to 5, and when n is 2 or more, W ₄ may be the same or different. In the general formula (E), W ₁ and W ₂ represent a condensed ring. May be formed).

The high-boiling organic solvent that can be used in the present invention is a compound that is not miscible with water having a melting point of 100 ° C. or less and a boiling point of 140 ° C. or more other than the general formulas (A) to (E). Can be used. The high boiling point organic solvent preferably has a melting point of 80 ° C. or lower. The boiling point of the high boiling organic solvent is preferably 160 ° C.
And more preferably 170 ° C. or higher.

Details of these high-boiling organic solvents are described in
No. 215272, page 137, lower right column to page 144, upper right column.

These couplers may be impregnated with a loadable latex polymer (for example, U.S. Pat.No. 4,203,716) in the presence or absence of the high-boiling organic solvent or dissolved in a water-insoluble and organic solvent-soluble polymer. It can be emulsified and dispersed in a hydrophilic colloid aqueous solution.

Preferably, pages 12 to 30 of WO 88/00723
The homopolymers or copolymers described on the page are used, and the use of an acrylamide polymer is particularly preferred for stabilizing a color image.

The light-sensitive material prepared by using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, and the like as a color fogging inhibitor.

Various anti-fading agents can be used in the light-sensitive material of the present invention. That is, hydroquinones as organic anti-fading agents for cyan, magenta and / or yellow images,
6-hydroxychromans, 5-hydroxycoumarins, spirochromans, p-alkoxyphenols,
Representative examples include hindered phenols, mainly bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds. No. Further, metal complexes represented by (bissalicylaldoximato) nickel complex and (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

Specific examples of the organic anti-fading agent are described in the specifications of the following patents.

Hydroquinones are disclosed in U.S. Pat.Nos. 2,360,290 and 2,4
No. 18,613, No. 2,700,453, No. 2,701,197, No. 2,
No. 728,659, No. 2,732,300, No. 2,735,765, No.
No. 3,982,944, No. 4,430,425, UK Patent No. 1,363,921
No., U.S. Pat.Nos. 2,710,801 and 2,816,028,
6-Hydroxychromans, 5-hydroxycoumarins, and spirochromans are described in U.S. Pat.
No. 3,573,050, No. 3,574,627, No. 3,698,909, No. 3,764,337, JP-A-52-152225, Spiroindanes in U.S. Pat.No. 4,360,589, p-Alkoxyphenols in U.S. Pat. UK Patent 2,0
No. 66,975, JP-A-59-10539, JP-B-57-19765, and the like, hindered phenols are disclosed in U.S. Pat.
No., JP-A-52-72224, U.S. Pat.
Nos. 52-6623, gallic acid derivatives, methylenedioxyibenzenes, and aminophenols are described in U.S. Pat.
No. 4,268,593, British Patent No. 1,326,889, No. 1,
Nos. 354,313, 1,410,846, JP-B-51-1420, JP-A-58-114036, JP-A-59-53846, and JP-A-59-78344, the metal complexes are U.S. Pat. 4,241,1
55 and British Patent 2,027,731 (A). These compounds can achieve the purpose by adding 5 to 100% by weight of the corresponding coupler to the photosensitive layer, usually by co-emulsifying the coupler with the coupler. In order to prevent the deterioration of the cyan dye image due to heat and particularly to light, it is more effective to introduce an ultraviolet absorber into the cyan coloring layer and the layers on both sides adjacent thereto.

Examples of the ultraviolet absorber include benzotriazole compounds substituted with an aryl group (for example, those described in U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (for example, those described in U.S. Pat. Nos. 3,314,794 and 3,352,681),
Benzophenone compounds (for example, those described in JP-A-46-2784) and cinnamate compounds (for example, US Pat.
3,705,805 and 3,707,395), butadiene compounds (described in U.S. Pat. No. 4,045,229),
Alternatively, benzooxide compounds (for example, US Pat.
3,406,070 and 3,677,672 and 4,271,307) can be used. UV-absorbing couplers (eg, α-naphthol-based cyan dye-forming couplers)
Alternatively, an ultraviolet absorbing polymer or the like may be used. These ultraviolet absorbers may be mordanted to a specific layer.

Above all, a benzotriazole compound substituted with the above-mentioned aryl group is preferable.

It is particularly preferable to use the following compounds together with the above-mentioned coupler. In particular, combination use with a pyrazoloazole coupler is preferred.

That is, the compound (F) which forms a chemically inert and substantially colorless compound by chemically bonding with the aromatic amine-based developing agent remaining after the color developing process and / or the aromatic compound remaining after the color developing process. The compound (G) which forms a chemically inert and substantially colorless compound by chemically bonding with an oxidized form of an aromatic amine color developing agent can be used simultaneously or alone, for example, in storage after processing. It is preferable in order to prevent the generation of stains and other side effects due to the formation of a coloring dye due to the reaction between the color developing agent or its oxidized product and the coupler remaining in the film.

Preferred as the compound (F) is a compound having a secondary reaction rate constant k ₂ (in trioctyl phosphate at 80 ° C.) of 1.0 / mol · sec to 1 × 10 ⁻⁵ / mol · sec with the second reaction rate constant with p-anisidine. Compound. The secondary reaction rate constant can be measured by the method described in JP-A-63-158545.

If k ₂ is greater than this range, the compound itself becomes unstable, resulting in decomposition reacts with gelatin or water. On the other hand, if k ₂ is smaller than this range, the reaction with the remaining aromatic amine-based developing agent is slow, and as a result, the side effect of the remaining aromatic amine-based developing agent may not be prevented.

More preferable compound (F) can be represented by the following general formula (FI) or (F II).

General formula (FI) R _1- (A) _n -X General formula (F II) In the formula, R ₁ and R ₂ each represent an aliphatic group, an aromatic group, or a heterocyclic group. n represents 1 or 0. A represents a group which forms a chemical bond by reacting with an aromatic amine-based developer, and X represents a group which is eliminated by reacting with an aromatic amine-based developer. B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, or a sulfonyl group, and Y represents that an aromatic amine-based developing agent is added to the compound of the general formula (F II). Represents a promoting group. Here, R ₁ and X, Y and R ₂ or B may be bonded to each other to form a cyclic structure.

Representative methods of chemically bonding with the residual aromatic amine-based developing agent are a substitution reaction and an addition reaction.

Specific examples of the compounds represented by formulas (FI) and (F II) are described in JP-A-63-158545, JP-A-62-283338,
Those described in specifications such as European Patent Publication Nos. 298321 and 277589 are preferable.

On the other hand, the compound (G) which forms a chemically inactive and colorless compound by chemically bonding to an oxidized form of an aromatic amine-based developing agent remaining after the color development treatment is more preferably represented by the following general formula (GI) ).

Formula (GI) RZ In the formula, R represents an aliphatic group, an aromatic group, or a heterocyclic group. Z represents a nucleophilic group or a group which decomposes in the light-sensitive material to release a nucleophilic group. In the compound represented by the general formula (GI), Z is Pearson's nucleophilicity “CH ₃ I value (RGPearso
n, et al., J. Am. Chem. Soc., 90 , 319 (1968)) or a group derived therefrom is preferred.

Specific examples of the compound represented by the general formula (GI) are described in EP-A-255722, JP-A-62-143048 and JP-A-62-143048.
Preferred are those described in 229145, Japanese Patent Application Nos. 63-136724 and 62-214681, and European Patent Publications 298321 and 227589.

The details of the combination of the compound (G) and the compound (F) are described in EP-A-277589.

The light-sensitive material prepared according to the present invention contains a water-soluble dye or a dye which becomes water-soluble by photographic processing as a filter dye in the hydrophilic colloid layer, or for various purposes such as prevention of irradiation or halation. You may. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful.

As the binder or protective colloid that can be used in the emulsion layer of the light-sensitive material of the present invention, gelatin is advantageously used, but other hydrophilic colloids can be used alone or together with gelatin.

In the present invention, gelatin is lime-treated,
Either one treated with an acid may be used. The details of the method for producing gelatin are described in Arthur Wuice, The Macromolecular Chemistry of Gelatin (Academic Press, 1964).

As the support used in the present invention, a transparent film such as a cellulose nitrate film or a polyethylene terephthalate, which is usually used for a photographic light-sensitive material, or a reflective support can be used. For the purposes of the present invention, the use of a reflective support is more preferred.

The term "reflective support" used in the present invention refers to a material which enhances reflectivity and sharpens a dye image formed in a silver halide emulsion layer. Examples include those coated with a hydrophobic resin dispersedly containing a light reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, and calcium sulfate, and those using a hydrophobic resin dispersedly containing a light reflecting substance as a support. For example, baryta paper, polyethylene-coated paper, polypropylene-based synthetic paper, a transparent support provided with a reflective layer or combined with a reflective substance, such as a glass plate, polyethylene terephthalate, a polyester film such as cellulose triacetate or cellulose nitrate, Examples include a polyamide film, a polycarbonate film, a polystyrene film, and a vinyl chloride resin.

Other reflective supports include specular or secondary
A support having a seed diffuse reflective metal surface can be used. The metal surface has a spectral reflectance of 0.5 in the visible wavelength range.
The above materials are preferred, and the metal surface is preferably roughened or diffusely reflective using metal powder. As the metal, aluminum, tin, silver, magnesium or an alloy thereof is used, and the surface may be the surface of a metal plate, a metal foil, or a metal thin layer obtained by rolling, vapor deposition, plating, or the like.
Above all, it is preferable to obtain a metal by vapor deposition on another substrate. It is preferable to provide a water-resistant resin, especially a thermoplastic resin layer, on the metal surface. An antistatic layer is preferably provided on the side of the support of the present invention opposite to the side having the metal surface. For details of such a support, see, for example, JP-A-61-210346.
Nos. 63-24247, 63-24251 and 63-24255.

 These supports can be appropriately selected depending on the purpose of use.

As the light-reflective substance, it is preferable to sufficiently knead a white pigment in the presence of a surfactant.
It is preferable to use those treated with a to tetravalent alcohol.

The occupied area ratio (%) per defined unit area of the white pigment fine particles is most typically obtained by dividing the observed area into adjacent 6 μm × 6 μm unit areas and projecting the unit area. It can be determined by measuring the occupied area ratio (%) (R ₁ ) of the fine particles. Variation coefficient of the occupied area ratio (%) is the ratio of the standard deviation s of R ₁ to the average value of R _i () s /
Can be obtained by The number (n) of the target unit areas is preferably 6 or more. Therefore the coefficient of variation s / Can be obtained by

In the present invention, the occupied area ratio of the pigment fine particles (%)
Is preferably 0.15 or less, particularly preferably 0.12 or less. 0.08
In the following cases, it can be said that the dispersibility of the particles is substantially “uniform”.

The color photographic light-sensitive material according to the present invention includes color development,
It is preferable to perform bleach-fixing and washing (or stabilization). Bleaching and fixing may be performed in a single bath or separately.

The color developing solution used in the present invention contains a known aromatic primary amine color developing agent. A preferred example is a p-phenylenediamine derivative, examples of which are shown below, but are not limited thereto.

D-1 N, N-diethyl-p-phenylenediamine D-2 2-amino-5-diethylaminotriene D-3 2-amino-5- (N-ethyl-N-laurylamino) toluene D-4 4- [ N-ethyl-N- (β-hydroxyethyl) amino] aniline D-5 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino) aniline D-6 2-methyl-4 [N -Ethyl-N- (3-hydroxypropyl) amino] aniline D-7 4-amino-3-methyl-N-ethyl-N-
[Β- (methanesulfonamido) ethyl] -aniline D-8 N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide D-9 N, N-dimethyl-p-phenylenediamine D-10 4-amino -3-Methyl-N-ethyl-N-methoxyethylaniline D-11 4-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-12 4-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline Particularly preferred exemplary compounds among the above-mentioned p-phenylenediamine derivatives are D-4 and D-6. Further, if necessary, a developing agent can be mixed and used. In addition, these p-phenylenediamine derivatives may be salts such as sulfate, hydrochloride, sulfite, and p-toluenesulfonate. The amount of the aromatic primary amine developing agent to be used is preferably about 0.1 g to about 20 g, more preferably about 0.5 g to about 12 g, per developer 11.

In the practice of the present invention, it is preferable to use a developer that does not substantially contain benzyl alcohol. Here, "substantially free" means that the benzyl alcohol concentration is preferably 2 ml / l or less, more preferably 0.5 ml / l or less, and most preferably no benzyl alcohol is contained.

More preferably, the developer used in the present invention does not substantially contain sulfite ions. Sulfite ions have a function of dissolving silver halide and a function of reducing the efficiency of dye formation by reacting with an oxidized developing agent simultaneously with the function as a preservative of the developing agent. Such an effect is presumed to be one of the causes of the increase in the fluctuation of the photographic characteristics due to the continuous processing. Here, “substantially free” means that the concentration of sulfite ions is preferably 3.0 × 10 ⁻³ mol / l or less, and most preferably no sulfite ions are contained. However, in the present invention, a very small amount of sulfite ion used for preventing oxidation of a processing agent kit in which a developing agent is concentrated before preparing a working solution is excluded.

The developer used in the present invention preferably does not substantially contain sulfite ions, and more preferably does not substantially contain hydroxylamine. this is,
This is because hydroxylamine itself has a silver developing activity at the same time as functioning as a preservative of the developer, and fluctuations in the concentration of hydroxylamine are considered to greatly affect photographic characteristics. The term "substantially free of hydroxylamine" as used herein means that the hydroxylamine concentration is preferably 5.0 × 10 ⁻³ mol / l or less, and most preferably contains no hydroxylamine.

More preferably, the developer used in the present invention contains an organic preservative in place of the hydroxylamine and sulfite ions.

Here, the organic preservative refers to any organic compound that reduces the deterioration rate of an aromatic primary amine color developing agent by being added to a processing solution of a color photographic light-sensitive material. That is, organic compounds having a function of preventing oxidation of a color developing agent by air or the like, among which hydroxylamine derivatives (excluding hydroxylamine; the same applies hereinafter), hydroxamic acids, hydrazines, hydrazides, phenols, α-hydroxy ketones, α-amino ketones,
Sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, condensed amines, and the like are particularly effective organic preservatives. These are disclosed in
−4235, 63−30845, 63−21647, 63−4465
No. 5, 63-53551, 63-43140, 63-56654,
63-58346, 63-43138, 63-146041, 63
-44657, 63-44656, U.S. Patent No. 3,615,503,
No. 2,494,903, JP-A-52-143020, JP-B-48-30496
No., etc.

Other preservatives include JP-A Nos. 57-44148 and 57-5.
Various metals described in 3749, salicylic acids described in JP-A-59-180588, alkanolamines described in JP-A-54-3532, polyethyleneimines described in JP-A-56-94349, U.S. Pat. An aromatic polyhydroxy compound described in 3,746,544 or the like may be contained as necessary. In particular, addition of alkanolamines such as triethanolamine, dialkylhydroxylamine such as diethylhydroxylamine, hydrazine derivatives or aromatic polyhydroxy compounds is preferred.

Among the above organic preservatives, hydroxylamine derivatives and hydrazine derivatives (hydrazines and hydrazides)
Are particularly preferred, and details thereof are described in JP-A-1-9795.
No. 3, No. 1-186939, No. 1-186940, No. 1-187557
No. etc.

It is more preferable to use the hydroxylamine derivative or the hydrazine derivative in combination with an amine in terms of improving the stability of the color developing solution, and further improving the stability during continuous processing.

Examples of the amines include cyclic amines described in JP-A-63-239447, amines described in JP-A-63-128340, and other amines described in JP-A-1-186939 and JP-A-1-186939. Amines such as those described in US Pat.

In the present invention, 3.5 × 1 chloride ion in the color developer
It is preferably contained in an amount of 0 ^{-2 to} 1.5 × 10 ^-1 mol / l. Particularly preferred is 4 × 10 ^-2 to 1 × 10 ^-1 mol / l. If the chloride ion concentration is more than 1.5 × 10 ^-1 to 10 ^-1 mol / l, it has the disadvantage of delaying the development, and is not preferred for achieving the object of the present invention of rapid and high maximum concentration. Also, 3.5
If it is less than × 10 ^-2 mol / l, it is not preferable in preventing fog.

In the present invention, the bromine ion in the color developer is 3.0
It is preferable to contain from × 10 ⁻⁵ mol / l to 1.0 × 10 ⁻³ mol / l. More preferably, it is 5.0 × 10 ^{−5 to} 5 × 10 ⁻⁴ mol / l. When the bromine ion concentration is more than 1 × 10 ^-3 mol / l, the development is delayed, and the maximum concentration and sensitivity are reduced. When the bromine ion concentration is less than 3.0 × 10 ^-5 mol / l, fog cannot be sufficiently prevented. .

Here, chlorine ions and bromine ions may be directly added to the developer or may be eluted from the photosensitive material into the developer during the development processing.

When directly added to the color developer, examples of the chloride ion supply material include sodium chloride, potassium chloride, ammonium chloride, lithium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride, and cadmium chloride, with the preferred ones being preferred. Are sodium chloride and potassium chloride.

Further, it may be supplied from a fluorescent whitening agent added to the developer.

Sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide, thallium bromide Among them, preferred are potassium bromide and sodium bromide.

When eluted from the light-sensitive material during the development processing, both chloride ions and bromine ions may be supplied from the emulsion, or may be supplied from sources other than the emulsion.

The color developer used in the present invention is preferably pH 9
To 12, more preferably 9 to 11.0, and the color developer may further contain a compound of a known developer component.

In order to maintain the above pH, it is preferable to use various buffers. Buffers include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt,
N, N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-methyl-1,3-propanediol salt, valine salt , Proline salts, trishydroxyaminomethane salts, lysine salts, and the like. In particular, carbonate, phosphate, tetraborate, and hydroxybenzoate are soluble and have a high pH of 9.0 or more.
It is excellent in the buffering capacity in the H region, has no adverse effects on photographic performance (such as fog) even when added to a color developer, and has the advantages of being inexpensive, and it is particularly preferable to use these buffers.

Specific examples of these buffers include sodium carbonate,
Potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), tetraborate Potassium, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-
Sodium sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate)
And the like. However, the invention is not limited to these compounds.

The amount of the buffer added to the color developer is preferably at least 0.1 mol / l, particularly preferably from 0.1 mol / l to 0.4 mol / l.

In addition, various chelating agents can be used in the color developer as a precipitation inhibitor for calcium or magnesium, or for improving the stability of the color developer.
For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenesulfonic acid, transsilohexanediaminetetraacetic acid, 1 , 2-Diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N'- Bis (2-hydroxylbenzyl) ethylenediamine-N, N'-diacetic acid and the like can be mentioned.

These chelating agents may be used in combination of two or more as required.

These chelating agents may be added in an amount sufficient to block the metal ions in the color developer. For example, 11
It is about 0.1g to 10g per unit.

An optional development accelerator can be added to the color developer if desired.

As development accelerators, JP-B-67-16088 and JP-B-37-598
No. 7, No. 38-7826, No. 44-12380, No. 45-9919, and thioether compounds represented by U.S. Pat. p-phenylenediamine compound, JP-A-50-1377
No. 26, JP-B-44-30074, JP-A-56-156826 and 5
Quaternary ammonium salts represented by 2-43429 and the like, U.S. Pat.Nos. 2,494,903, 3,128,182, 4,230,796,
No. 3,253,919, JP-B-41-11431, U.S. Pat.
Nos. 546, 2,596,926 and 3,582,346, amine compounds described in JP-B-37-16088, JP-B-42-25201, U.S. Pat.No. 3,128,183, JP-B-41-11431, JP-B-42-2388.
No. 3, US Pat. No. 3,532,501, etc., polyalkylene oxides, 1-phenyl-3-pyrazolidones, imidazoles, and the like can be added as desired.

In the present invention, an optional antifoggant can be added as desired. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-
Nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-
Representative examples include nitrogen-containing heterocyclic compounds such as thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

The color developer applicable to the present invention preferably contains a fluorescent whitening agent. 4,4 'as fluorescent whitening agent
-Diamino-2,2'-disulfostilbene compounds are preferred. The addition amount is 0 to 5 g / l, preferably 0.1 g to 4 / l.

Further, various surfactants such as alkyl sulfonic acid, aryl sulfonic acid, aliphatic carboxylic acid and aromatic carboxylic acid may be added as required.

The processing temperature of the color developer applicable to the present invention is 20 to
50 ° C, preferably 30 to 45 ° C. Processing time is virtually 20
Within seconds. The replenishment amount is preferably smaller, but ^{20 to} 600 ml per 1 m2 of the light-sensitive material is appropriate, preferably 50 to 30 ml.
0 ml. More preferably 60ml-200ml most preferably
It is between 60 ml and 150 ml.

In the present invention, the development time is preferably substantially within 20 seconds, but "substantially 20 seconds" as used herein means that the photosensitive material is transferred from the time when the photosensitive material is put into the developer tank to the next tank. , And includes the time in the air from the developer tank to the next tank.

Next, the desilvering step applicable to the present invention will be described. As the desilvering step, generally, any steps such as a bleaching step-fixing step, a fixing step-bleach-fixing step, a bleaching step-bleach-fixing step and a bleach-fixing step may be used.

The bleaching solution, bleach-fixing solution and fixing solution applicable to the present invention will be described below.

As the bleaching agent used in the bleaching solution or the bleach-fixing solution, any bleaching agent can be used. In particular, organic complex salts of iron (III) (for example, ethylenediaminetetraacetic acid,
Preferred are aminopolycarboxylic acids such as diethylenetriaminepentaacetic acid and complex salts such as aminopolyphosphonic acid, phosphonocarboxylic acid and organic phosphonic acid) or organic acids such as citric acid, tartaric acid and malic acid; persulfates; hydrogen peroxide and the like. .

Among these, organic complex salts of iron (III) are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution. Aminopolycarboxylic acids, aminopolyphosphonic acids, or organic phosphonic acids or salts thereof useful for forming organic complex salts of iron (III) include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminopropane. Examples thereof include tetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, iminodiacetic acid, and glycol ether diaminetetraacetic acid. These compounds may be any of the sodium, potassium, thylium or ammonium salts. Among these compounds, ethylenediaminetetraacetic acid,
Iron (III) complex salts of diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, and methyliminodiacetic acid are preferred because of their high bleaching power.

These ferric ion complex salts may be used in the form of a complex salt or a ferric salt such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate. And a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc., to form a ferric ion complex salt in a solution. In addition, the chelating agent may be used in excess of forming a ferric ion complex salt.
Of the iron complexes, aminopolycarboxylate iron complexes are preferred, and the amount added is 0.01 to 1.0 mol / l, preferably 0.05 to 1.0 mol / l.
0.50 mol / l.

In the bleaching solution, the bleach-fixing solution and / or the prebath thereof,
Various compounds can be used as a bleaching accelerator.
For example, U.S. Pat.No. 3,893,858, German Patent No.
No. 1,290,812, JP-A-53-95630, and compounds having a mercapto group or a disulfide bond described in Research Disclosure No. 17129 (July, 1978); Thiourea-based compounds described in JP-A Nos. 52-20832, 53-32735, U.S. Pat. No. 3,706,561 and the like, or halogen compounds such as iodine and bromine ions are preferred in terms of excellent bleaching power.

Other bleaching solutions or bleach-fixing solutions applicable to the present invention include bromide (eg, potassium bromide, sodium bromide, ammonium bromide) or chloride (eg, potassium chloride, sodium chloride, ammonium chloride) or iodine. A rehalogenating agent such as an iodide (eg, ammonium iodide). One or more inorganic acids having a pH buffering capacity, such as borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, if desired; Organic acids and their alkali metal or ammonium salts or corrosion inhibitors such as ammonium nitrate and guanidine can be added.

Fixing agents used in the bleach-fixing solution or the fixing solution include known fixing agents, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylenebisthioglycolic acid Thioether compounds such as 3,6-dithia-1,8-octanediol and water-soluble silver halide dissolving agents such as thioureas, which can be used alone or in combination of two or more. .

Also, a special bleach-fixing solution comprising a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can be used. In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred. The amount of fixing agent per liter is 0.3 to 2
Mole is preferred, more preferably in the range of 0.5 to 1.0 mole. The pH range of the bleach-fixing solution or fixing solution is preferably 3 to 10, more preferably 5 to 9.

Further, the bleach-fixing solution may contain other various types of fluorescent whitening agents, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

Bleach-fixing solutions and fixing solutions include sulfites (eg, sodium sulfite, potassium sulfite, ammonium sulfite, etc.) and bisulfites (eg, ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.) as preservatives,
It preferably contains a sulfite ion releasing compound such as metabisulfite (for example, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.). These compounds are converted to sulfite ions from about 0.02 to
It is preferable to contain 0.05 mol / l, more preferably
0.04 to 0.40 mol / l.

As a preservative, sulfite is generally added,
In addition, you may add ascorbic acid, a carbonyl bisulfite adduct, a carbonyl compound, etc.

Further, a buffer, an optical brightener, a chelate, an antifoaming agent, a fungicide, and the like may be added as required.

After desilvering such as fixing or bleach-fixing, washing and / or stabilization are generally performed.

The amount of rinsing water in the rinsing step can be set in a wide range depending on the characteristics of the photosensitive material (for example, depending on the material used such as a coupler), the use, the rinsing water temperature, the number of rinsing tanks (the number of stages), and various other conditions. Of these, the relationship between the number of washing tanks and water volume in the multi-stage countercurrent method is described in the Journal of the Society of Motion Picture and Television Engineers (Journal of the Society of Moti
on Picture and Television Engineers) Volume 64, p.248
253 (May 1955). Usually, the number of stages in the multistage countercurrent system is preferably 2 to 6, and particularly preferably 2 to 5.

According to the multi-stage countercurrent method, the amount of washing water can be greatly reduced,
For example, 300 ml or less per 1 m ^{2 of the} photosensitive material is possible, and the effect of the present invention is remarkable.However, due to an increase in the residence time of water in the tank, bacteria propagate, and the generated suspended matter adheres to the photosensitive material. Problem arises. As a solution to such a problem, the method of reducing calcium and magnesium described in JP-A-62-288838 can be used very effectively. Further, isothiazolone compounds and thiabendazoles described in JP-A-57-8542, chlorine-based germicides such as chlorinated sodium isocyanurate described in JP-A-61-120145, and JP-A-61-26761. Benzotriazole, Copper Ions and Others by Hiroshi Horiguchi, "The Chemistry of Bactericidal and Antifungal Activities" (1986
Year) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan Society of Antimicrobial and Antifungal, "Encyclopedia of Antifungal Agents" (1986). The bactericides described can also be used.

Further, in the washing water, a surfactant as a draining agent and a chelating agent represented by EDTA as a hardening agent can be used.

It is possible to carry out the treatment with the stabilizing solution directly after the washing step or without the washing step. A compound having an image stabilizing function is added to the stabilizing solution, for example, an aldehyde compound represented by formalin, or a film suitable for stabilizing a dye.
Examples include a buffer for adjusting the pH, and an ammonium compound. Further, in order to prevent the growth of bacteria in the liquid and impart fungicidal properties to the processed photosensitive material, the above-mentioned various bactericides and fungicides can be used.

Further, a surfactant, a fluorescent whitening agent and a hardening agent may be added. In the processing of the light-sensitive material of the present invention, when stabilization is directly performed without going through a washing step, a method disclosed in
Known methods described in JP-A Nos. 8543, 58-14834, 60-220345, etc. can all be used.

Further, an organic phosphonic acid and / or an organic phosphonate can be preferably used as a chelating agent for the purpose of preventing stain.

These organic phosphonic acids and / or organic phosphonates may be used alone or in combination of two or more.

The amount of the organic phosphonic acid and / or organic phosphonate added to the washing or stabilizing bath can be determined by the amount of ferric ethylenediaminetetraacetate contained in the photosensitive material. 2.9 mmol-2 per liter
An addition amount of 90 mmol is preferred. More preferably, 14.6 mmol
146 mmol. If the amount is too large, the surface may be sticky, while if it is too small, the original effect of improving stain cannot be obtained.

It is also a preferred embodiment to use a magnesium or bismuth compound.

In addition, it is also a preferred embodiment to use a chelating agent such as 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, or a magnesium or bismuth compound.

A so-called rinsing liquid is also used as a washing liquid or a stabilizing liquid used after the desilvering treatment.

The preferred pH of the washing step or the stabilization step is 4 to 10, more preferably 5 to 8. The temperature can be set variously depending on the use and characteristics of the photosensitive material, but is generally 30 to 45 ° C, preferably 35 to 42 ° C. The time can be set arbitrarily,
Shorter is desirable from the viewpoint of reduction of processing time. It is preferably 10 seconds to 45 seconds, more preferably 10 seconds to 40 seconds. It is preferable that the replenishing amount is small in view of running cost, reduction of discharge amount, handleability, and the like.

A specific preferred replenishment amount is 0.5 to 50 times, preferably 2 to 1 times the photosensitive material and the amount brought in from the previous bath per unit area.
5 times. Alternatively, the amount is 300 ml or less, preferably 150 ml or less, per 1 m ^{2 of the} photosensitive material. Even if replenishment is performed continuously,
It may be performed intermittently.

The liquid used in the washing and / or stabilizing step can be used in the previous step. As an example of this, the overflow of the washing water reduced by the multi-stage countercurrent method is caused to flow into a bleach-fix bath preceding the bath, and the bleach-fix bath is replenished with a concentrated solution to reduce the amount of waste liquid.

Next, a drying step usable in the present invention will be described.

In order to complete an image by the ultra-rapid processing of the present invention, a drying time of 20 to 40 seconds is desired.

As a means for shortening the drying time, a means on the photosensitive material side can be improved by reducing the amount of water carried into the film by reducing the amount of a hydrophilic binder such as gelatin. Also, from the viewpoint of reducing the amount of carry-in, it is possible to speed up drying by absorbing water with a squeeze roller or cloth immediately after leaving the washing bath. Naturally, as a means for improving the dryer, it is possible to speed up the drying by increasing the temperature or increasing the drying air. Further, the drying can be accelerated by adjusting the irradiation angle of the drying air to the photosensitive material or by removing the exhaust air.

Example 1 (Preparation of Emulsion A) 3.3 g of sodium chloride was added to a 3% aqueous solution of lime-processed gelatin.
Was added, and 3.2 ml of N, N'-dimethylimidazolidin-2-thione (1% aqueous solution) was added. To this aqueous solution, an aqueous solution containing 0.2 mol of silver nitrate and an aqueous solution containing 0.2 mol of sodium chloride were added and mixed at 56 ° C. with vigorous stirring. Subsequently, an aqueous solution containing 0.780 mol of silver nitrate and sodium chloride
An aqueous solution containing 0.780 mol was added and mixed at 56 ° C. with vigorous stirring. Five minutes after the addition of the aqueous silver nitrate solution and the aqueous alkali halide solution was completed, an aqueous solution containing 0.020 mol of silver nitrate and an aqueous solution containing 0.015 mol of potassium bromide, 0.005 mol of sodium chloride and 0.8 mg of potassium hexachloroiridium (IV) acid were vigorously added. 40 with stirring
C. and mixed. Then, isobutene maleic acid 1
-A sodium salt copolymer was added, and the mixture was washed by settling and desalted. Further, 90.0 g of lime-processed gelatin was added, and a sulfur sensitizer and a gold sensitizer were further added to perform optimal chemical sensitization.

(Preparation of emulsion B) 3.3 g of sodium chloride in a 3% aqueous solution of lime-processed gelatin
Was added, and 3.2 ml of N, N'-dimethylimidazolidin-2-thione (1% aqueous solution) was added. To this aqueous solution, an aqueous solution containing 0.2 mol of silver nitrate and an aqueous solution containing 0.2 mol of sodium chloride were added and mixed at 56 ° C. with vigorous stirring. Subsequently, an aqueous solution containing 0.780 mol of silver nitrate and sodium chloride
An aqueous solution containing 0.780 mol and potassium hexacyanoruthenate (II) 4.7 mg (1 × 10 ⁻⁵ mol) was added and mixed at 56 ° C. with vigorous stirring. Five minutes after the addition of the aqueous silver nitrate solution and the aqueous alkali halide solution was completed, an aqueous solution containing 0.020 mol of silver nitrate and an aqueous solution containing 0.015 mol of potassium bromide, 0.005 mol of sodium chloride and 0.8 mg of potassium hexachloroiridium (IV) acid were vigorously added. The mixture was added and mixed at 40 ° C. with stirring. Thereafter, a copolymer of 1-sodium inbutene maleic acid was added, and the mixture was washed by settling and desalting. Further, 90.0 g of lime-processed gelatin was added, and a sulfur sensitizer and a gold sensitizer were further added to perform optimal chemical sensitization.

(Preparation of emulsion C) 3.3 g of sodium chloride in a 3% aqueous solution of lime-processed gelatin
Was added, and 3.2 ml of N, N'-dimethylimidazolidin-2-thione (1% aqueous solution) was added. To this aqueous solution, an aqueous solution containing 0.780 mol of silver nitrate and an aqueous solution containing 0.780 mol of sodium chloride were added and mixed at 56 ° C. with vigorous stirring.
Subsequently, an aqueous solution containing 0.20 mol of silver nitrate and an aqueous solution containing 0.20 mol of sodium chloride and 4.7 mg (1 × 10 ⁻⁵ mol) of potassium hexacyanoruthenate (II) were added and mixed at 56 ° C. with vigorous stirring. Five minutes after the addition of the aqueous silver nitrate solution and the aqueous alkali halide solution was completed, an aqueous solution containing 0.020 mol of silver nitrate and an aqueous solution containing 0.015 mol of potassium bromide, 0.005 mol of sodium chloride and 0.8 mg of potassium hexachloroiridium (IV) acid were vigorously added. The mixture was added and mixed at 40 ° C. with stirring. Thereafter, a copolymer of isobutene maleic acid 1-sodium salt was added, and the mixture was washed by settling and desalting. Further, 90.0 g of lime-processed gelatin was added, and a sulfur sensitizer and a gold sensitizer were further added to perform optimal chemical sensitization.

About the obtained silver chlorobromide (A), (B), (C),
The particle shape, particle size and particle size distribution were determined from the electron micrograph. All of these silver halide grains are cubic, and the grain size is 0.52 μm, and the coefficient of variation is 0.
08. The particle size was represented by the average value of the diameter of a circle equivalent to the projected area of the particle, and the particle size distribution was obtained by dividing the standard deviation of the particle size by the average particle size.

Next, the halogen composition of the emulsion grains was determined by measuring X-ray diffraction from silver halide crystals. The diffraction angle from the (200) plane was measured in detail using the monochromatic CuKα ray as a radiation source. Diffraction lines from crystals having a uniform halogen composition give a single peak, whereas diffraction lines from crystals having localized phases with different compositions give a plurality of peaks corresponding to those compositions. By calculating the lattice constant from the measured diffraction angle of the peak, the halogen composition of the silver halide constituting the crystal can be determined. The measurement results of the silver chlorobromide emulsions (A), (B) and (C)
Observe a broad diffraction pattern centered on 70% silver chloride (30% silver bromide) and skirted to 60% silver chloride (40% silver bromide) in addition to the 10% main peak. Was completed.

(Preparation of Sensitive Material) After a corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided, and various photographic constituent layers were further coated as shown below. A multilayer color photographic paper (1) having a layer configuration was produced. The coating solution was prepared as follows.

Preparation of first layer coating solution 19.1 gg of yellow coupler (ExY) and color image stabilizer (C
To 4.4 g of pd-1) and 0.7 g of color image stabilizer (Cpd-7), 27.2 cc of ethyl acetate and solvents (Solv-3) and (Solv-7)
Was dissolved in 185 cc of a 10% aqueous gelatin solution containing 8 cc of 10% sodium dodecylbenzenesulfonate to prepare an emulsified dispersion. On the other hand, an emulsion was prepared by adding a spectral sensitizing dye (Dye-1) to the silver chlorobromide emulsion (A). The above-mentioned emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution having the following composition.

Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As the gelatin hardener for each layer, 1-
Oxy-3,5-dichloro-s-triazine sodium salt was used.

The total amount of Cpd-10 and Cpd-11 in each layer was 25.0% each.
It was added to a mg / m ² and 50.0 mg / m ^2.

(Layer Configuration) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.

Support Polyethylene laminated paper [The first layer side polyethylene contains white pigment (TiO2) and blue dye (ultra blue)] First layer (yellow color forming layer) Silver chlorobromide emulsion 0.30 Gelatin 1.86 Spectral sensitizing dye ( Dye-1) Yellow coupler (ExY) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Soly-3) 0.18 Solvent (Solv-7) 0.18 Color image stabilizer (Cpd-7) 0.06 Second layer (color mixing prevention) Layer) Gelatin 0.99 Color mixing inhibitor (Cpd-5) 0.08 Solvent (Solv-1) 0.16 Solvent (Solv-4) 0.08 Third layer (Magenta coloring layer) Silver chlorobromide emulsion 0.12 Spectral sensitizing dye (Dye-2) Gelatin 1.24 Magenta coupler (ExM) 0.23 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-3) 0.16 Color image stabilizer (Cpd-4) 0.02 Color image stabilizer (Cpd-9) 0.02 Solvent ( Solv-2) 0.40 4th layer (ultraviolet absorbing layer) Gelatin 1.58 Ultraviolet absorber (UV-1) 0.47 Anti-color mixing Agent (Cpd-5) 0.05 Solvent (Solv-5) 0.24 Fifth layer (cyan coloring layer) Silver chlorobromide emulsion 0.23 Spectral sensitizing dye (Dye-3) Gelatin 1.34 Cyan coupler (ExC) 0.32 Color image stabilizer ( Cpd-2) 0.03 Color image stabilizer (Cpd-4) 0.02 Color image stabilizer (Cpd-6) 0.18 Color image stabilizer (Cpd-7) 0.40 Color image stabilizer (Cpd-8) 0.05 Solvent (Solv-6) 0.14 6th layer (UV absorption layer) Gelatin 0.53 UV absorber (UV-1) 0.16 Color mixing inhibitor (Cpd-5) 0.02 Solvent (Solv-5) 0.08 7th layer (protection layer) Gelatin 1.33 Acrylic of polyvinyl alcohol Modified copolymer (degree of modification
17%) 0.17 Liquid paraffin 0.03 Each layer was spectrally sensitized using the following spectral sensitizing dyes. The spectral sensitization maximum wavelengths of the first, third, and fifth layers were 670 nm, 735 nm, and 850 nm, respectively.

(First layer: red-sensitive yellow coloring layer) 1.0 × 10 ^-4 mol per mol of silver halide 1.0 × 10 ^-4 mol (third layer infrared-sensitive magenta coloring layer) 4.5 × 10 ^-5 mol per mole of silver halide (fifth layer infrared-sensitive cyan coloring layer) (0.5 × 10 ⁻⁵ mol per mol of silver halide) When (Dye-2) and (Dye-3) were used, 1.8 × 10 ⁻³ mol of the following compound was added per mol of silver halide.

Further, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to each of the yellow, magenta and cyan coloring emulsion layers in an amount of 8.0 × 10 ^-4 mol per mol of silver halide.

The following dyes were added to the emulsion layer to prevent irradiation.

and and and (Solv-3) Solvent O = PO-C ₉ H ₁₉ (iso)] ₃ As shown in Table 2, similar emulsions D to U were prepared by changing the amount of potassium hexacyanoruthenate (II) in the emulsions B and C or the kind of the complex, and using these emulsions, 21 was created.

The sensitized materials were stored in a refrigerator and at room temperature for 3 months, and then the semiconductor laser AlGaInP (oscillation wavelength, about 670n
m), semiconductor laser GaAlAs (oscillation wavelength, about 750 nm), Ga
AlAs (oscillation wavelength, about 810 nm) was used. The laser beam was rotated by a rotating polyhedron to assemble an apparatus capable of sequentially scanning and exposing on color photographic paper moving in a direction perpendicular to the scanning direction, and the photosensitive material was exposed using the apparatus. Regarding the exposure amount, the exposure time and the emission amount of the semiconductor laser were electrically controlled.

The exposed sample was subjected to continuous processing (running test) using a paper processor until the replenishment was twice the tank capacity for color development in the next processing step. Process temperature Time Replenisher ^* Tank capacity Color development 35 ° C. 45 seconds 161 ml 17 l Bleach fixing 30 to 35 ° C. 45 seconds 215 ml 17 l Rinse 30 to 35 ° C. 20 seconds - 10 l Rinse 30 to 35 ° C. 20 seconds - 10 l rinse 30 to 35 ° C. 20 seconds 350 ml 10 l drying 70 to 85 ° C. 60 seconds * replenishment rate (set to 3 tank countercurrent system to rinse →.) per photosensitive material 1 m ² had the following composition of each processing solution It is.

Bleach-fix solution (same as tank solution and replenisher) Water 400 ml Ammonium thiosulfate (700 g / l) 100 ml Sodium sulfite 17 g Ammonium iron (III) ethylenediaminetetraacetate 55 g Disodium ethylenediaminetetraacetate 5 g Ammonium bromide 40 g Add water to 1000 ml pH (25 ℃) 6.0 rinse solution (same as tank solution and replenisher) Deionized water (calcium and magnesium are 3ppm each)
The sensitivity is the logarithm of the reciprocal of the amount of light required to obtain a density of 1.0 for the cyan coloring layer of the obtained sample, and the sensitivity S (RT.) Of the sample stored at room temperature for 3 months and the sensitivity of the sample stored in the freezer. The sensitivity difference ΔS from S (Fr) was determined and used as a measure of the temporal stability of the photosensitive material. (When desensitization occurs, the value is negative, and the greater the degree, the more negative the value.) Table 2 shows the obtained results.

Table 2 shows that the use of the metal complex of the present invention improves the desensitization of the photographic material over time. In addition, it can be seen that the effect is larger when doped near the surface of the particles.

Example 2 The photographic material used in Example 1 was stored and exposed in the same manner. The exposed sample is processed using a paper processor.
The color processing was performed in the next processing step. Processing process temperature Time replenisher ^* tank capacity Color development 35 ° C 20 seconds 60ml 2l Bleaching and fixing 30-35 ° C 20 seconds 60ml 2l Rinse 30-35 ° C 10 seconds-1l Rinse 30-35 ° C 10 seconds-1l Rinse 30-35 ° C. 10 seconds 120 ml 1l drying 70 to 80 ° C. 20 seconds * replenishment rate is composition (3 and a tank countercurrent system. to rinse →) each processing solution per photosensitive material 1 m ² is as follows.

Bleach-fix solution (same as tank solution and replenisher) Water 400 ml Ammonium thiosulfate (700 g / l) 100 ml Sodium sulfite 17 g Iron (III) ethylenediaminetetraacetate 55 g Sodium ethylenediaminetetraacetate 5 g Ammonium bromide 40 g Water Add 1000 ml pH (25 ℃) 6.0 rinse solution (same as tank solution and replenisher) Deionized water (calcium and magnesium are 3ppm each)
Hereinafter, the same evaluation as in Example 1 was performed on the developed sample. As a result, as in the case of Example 1, the storability of the photographic material was improved by the constitution of the present invention.

(Effect of the Invention) According to the present invention, a silver halide light-sensitive material which can be rapidly processed for infrared exposure, which has a small change in sensitivity due to storage of the light-sensitive material, can be obtained.

Claims (4)

(57) [Claims] 1. A silver halide photographic material having at least one photosensitive emulsion layer containing a silver halide emulsion on a support, wherein at least one of said photosensitive emulsion layers is 73.
Co, Ni, Ru, R having a spectral sensitivity maximum at 0 nm or more and having at least two cyanogen ligands in the photosensitive emulsion layer
A silver halide photographic material comprising silver halide grains containing at least one selected from metal complexes of e, Os, Pt, and Au and having a silver chloride content of 80 mol% or more. 2. 50% of the total content of at least one selected from metal complexes of Co, Ni, Ru, Re, Os, Pt or Au having at least two cyanide ligands contained in silver halide grains. The silver halide photographic material according to claim 1, wherein the above is contained in a surface layer having a particle volume of 50% or less. 3. A support having at least three types of silver halide photosensitive layers having different color sensitivities each containing a coupler which develops a yellow, magenta or cyan color on a support. At least one of a metal complex of Co, Ni, Ru, Re, Os, Pt or Au having at least two cyanogen ligands in the photosensitive emulsion layer, wherein one of the layers has a spectral sensitivity maximum at 730 nm or more. A silver halide photographic light-sensitive material comprising silver halide grains having a silver chloride content of at least 80 mol% containing seeds. 4. The method according to claim 1, wherein the total content of at least one selected from metal complexes of Co, Ni, Ru, Re, Os, Pt or Au having at least two cyanide ligands contained in the silver halide grains is halogen. The silver halide photographic light-sensitive material according to claim 1, wherein the amount is 1 × 10 ^-6 mol or more and 1 × 10 ^-3 mol or less per mol of silver halide. material.