JPH0754401B2 - Silver halide photographic light-sensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material having a dyed hydrophilic colloid layer. is there.

(Prior Art) In a silver halide photographic light-sensitive material, a photographic emulsion layer or other layers are often colored for the purpose of absorbing light in a specific wavelength range.

When it is necessary to control the spectral composition of light to be incident on the photographic emulsion layer, a coloring layer is provided on the side of the photographic light-sensitive material farther from the support than the photographic emulsion layer. Such a colored layer is called a filter layer. When there are a plurality of photographic emulsion layers as in a multi-layer color light-sensitive material, the filter layer may be located between them.

Based on the fact that the light scattered during or after passing through the photographic emulsion layer is reflected at the interface between the emulsion layer and the support or at the surface of the light-sensitive material opposite to the emulsion layer and re-enters the photographic emulsion layer. Between the photographic emulsion layer and the support for the purpose of preventing image blurring, that is, halation,
Alternatively, a coloring layer is provided on the surface of the support opposite to the photographic emulsion layer. Such a colored layer is called an antihalation layer. When there are a plurality of photographic emulsion layers such as a multi-layer color light-sensitive material, an antihalation layer may be placed between the layers.

Decrease in image sharpness due to light scattering in photographic emulsion layer (This phenomenon is generally called irradiation)
Coloring of the photographic emulsion layer is also carried out in order to prevent this.

These layers to be colored are often composed of hydrophilic colloids and therefore for their coloring usually water-soluble dyes are included in the layers. This dye is required to satisfy the following conditions.

(1) It has a proper spectral absorption according to the purpose of use.

(2) Photochemically inactive. That is, it should not adversely affect the performance of the silver halide photographic emulsion layer in a chemical sense, such as reduction in sensitivity, latent image regression, or fog.

(3) It should not be decolorized or dissolved and removed in the course of photographic processing to leave no harmful coloring on the photographic light-sensitive material after processing.

In order to satisfy such a condition, many dyes that absorb visible light or ultraviolet light are conventionally known.
Suitable for image-improving purposes in conventional photographic elements sensitized to sub-m wavelengths. Particularly triarylmethane and oxonol dyes are widely used in this connection.

On the other hand, development of antihalation and antiirradiation dyes which absorb in the infrared region of the spectrum for recording materials sensitized to infrared wavelengths in recent years, for example, photographic light-sensitive materials as recording materials for recording the output of near infrared laser Is required.

For example, one of the exposure methods for such a photographic light-sensitive material is scanning the original image, and the silver halide photographic light-sensitive material is exposed on the basis of the image signal to expose a negative image or a positive image corresponding to the image of the original image. There is known an image forming method using a so-called Scanner method for forming a sheet. In this method, a semiconductor laser is most preferably used as a scanner type recording light source. This semiconductor laser is small, inexpensive, easy to modulate, has a longer life than other He-Ne lasers, argon lasers, etc., and emits light in the infrared region. Therefore, a photosensitive material sensitive to the infrared region is used. When,
Since a bright safelight can be used, there is an advantage that handling workability is improved.

Regarding such dyes for photographic light-sensitive materials having photosensitivity in the infrared region, (a) use of indoalinine dyes as infrared absorbing dyes in JP-A-50-100116 and (B) JP-A-55 -21094, 55-21095, 55-21096 and Research Disclosure 22338, an infrared dye is formed in a hydrophilic colloid layer from a 2-carbamoyl-1-naphthol coupler and a color developing agent. It is described that it is possible.

(Problems to be Solved by the Invention) However, the above-mentioned (a) indoaniline dye has a drawback that the absorption wavelength is practically short. Further, since the infrared dye formed from 2-carbamoyl-1-naphthol and the color developing agent of the above (b) is water-insoluble, an oil-soluble material is required when incorporated in the hydrophilic colloid layer. As a result, an unfavorable phenomenon such as an increase in film thickness and a decrease in film strength is caused. Further, since these dyes are water-insoluble, they have a drawback that they are difficult to be eluted and decolorized in the course of photographic processing. Therefore, the conventional dye cannot satisfy all the above-mentioned conditions (1) to (3) required for it, and therefore, a photographic light-sensitive material having the excellent performance of the semiconductor laser as described above can be obtained. I couldn't.

Therefore, a first object of the present invention is to provide a silver halide photographic light-sensitive material having a hydrophilic colloid layer colored with a water-soluble dye which does not adversely affect the photographic characteristics of a photographic emulsion and is decolorized by photographic processing. Is. A second object of the present invention is to provide a silver halide photographic light-sensitive material which has a good image and does not impair the sensitivity in the infrared region. A third object of the present invention is to provide a silver halide photographic light-sensitive material having high sensitivity to infrared light which has less residual color after development processing.

(Means for Solving Problems) An object of the present invention is to provide a silver halide photographic light-sensitive material comprising a hydrophilic colloid containing at least one dye represented by the following general formula (I). Achieved

General formula (I) In the formula, R ¹ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group (eg, a phenyl group, a naphthyl group, etc.), a substituted or unsubstituted heterocyclic group, and R ² represents a hydrogen atom or a substituted one thereof. Represents a possible group, R ³ and
R ^{4 s} may be the same as or different from each other, and may be a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms (for example, a methyl group,
(Ethyl group, propyl group, isopropyl group, t-butyl group, etc.), R ⁵ represents a hydrogen atom, and R ⁶ and R ⁷ may be the same or different from each other and represent a substituted or unsubstituted alkyl group. However, at least one, preferably 2 to 5 of the groups represented by R ¹ , R ² , R ³ , R ⁴ , R ⁶ and R ⁷ has a sulfo group or a salt thereof or a carboxyl group or a salt thereof.

The alkyl groups represented by R ¹ , R ³ , R ⁴ , R ⁶ or R ⁷ may be the same as or different from each other, and may have a substituent (for example, a sulfo group, a carboxyl group, a hydroxyl group, etc.). The alkyl group represented by R ¹ , R ⁶ or R ⁷ has 1 carbon atom.
A lower alkyl group of 5 to 5 (eg, methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, etc.) is preferable.

The aryl groups represented by R ¹ may be the same as or different from each other, and may be a substituted or unsubstituted phenyl group (as a substituent, for example, a sulfo group, a carboxyl group, a hydroxyl group, a cyano group, a halogen atom (for example, a chlorine atom, a fluorine atom, etc. ), An acyl group having 2 to 5 carbon atoms (eg, acetyl group, propionyl group, etc.), a sulfonyl group having 1 to 5 carbon atoms (eg, methanesulfonyl group, ethanesulfonyl group, 2-sulfoethanesulfonyl group, 3-sulfopropanesulfonyl) Group), a carbamoyl group having 1 to 5 carbon atoms (for example, an unsubstituted carbamoyl group, a methylcarbamoyl group, a 2-sulfoethylcarbamoyl group, a 2-carboxyethylcarbamoyl group, a 2-hydroxyethylcarbamoyl group, etc.), a carbon number of 1 ~ 5 sulfamoyl groups (eg unsubstituted sulfamoyl groups, methyl Sulfamoyl group, ethylsulfamoyl group, 2-sulfoethylsulfamoyl group, 2-carboxyethylsulfamoyl group, etc.), alkoxycarbonyl group having 2 to 5 carbon atoms (for example, methoxycarbonyl group, ethoxycarbonyl group, trichloroethoxy) Carbonyl group, trifluoroethoxycarbonyl group, etc.), alkoxy group having 1 to 5 carbon atoms (eg methoxy group, ethoxy group etc.), amino group (eg dimethylamino group, diethylamino group etc.)} or substituted or unsubstituted naphthyl A group (preferably the same substituent as the substituent in the case of a phenyl group) is preferable.

The substituted or unsubstituted heterocycle represented by R ¹ represents a monocyclic heterocycle or a condensed heterocycle, for example, 1,3-thiazole ring, 1,3,4-triazole ring, benzothiazole ring, benzimidazole ring, Benzoxazole ring, 1,3,4-
A thiadiazole ring and the like (substituents such as a lower alkyl group such as a methyl group and an ethyl group, a lower alkoxy group such as a methoxy and ethoxy group, a sulfo group, a hydroxyl group and a carboxyl group) are preferable.

The group capable of substituting the hydrogen atom represented by R ² includes a halogen atom (for example, F, Cl, Br, etc.), a hydroxyl group, a sulfo group, a carboxyl group, a cyano group, or a substituent bonded directly or through a divalent continuous group. Or, it represents an unsubstituted alkyl group having 1 to 5 carbon atoms [eg, methyl group, ethyl group, etc. (as a substituent, sulfo group, carboxyl group, hydroxyl group, etc.)], and the divalent linking group is, for example, —O—, — NHCO−, −NHSO ₂
-, - NHCOO -, - NHCONH -, - COO -, - CO -, - SO 2
-Indicates etc.

Specific examples of the dye compound represented by the general formula (I) used in the present invention are shown below, but the scope of the present invention is not limited thereto.

The compound represented by the general formula (I) is a method of condensing α-naphthols and p-phenylenediamines in the presence of a base and an oxidizing agent, and 4-amino-1-naphthols and dialkylanilines with hypochlorous acid. It can be synthesized by a method such as oxidative condensation with a sodium chlorate solution. For example, it can be synthesized according to the method described in JP-A-50-100116 and JP-A-60-32851.

Synthesis Example 1 (Synthesis of Exemplified Compound 1) 5.5 g of 2- (3′-sulfophenylcarbamoyl) -1-naphthol, 30 ml of methanol and 5.8 m of triethylamine
A solution of 11 g of ammonium persulfate and 20 ml of water is added to the solution of 1 and the internal temperature is cooled to 10 ° C, and 3.7 g of 4-diethylamino-2,6-dimethylaniline is gradually added with vigorous stirring.
After stirring at an internal temperature of 10 to 15 ° C for 1 hour, a solution of 1.7 g of potassium acetate and 60 ml of methanol is added and the mixture is stirred for 30 minutes. The precipitated crystals were collected by filtration, washed with methanol, and recrystallized from methanol to obtain 2.8 g of a greenish blue crystal of Exemplified Compound 1. Melting point 260
℃ or more, Synthesis Example 2 (Synthesis of Exemplified Compound 8) A solution of 4.7 g of sodium chloride and 40 ml of water was added dropwise to a solution of 13.6 g of silver nitrate and 30 ml of water while stirring, and the white precipitate thus deposited was collected by filtration, washed with water and then washed with methanol. Used for the following reactions.

To a solution of 2- (4'-sulfophenylcarbamyl) -1-naphthol (5.5 g), methanol (25 ml) and triethylamine (3.8 ml) was added the silver chloride prepared above, the mixture was cooled to 10 ° C, and 4-N-ethyl was added with stirring. -N-4'-sulfobutylamino-2,6-dimethylaniline 5.4g, triethylamine 3.8m
A solution of l and 40 ml of methanol was added dropwise in about 20 minutes. After completion of dropping, the mixture was stirred at 10 to 15 ° C. for 1 hour, silver was filtered off, a solution of 4 g of potassium acetate and 25 ml of methanol was added to the filtrate, and the mixture was stirred for 30 minutes.
The deposited crystal was collected by filtration and washed with methanol to obtain 4.7 g of a greenish blue powder of Exemplified Compound 8. Melting point 260 ° C
that's all.

Synthesis Example 3 (Synthesis of Exemplified Compound 9) 2- (4′-sulfoethylsulfamoylphenylcarbamoyl) -1-naphthol (6.7 g) in a solution of methanol (25 ml) and triethylamine (3.8 ml) was obtained in the same manner as in Synthesis Example 2. After adding silver and cooling to 10 ° C, a solution of 3.5 g of 4-diethylamino-2,6-dimethylaniline, 3.8 ml of triethylamine and 40 ml of methanol was added dropwise with stirring for about 20 minutes. After dropping, the mixture was stirred at 10 to 15 ° C. for 1 hour, silver was filtered off, a solution of 2 g of potassium acetate and 15 ml of methanol was added to the filtrate, and the mixture was stirred for 30 minutes. The precipitated crystals were collected by filtration and washed with methanol to obtain 3.9 g of greenish blue powder of Exemplified Compound 9. Melting point
260 ° C or higher.

Synthesis Example 4 (Synthesis of Exemplified Compound 13) 2- (4′-propanesulfonylphenylcarbamoyl) -1-naphthol 3.7 g, 4-N-ethyl-N-4 ′
-Sulfobutylamino-2,6-dimethylaniline 3.6 g,
A mixed solution of 2.1 g of sodium carbonate, 100 ml of methanol, and 30 ml of water was cooled with ice, 4.6 g of ammonium persulfate was added, and the mixture was further stirred under ice cooling for 2 hours. The precipitated dark green crystals were collected by filtration and recrystallized from ethanol to prepare the exemplified compound 13
To obtain 1.9 g of a blue-green powder. Melting point 182-189 ° C (decomposition) Synthesis Example 5 (Synthesis of Exemplified Compound 14) 2- (4-Cyanophenylcarbamoyl) -1-naphthol 2.9 g, 4-N-ethyl-N-4′-sulfobutyl-
While cooling a mixed solution of 2,6-dimethylaniline (3.6 g), sodium carbonate (2.1 g), methanol (100 ml) and water (30 ml) with ice, 4.6 g of ammonium persulfate was added, and the mixture was further stirred under ice cooling for 2 hours. The precipitated dark green crystals were collected by filtration and recrystallized from methanol to obtain 1.5 g of Exemplified Compound 14 green crystals. Melting point 238-240 ° C (decomposition).

Synthesis Example 6 (Synthesis of Exemplified Compound 23) 3.2 g of 2- (4-acetylphenylcarbamoyl) -1-naphthol, 3.6 g of 4-N-ethyl-N-4′-sulfobutylamino-2,6-dimethylaniline, sodium carbonate
4.6 g of ammonium persulfate was added while ice-cooling a mixed solution of 2.1 g, methanol 80 ml, and water 20 ml, and the mixture was further stirred under ice cooling for 2 hours. 1.1g of blue-green crystal of Exemplified Compound 23 by filtering the precipitated dark green crystal and recrystallizing from methanol
Got Melting point 227-228 ° C In the present invention, the above dye is dissolved in an appropriate solvent [for example, water, alcohol (for example, methanol, ethanol, etc.), methyl cellosolve, etc., or a mixed solvent thereof] and added to the coating solution for the hydrophilic colloid layer.

These dyes can be used in combination of two or more kinds.

The specific amount of dye used is difficult to determine uniformly, but in general
^{10 -3 g / m 2 ~1g /} m 2, it is possible to find particular preferred amounts in the range of ^{10 -3 g / m 2 ~0.5g /} m 2.

In the present invention, the dye may be added to any of the hydrophilic colloid layers constituting the silver halide photographic light-sensitive material,
Examples thereof include a protective layer, a silver halide emulsion layer, an antihalation layer and a back layer.

In the present invention, the dye may be contained only in the substantially non-photosensitive hydrophilic colloid layer by preventing the dye from diffusing from the non-photosensitive hydrophilic colloid layer into the emulsion layer. For example, a method may be used in which a silver halide emulsion layer is coated and completely set, and then a non-photosensitive hydrophilic colloid layer containing a non-diffusible dye is coated on the emulsion layer.
Further, when simultaneously coating the emulsion layer and the non-photosensitive hydrophilic colloid layer by the multi-layer simultaneous coating method, it is most preferable to add the non-diffusible dye or the polymer mordant together with the dye to the non-photosensitive hydrophilic colloid layer. .

Examples of the light-sensitive material to which the present invention is applied include a black-and-white photographic light-sensitive material and a color photographic light-sensitive material. Examples of the former include a photosensitive material for printing and an infrared photosensitive material. At this time, the silver halide emulsion layer is 2
It is also possible to provide more than one layer. When the infrared light-sensitive material, silver coverage in the range of 1g / m ² ~8g / m ² is desirable.

The silver halide used in the present invention may be any of silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide and silver chloroiodobromide.

For black and white light-sensitive materials, the average grain size of silver halide is 1.
It is preferably 0 μm or less, and particularly preferably 0.7 μm or less.

The silver halide grains in the photographic emulsion may be so-called regular grains having regular crystal bodies such as cubes, octahedra and tetradecahedrons, and those having an irregular crystal shape such as spheres, It may have a crystal defect such as a twin plane or a composite form thereof.

The grain size of silver halide may be a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution.

The silver halide photographic emulsion which can be used in the present invention can be produced by a known method, for example, Research Disclosure (RD), No. 17643 (December 1978), pp. 22-23, "I. Emulsion preparatipn ans types) ”and the same, N
o. 18716 (November, 1979) p.648 can be followed.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Graphide, published by Paul Monten (P.Glafkides, Chim.
ie et Physipue Photographique Paul Montel, 1967),
Duffin, "Photoemulsion Chemistry", published by Focal Press (GFDuffin, Photographec Emulsion Chemstry (Focal
Press, 1966), "Manufacturing and coating of photographic emulsions" by Zelikman et al., Published by Focal Press (VLZelikman et al, Mak).
ing and Coating Photographic Emulsion, Focal Press,
1964) and the like.

During the formation of silver halide grains used in the present invention, silver halide emulsions such as ammonia, rodancali, rhodammone, and thioether compounds (e.g., U.S. Pat.Nos. 3,271,157, 3,574,628 and No. 3,704,130, No. 4,297,439,
No. 4,276,347, etc.), thione compounds (for example, JP-A-5
No. 3-144319, No. 53-82408, No. 55-77737, etc.), amine compounds (for example, JP-A No. 54-100717, etc.) and the like can be used.

In the present invention, a water-soluble rhodium salt or a water-soluble iridium salt can be used.

As the method of reacting the soluble silver salt and the soluble halogen salt in the present invention, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used.

A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. PAg in the liquid phase in which silver halide is formed as a form of simultaneous mixing method.
To keep constant, that is, so-called controlled
The double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

The silver halide emulsion used in the method of the present invention may or may not be chemically sensitized.

In the case of chemical sensitization, usual ion sensitization, reduction sensitization, noble metal sensitization and a combination thereof are used.

More specific chemical sensitizers include sulfur sensitizers such as allyl thiocarbamide, thiourea, thiosulfate, thioether and cystine; potassium chloroaurate, aurous, thiosulfate and potassium chloroparadate ( Potassim chloro pa
Noble metal sensitizers such as lladate); reduction sensitizers such as tin chloride, phenylhydrozine and reductone.

The silver halide emulsion used in the present invention is spectrally sensitized with a known spectral sensitizing dye, if necessary. Examples of the spectral sensitizing dye used include Research Disclosure 9 (176), No. 17643, Item IV (1
The one described in the February issue, 1978) can be used.

The silver halide emulsion of the present invention is preferably infrared sensitized so as to have a maximum sensitization in the wavelength region of 750 nm or more. Any sensitizing dye for infrared sensitization may be used, but from the viewpoint of sensitizing performance and stability, a tricarbocyanine dye and / or a 4-quinoline nucleus-containing dicarbocyanine dye is particularly preferable. preferable. Infrared spectral sensitization of silver halide emulsions can sometimes result in poor stability of the emulsion in solution. In order to prevent this, it is effective to add a water-soluble bromide to the emulsion.

Among the tricarbocyanine dyes used in the present invention, particularly useful are those represented by the following general formula (IIa) or (IIb).

General formula (IIa) General formula (IIb) In the formula, R ¹¹ and R ¹² may be the same or different and each is an alkyl group (preferably having a carbon number of 1 to 1).
8, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a heptyl group, etc.), a substituted alkyl group {as a substituent, for example, a carboxy group, a sulfo group, a cyano group, a halogen atom (eg, a fluorine atom, a chlorine atom) , Bromine atom, etc.), hydroxy group, alkoxycarbonyl group (having 8 or less carbon atoms, for example, methoxycarbonyl group, ethoxycarbonyl group, benzyloxycarbonyl group, etc.), alkoxy group (having 7 or less carbon atoms, for example, methoxy group, ethoxy group) , Propoxy group, butoxy group, benzyloxy group etc.), aryloxy group (eg phenoxy group, p-tolyloxy group etc.), acyloxy group (C3 or less, eg acetyloxy group, propionyloxy group etc.), acyl group (C8 or less, such as acetyl group, propio Group, a benzoyl group, etc. mesyl group), a carbamoyl group (e.g. carbamoyl group, N,
N-dimethylcarbamoyl group, morpholylcarbamoyl group, piperidinocarbamoyl group, etc.), sulfamoyl group (eg sulfamoyl group, N, N-dimethylsulfamoyl group, morpholinosulfonyl group etc.), aryl group (eg phenyl group, p -Hydroxyphenyl group, p-
An alkyl group (having 6 or less carbon atoms in the alkyl portion) substituted with a carboxyphenyl group, a p-sulfophenyl group, an α-naphthyl group, or the like). However, two or more of these substituents may be combined and substituted with an alkyl group. } Is represented.

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

R ¹³ and R ¹⁴ are each a hydrogen atom, a lower alkyl group (eg, methyl group, ethyl group, propyl group, etc.), a lower alkoxy group (eg, methoxy group, ethoxy group, propoxy group, butoxy group, etc.), phenyl group, benzyl group. Represents

R ¹⁵ is a hydrogen atom, a lower alkyl group (eg, methyl group, ethyl group, propyl group, etc.), a lower alkoxy group (eg, methoxy group, ethoxy group, propoxy group, butoxy group, etc.), phenyl group, benzyl group, Represents Here, W ₁ and W ₂ are each a substituted or unsubstituted alkyl group (having 1 to 18 carbon atoms in the alkyl portion, preferably 1 to 4, for example, methyl group, ethyl group, propyl group, butyl group, benzyl group, phenyl group). Ethyl group), an aryl group (for example, a phenyl group, a naphthyl group, a tolyl group, a p-chlorophenyl group, etc.), and W ₁ and W ₂ are linked to each other to form a 5- or 6-membered nitrogen-containing heterocycle. You can also

D represents a group of atoms necessary to complete a divalent ethylene bond, such as ethylene or triethylene, wherein the ethylene bond is one, two or more suitable groups, such as those having 1 to 4 carbon atoms. Alkyl group (eg, methyl group, ethyl group, propyl group, isopropyl group, butyl group, etc.),
Halogen atom (for example, chlorine atom, bromine atom, etc.) or alkoxy group (having 1 to 4 carbon atoms, for example, methoxy group,
Ethoxy group, propoxy group, isopropoxy group, butoxy group, etc.) and the like.

D ₁ and D ₂ each represent a hydrogen atom. However, it is also possible that D ₁ and D ₂ cooperate to form a divalent ethylene bond having the same meaning as D above.

Z and Z ₁ each represent a non-metal atom group necessary for completing a 5- or 6-membered nitrogen-containing heterocycle, for example, a thiazole nucleus [eg, benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6 -Chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole,
6-bromobenzothiazole, 5-iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-
Ethoxybenzothiazole, 5-carboxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5
-Phenethylbenzothiazole, 5-fluorobenzothiazole, 5-trifluoromethylbenzothiazole,
5,6-dimethylbenzothiazole, 5-hydroxy-6
-Methylbenzothiazole, tetrahydrobenzothiazole, 4-phenylbenzothiazole, naphtho [2,1-
d] thiazole, naphtho [1,2-d] thiazole, naphtho [2,3-d] thiazole, 5-methoxynaphtho [1,2-
d] thiazole, 7-ethoxynaphtho [2,1-d] thiazole, 8-methoxynaphtho [2,1-d] thiazole,
5-methoxynaphtho [2,3-d] thiazole and the like], zenerazole nucleus [eg, benzozelenazole, 5-chlorobenzozelenazole, 5-methoxybenzozerenazole, 5-methylbenzozerenazole, 5- Hydroxybenzozelenazole, naphtho [2,1-d] zerenazole,
Naphtho [1,2-d] zelenazole etc.], oxazole nucleus [benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-bromobenzoxazole, 5-fluorobenzoxazole, 5-
Phenylbenzoxazole, 5-methoxybenzoxazole, 5-trifluorobenzoxazole, 5-
Hydroxybenzoxazole, 5-carboxybenzoxazole, 6-methylbenzoxazole, 6-chlorobenzoxazole, 6-methoxybenzoxazole, 4,6-dimethylbenzoxazole, 5-ethoxybenzoxazole, naphtho [2,1-d] Oxazole, naphtho [1,2-d] oxazole, naphtho [2,3-
d] oxazole etc.], quinoline nucleus [eg 2-quinoline, 3-methyl-2-quinoline, 5-ethyl-2-quinoline, 6-methyl-2-quinoline, 8-fluoro-2]
-Quinoline, 6-methoxy-2-quinoline, 6-hydroxy-2-quinoline, 8-chloro-2-quinoline, 8-
Fluoro-4-quinoline, etc.], 3,3-dialkylindolenine nucleus (eg, 3,3-dimethylindolenine, 3,3
-Diethyl indolenine, 3,3-dimethyl-5-cyanoindolenine, 3,3-dimethyl-5-methoxyindolenine, 3,3-dimethyl-5-methylindolenine, 3,3-
Dimethyl-5-chloroindolenine, etc., imidazole nucleus (e.g., 1-methylbenzimidazole, 1-ethylbenzimidazole, 1-methyl-5-chlorobenzimidazole, 1-methyl-5,6-dichlorobenzimidazole, 1-ethyl-5,6-dichlorobenzimidazole, 1-alkyl-5-methoxybenzimidazole, 1-methyl-5-cyanobenzimidazole, 1-
Ethyl-5-cyanobenzimidazole, 1-methyl-
5-fluorobenzimidazole, 1-ethyl-fluorobenzimidazole, 1-phenyl-5,6-dichlorobenzimidazole, 1-allyl-5,6-dichlorobenzimidazole, 1-allyl-5-chlorobenzimidazole, 1-phenylbenzimidazole, 1-phenyl-5-chlorobenzimidazole, 1-methyl-5-
Trifluoromethylbenzimidazole, 1-ethyl-
5-trifluoromethylbenzimidazole, 1-ethylnaphtho [1,2-d] imidazole, etc.), pyridine nucleus (eg, pyridine, 5-methyl-2-pyridine, 3-methyl-4-pyridine, etc.) and the like. it can. Of these, a thiazole nucleus and an oxazole nucleus are advantageously used. More preferably, a benzothiazole nucleus, a naphthothiazole nucleus, a naphthoxazole nucleus or a benzoxazole nucleus is advantageously used.

X represents an acid anion.

n represents 1 or 2.

Of the 4-quinoline nucleus-containing dicarbocyanine dyes used in the present invention, particularly useful ones are represented by the following general formula (IIc).

General formula (IIc) In the formula, R ¹⁶ and R ¹⁷ have the same meanings as R ¹¹ and R ¹² , respectively.

R ¹⁸ has the same meaning as R ¹³ . However, R ¹⁸ is preferably a lower alkyl group or a benzyl group.

V is a hydrogen atom, a lower alkyl group (eg, methyl group, ethyl group, propyl group, etc.), an alkoxy group (eg, methoxy group, ethoxy group, butoxy group, etc.), a halogen atom (eg, fluorine atom, chlorine atom, etc.), substituted alkyl Represents a group (eg, trifluoromethyl group, carboxymethyl group, etc.).

Z ₂ has the same meaning as Z and Z ₁ .

X ₁ has the same meaning as X.

m, n ₁ and p each represent 1 or 2.

Specific examples of the sensitizing dye used in the present invention are shown below. However, the present invention is not limited to these sensitizing dyes.

The above infrared sensitizing dye used in the present invention is 5 × 10 ^{−7 to} 5 × 10 ⁻³ mol, preferably 1 × 1 mol per mol of silver halide.
It is contained in the silver halide photographic emulsion at a ratio of x10 ^-6 mol to 1 x 10 ^-3 mol, particularly preferably 2 x 10 ^-6 mol to 5 x 10 ^-4 mol.

The infrared sensitizing dye used in the present invention can be directly dispersed in the emulsion layer. In addition, these are first a suitable solvent,
For example, it can be dissolved in methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine or a mixed solvent thereof, and added to the emulsion in the form of a solution. Ultrasonic waves can also be used for dissolution. Further, as a method of adding the infrared sensitizing dye, as described in U.S. Pat.No. 3,469,987, the dye is dissolved in a volatile organic solvent, and the solution is dispersed in a hydrophilic colloid. A method of adding a dispersion to an emulsion, a method of dispersing a water-insoluble dye in a water-soluble solvent without dissolving, and adding the dispersion to an emulsion as described in JP-B-46-24185 and the like; US As described in Japanese Patent No. 3,822,135, a method in which a dye is dissolved in a surfactant and the solution is added to an emulsion; dissolution is performed by using a compound for red-shifting as described in JP-A-51-74624. Then, a method of adding the solution to the emulsion; a method of dissolving a dye as described in JP-A-50-80826 with an acid containing substantially no water and adding the solution to the emulsion is used. . In addition, U.S. Pat.Nos. 2,912,343 and 3,342,605 are added to the emulsion.
No. 2,996,287, No. 3,429,835 and the like can also be used. The infrared sensitizing dye of the above general formula (II) may be uniformly dispersed in the silver halide emulsion before being coated on a suitable support, but it goes without saying that any step in the preparation of the silver halide emulsion can be carried out. Can also be dispersed.

The sensitizing dye according to the present invention can be used in combination with other sensitizing dyes. For example, U.S. Pat.
No. 2, No. 2,688,545, No. 3,397,060, No. 3,615,63
No. 5, No. 3,628,964, British Patent No. 1,242,588, No.
1,293,862, Japanese Patent Publication No. 43-4936, 44-14030, 43-1
0773, U.S. Pat.No. 3,416,927, Japanese Patent Publication No. 43-4930, U.S. Pat.Nos. 3,615,613, 3,615,632, 3,617,295
Nos. 3,635,721 and the like can be used.

In the present invention, the compound represented by the following general formula (III) can be used for the purpose of further enhancing the supersensitizing effect and / or further enhancing the preservability.

General formula (III) In the formula, -A- represents a divalent aromatic residue, and these are-
SO ₃ M group [wherein M represents a hydrogen atom or a cation imparting water solubility (eg, sodium, potassium, etc.). ] May be included.

As -A-, those selected from the following -A ₁ -or -A _2- are useful. However, in R ¹⁹ , R ²⁰ R ²¹ or R ²² , -SO ₃ M
When the not included, -A- is -A ₁ - is selected from the group consisting of.

Such. Here, M represents a hydrogen atom or a cation that imparts water solubility.

R ¹⁹ , R ²⁰ , R ²¹ and R ²² are each a hydrogen atom, a hydroxy group,
Lower alkyl group (preferably having 1 to 8 carbon atoms, for example, methyl group, ethyl group, n-propyl group, n-
Butyl group, etc., alkoxy group (1 as the number of carbon atoms)
To 8 are preferable, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc., an aryloxy group (for example, a phenoxy group, a naphthoxy group, an o-troxy group, a p-sulfophenoxy group, etc.), a halogen atom (for example, a 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, benzimidazolylthio group, phenyltetrazolylthio group) Etc.), arylthio group (eg phenylthio group, tolylthio group), amino group, alkylamino group or substituted alkylamino group, (eg methylamino group, ethylamino group, propylamino group, dimethylamino group, diethylamino group, dodecylamino group) , Shi B hexylamino group, beta-hydroxyethylamino group, di - (beta-hydroxyethyl) amino group, beta-sulfoethylamino group), an arylamino group or a substituted Aruru amino group (e.g. 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-anisino group, m-anisino group, p-anisino group, o-acetaminoanilino group, hydroxyanilino group, di- Sulfophenylamino group, naphthylamino group, sulfonaphthylamino group, etc.), heterocyclylamino group (eg, 2-benzothiazolylamino group, 2-pyrazyl-amino group, etc.), substituted or unsubstituted aralkylamino group (eg, benzyl) Amino group, o-anisylamino group, m-anisylamino group, p-anisylamino group, etc.), aryl group (eg, phenyl group), and mercapto group. R
¹⁹ , R ²⁰ , R ²¹ , and R ²² may be the same as or different from each other. When -A- is selected from the group of -A _2- , R ¹⁹ , R
^At least one of ²⁰ , R ²¹ and R ²² must have one or more sulfo groups (which may be a free acid group or may form a salt). W represents -CH = or -N =, preferably -CH = is used.

Next, specific examples of the compound contained in the general formula (III) used in the present invention will be given. However, the present invention is not limited to these compounds.

(III-1) 4,4'-bis [4,6-di (benzothiazolyl-2-thio) pyrimidin-2-ylamino] stilbene-2,2'-disulfonic acid disodium salt (III-2) 4,4 ′ -Bis [4,6-di (benzothiazolyl-2-amino) pyrimidin-2-ylamino)] stilbene-2,2′-disulfonic acid disodium salt (III-3) 4,4′-bis [4,6 -Di (naphthyl-2-
(Oxy) pyrimidin-2-ylamino] stilbene-2,
2'-Disulfonic acid disodium salt (III-4) 4,4'-bis [4,6-di (naphthyl-2-
(Oxy) pyrimidin-2-ylamino] bibenzyl-2,
2'-Disulfonic acid disodium salt (III-5) 4,4'-bis [4,6-dianilinopyrimidin-2-ylamino) stilbene-2,2'-disulfonic acid disodium salt (III-6) 4 , 4'-Bis [4-chloro-6- (2-naphthyloxy) pyrimidin-2-ylamino] biphenyl-2,2'-disulfonic acid disodium salt (III-7) 4,4'-bis [4, 6-Di (1-phenyltetrazolyl-5thio) pyrimidin-2-ylamino] stilbene-2,2'-disulfonic acid disodium salt (III-8) 4,4'-bis [4,6-di (Benzimidazolyl-2-thio) pyrimidin-2-ylamino] stilbene-2,2'-disulfonic acid disodium salt (III-9) 4,4'-bis [4,6- (diphenoxypyrimidin-2-ylamino) ) Stilbene-2,2'-disulfonic acid disodium salt (III-10 4,4'-bis (4,6-diphenylthiopyrimidin-2-ylamino) stilbene-2,2'-disulfonic acid disodium salt (III-11) 4,4'-bis (4,6-dimercapto Pyrimidin-2-ylamino) biphenyl-2,2'-disulfonic acid disodium salt (III-12) 4,4'-bis (4,6-dianilino-triazin-2-ylamino) stilbene-2,2'-disulfone Acid disodium salt (III-13) 4,4'-bis (4-anilino-6-hydrokira-triazin-2-ylamino) stilbene-2,
2'-Disulfonic acid disodium salt (III-14) 4,4'-bis [4-naphthylamino-6-
Anilino-triazin-2-ylamino) stilbene-
Among these specific examples, (III-1) to (III-12) are preferable, and (III-1), (III-2) and (III-) are preferred.
3), (III-4), (III-5) and (III-7) are preferred.

The compound of general formula (III) 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 of the present invention to the compound represented by the general formula (III) is as follows:
The compound represented by the general formula (III) = 1/1 to 1/100 is preferably used, and particularly 1/2 to 1/50 is preferably used.

The compound represented by the general formula (III) used in the present invention is used by adding in the same manner as the sensitizing dye of the general formula (II).

In the present invention, the compound of the following general formula (IV) can be further used in combination.

General formula (IV) In the formula, Z ₃ represents a group of non-metal atoms necessary for completing a 5- or 6-membered nitrogen-containing heterocycle, for example, thiazolium compounds {eg thiazolium, 4-methylthiazolium, benzothiazolium, 5-methyl Benzothiazolium, 5-chlorobenzothiazolium, 5-methoxybenzothiazolium, 6-methylbenzothiazolium, 6-methoxybenzothiazolium, naphtho [1,2-d] thiazolium, naphtho [2 , 1-d] thiazolium, etc.}, oxazoliums {eg, oxazolium, 4-methyloxazolium, benzoxazolium, 5-chlorobenzoxazolium, 5-phenylbenzoxazolium, 5-methylbenzoxazol Lithium, naphtho [1,2-d] oxazolium, etc.}, imidazoliums (eg, 1-methylbenzimidazolium, 1-propyl Pills chloro Benz imidazolium, 1-ethyl-5,6-dichloro-Benz imidazolium, 1-allyl-5-trichloromethyl -6
-Chloro-benzimidazolium, etc.), selenazoliums [eg benzoselenazolium, 5-chlorobenzoselenazolium, 5-methylbenzoselenazolium, 5
-Methoxybenzoselenazolium, naphtho [1,2-d]
Such as serenazolium]. R ²³ is a hydrogen atom,
It represents an alkyl group (having 8 or less carbon atoms, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, etc.) and an alkenyl group (for example, an allyl group, etc.). R ¹⁴ represents a hydrogen atom or a lower alkyl group (eg, methyl group, ethyl group, etc.). X ₂ is an acid anion (e.g. ^{Cl -, Br -, I -} ,
ClO ₄ −, p-toluene sulfone, etc.) and Z ₃ are preferably thiazolium compounds. More preferably, a substituted or unsubstituted benzothiazolium or naphthothiazolium is advantageously used.

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

The compound represented by the general formula (IV) is advantageously used in an amount of about 0.01 to 5 grams per mol of silver halide in the emulsion.

The ratio (weight ratio) of the infrared sensitizing dye of the present invention to the compound represented by the general formula (IV) is such that the infrared sensitizing dye of the present invention / the compound represented by the general formula (IV) = 1 The range from 1/1 to 1/300 is preferably used, and the range from 1/2 to 1/50 is particularly preferably used.

The compound represented by the general formula (IV) used in the present invention can be added in the same manner as the compound of the general formula (II).

The compound represented by the general formula (IV) may be added to the emulsion before or after the addition of the infrared sensitizing dye of the present invention described above. Further, the compound of the general formula (IV) and the infrared sensitizing dye may be separately dissolved and added to the emulsion separately and simultaneously, or may be mixed and then added to the emulsion.

Various compounds can be added to the photographic emulsion of the present invention in order to prevent the deterioration of sensitivity and the occurrence of fog during the manufacturing process, storage or processing of the light-sensitive material. These compounds include many heterocyclic compounds such as nitrobenzimidazole, ammonium chloroplatinate, 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene, 1-phenyl-5-mercaptotetrazole, An extremely large number of compounds such as mercury-containing compounds, mercapto compounds and metal salts have long been known. An example of a compound that can be used is “The Theory of the Photographic Process” by Mies (3rd edition, 1966) (K. Mees “The Theory of
The Photographic Phocess ") pp. 344 to 349 with reference to the original literature.

Silver halide photographic emulsions contain developing agents such as hydroquinones; catechols; aminophenols; 3-pyrazolidones; ascorbic acid and its derivatives; reductones and phenylenediamines, or combinations of developing agents. be able to.

In the case of a photosensitive material for printing, for the purpose of improving the cutting of the leg portion of the characteristic curve and obtaining a high-quality halftone dot or line image,
Polyalkylene amide compound (for example, having 2 to 4 carbon atoms)
An alkylene oxide of, for example, ethylene oxide,
Propylene-1,2-oxide, butylene-1,2-oxide, etc., preferably at least ethylene oxide
Condensation product of polyalkylene oxide consisting of 10 units and compound having at least one active hydrogen atom such as water, aliphatic alcohol, aromatic alcohol, fatty acid, organic amine, hexitol derivative, or two or more kinds of polyalkylene oxide Block copolymers and the like) are preferably used. That is, as the polyalkylene oxide compound, specifically, polyalkylene glycols, polyalkylene glycol alkyl ethers, polyalkylene glycol alkyl ethers, polyalkylene glycol (alkylaryl) ethers, polyalkylene glycol esters, polyalkylene glycols. Fatty acid amides, polyalkylene glycol amines, polyalkylene glycol / block copolymers, polyalkylene glycol graft polymers and the like can be used. The molecular weight should be 600 or more.

The number of polyalkylene oxide chains is not limited to one in the molecule, and may be two or more. The individual polyalkylene oxide chains may then consist of less than 10 alkylene oxide units, but the total number of alkylene oxide units in the molecule must be at least 10. If there are two or more polyalkylene oxide chains in the molecule, each of them may consist of different alkylene oxide units, eg ethylene oxide and propylene oxide. The polyalkylene oxide compound used in the present invention preferably contains 14 to 100 alkylene oxide units.

Specific compounds include JP-A-50-156423 and JP-A-52-10.
The polyalkylene oxide compounds described in 8130 and JP-A-53-3217 can be used. These polyalkylene oxide compounds may be used alone or in combination of two or more.

When adding these polyalkylene oxide compounds to the silver halide emulsion, as an aqueous solution of a suitable concentration or dissolved in a low boiling organic solvent miscible with water,
It can be added to the emulsion at a suitable time before coating, preferably after chemical ripening.

These polyalkylene oxide compounds are preferably used in the range of 1.times.10.sup.- ⁵ mol to 1.times.10.sup.- ² mol per mol of silver halide.

The polyalkylene oxide compound may be added to the non-photosensitive hydrophilic colloid layer such as an intermediate layer, a protective layer and a filter layer, instead of being added to the emulsion.

As the binder or protective colloid used for the light-sensitive material,
Although it is advantageous to use gelatin, hydrophilic synthetic polymers and the like can also be used. As the gelatin, lime-processed gelatin, acid-processed gelatin, derivative gelatin and the like can also be used.

In the light-sensitive material of the present invention, in addition to the above, desensitizers, brighteners, couplers, hardeners, coating aids, plasticizers, anti-slip agents, nut agents, high boiling organic solvents, stabilizers, A development accelerator, an antistatic agent, an antistaining agent, etc. can be used. For details of these additives, see Research Disclosure (Vol. 176, No. 176).
43 (December issue, 1978) I-XVI (p.22-28)
It is possible to use those described in (Page).

For the photographic processing of the light-sensitive material of the present invention, any known method can be used, and known processing solutions can be used. The treatment temperature is usually selected between 18 ° C and 50 ° C, but it may be lower than 18 ° C or higher than 50 ° C. Depending on the purpose, either a development process for forming a silver image (black and white photographic process) or a color photographic process including a development process for forming a dye image can be applied.

The black-and-white developer contains dihydroxybenzenes (for example, hyoloquinone), 3-pyrazolines (for example, 1-phenyl-3-pyrazolidone), aminophenols (for example, N).
-Methyl-p-aminophenol) and other known developing agents can be used alone or in combination (e.g., 1-phenyl-3-pyrazolidones and dihydroxybenzenes or p-aminophenols and dihydroxybenzenes). The light-sensitive material of the present invention may be processed with a so-called infectious developer using a sulfite ion buffer such as carponyl bisulfite and hydroquinone. PH of developer
Is usually set to 9 or more, preferably 9.7 or more.

Color developers generally consist of an alkaline aqueous solution containing a color developing agent. Color developing agents are known primary aromatic amine developers such as phenylenediamines (eg 4-
Amino-N, N-diethylaniline, 3-methyl-4-amino-N, N-diethylaniline, 4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-
4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β
-Methanesulfonamidoethylaniline, 4-amino-
3-methyl-N-ethyl-N-β methoxyethylaniline and the like) can be used.

In addition, LFA Messon's "Photographic Processing Chemistry", published by Focal Press (1966)
226-229, U.S. Pat.Nos. 2,193,015 and 2,59
Those described in 2,364, JP-A-48-64933 and the like may be used.

The developer may be a pH buffer such as alkali metal sulfite, carbonate, borate and phosphate, bromide, iodide,
A development inhibitor such as polyalkylene oxide and an organic antifoggant or an antifoggant can be contained. If necessary, a water softener, a preservative such as hydroxylamine, an organic solvent such as benzyl alcohol and diethylene glycol, a polyethylene glycol, a quaternary ammonium salt, a development accelerator such as amines, a dye-forming coupler, a competitive coupler, Fogging agents such as sodium boron hydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting agents, U.S. Pat. No. 4,083,723.
Published in Germany
S) The antioxidants described in 2,622,950 may be included.

A compound that gives free sulfite ion, such as sodium sulfite, potassium sulfite, potassium metabisulfite, sodium bisulfite, or hydroxylamine, is added to the developer as a preservative. In the case of an infectious developer, formaldehyde sodium bisulfite, which gives almost no free sulfite ion in the developer, may be used.

As the fixer, one having a commonly used composition can be used.

As the fixing agent, in addition to thiosulfate and thiocyanate, an organic sulfur compound having an effect as a fixing agent can be used.

The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

The fixing solution may contain a complex of ethylenediaminetetraacetic acid and a trivalent iron ion as a sulfiding agent.

(Effect of the Invention) The silver halide photographic light-sensitive material of the present invention has an excellent effect that it has a good image quality, does not impair the sensitivity in the infrared region, and has little residual color after development processing. Moreover, in the silver halide photographic light-sensitive material of the present invention, the hydrophilic colloid layer is colored with a water-soluble dye, has no adverse effect on the photographic characteristics of the photographic emulsion, and is easily decolorized by photographic processing. It is extremely excellent.

(Example) Next, an Example is given and this invention is demonstrated in more detail. However, the present invention is not limited to these examples.

Example 1 50 g of gelatin was dissolved in water, and the dyes shown in Table 1 were added thereto. Further, 30 ml of a 4 wt% aqueous solution of sodium dodecylbenzene sulfonate as a surfactant and 45 ml of a 1 wt% aqueous solution of 1-hydroxy-3,5-dichlorotriazine sodium salt as a hardening agent were added to prepare a total amount of 1. did. This gelatin-containing aqueous solution was applied onto a cellulose triacetate film so that the dry film thickness was 5 μm. On the other hand, silver chloroiodobromide chemically sensitized with gold and sulfur compounds (bromine content 70 mol%, iodine content 0.2 mol%, silver halide average diameter 0.45 μm
m) Sensitizing dye II-1 described in JP-A-59-192242 per 1 kg of emulsion
(See below) 0.05% by weight methanol solution of 60 ml and
1.0 of Compound III-1 (see below) described in 59-192242
40 ml of a wt% methanol solution was added, and further 30 ml of a 4.0 wt% aqueous solution of sodium dodecylbenzene sulfonate was added 1-
Hydroxy-3,5-dichlorotriazine sodium salt
35 ml of 1.0 wt% aqueous solution was added and stirred, and the film was coated on the surface opposite to the gelatin-coated surface. Further, an aqueous solution containing gelatin and sodium dodecylbenzenesulfonate was applied as a protective layer thereon.

The film thus prepared is exposed by (A) 760 nm light emitting diode (B) 783 nm semiconductor laser respectively, and an automatic developing machine is used using Fuji Photo Film developer LD-835.
It was treated with FG-800RA at 38 ° C for 20 seconds.

The image quality was evaluated in 5 grades from 1 (there are many fringes and the point quality is very poor) to 5 (the image is sharp without fringes).

The results are shown in Table 1.

(II-1) 4,4'-bis- [4,6-di (benzothiazolyl-2-thio) pyrimidin-2-ylamino] stilbene-2,2 '
-Disulfonic acid disodium salt The dye a is the same as the dye 1 (II-3) described in JP-A-50-100116, and the dye b is the same as the dye 3 (II-4) described in JP-A-50-100116. As is clear from Table 1, in the system using the dye of the present invention, good image quality can be obtained with both light emitting diode and semiconductor laser exposure.

Example 2 50 g of gelatin was dissolved in 800 cc of water, and the dye was added so that the amount thereof shown in Table 2 was present, and the mordant A shown below was added.
Was applied to the cellulose triacetate film added so as to be 1 g / m ² . The same infrared sensitized silver halide emulsion as in Example 1 was coated thereon, and further an aqueous solution containing gelatin and sodium dodecylbenzene sulfonate as a protective layer was coated thereon.

A dark red filter (SC from Fuji Photo Film Co., Ltd.
-72) and exposed to light with a wedge, developed with the following developer at 20 ° C. for 4 minutes, stopped, fixed and washed with water. The density was measured using a P-type densitometer manufactured by Fuji Photo Film Co., Ltd.
The fog value was obtained (sensitivity is represented by the reciprocal of the amount of light giving an optical density of fog + 0.3). The image quality evaluation criteria are the same as in the first embodiment.

Formulation of development process Metol 0.31 g Anhydrous sodium sulfite 39.6 g Hydroquinone 6.0 g Anhydrous sodium carbonate 18.7 g Potassium bromide 0.86 g Citric acid 0.68 g Potassium metabisulfite 1.5 g Add water 1 (mordanting agent A) As is clear from Table 2, the use of the dye of the present invention causes a slight decrease in sensitivity, but the decrease in sensitivity is less than that of the comparative dye, and the fog does not increase, and the image quality is good.

The sample prepared above was exposed with a semiconductor laser and developed with a GS-1 processing solution manufactured by Fuji Photo Film Co., Ltd.

The image quality at that time was as shown in Table 3.

As is clear from Table 3, the image quality of the system of the present invention is good,
A light-sensitive material with less fog can be obtained.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Keiichi Adachi, 210 Nakamura, Minamiashigara City, Kanagawa Prefecture, Fuji Photo Film Co., Ltd. ) References JP-A-50-100116 (JP, A)

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having a hydrophilic colloid layer containing at least one dye represented by the following general formula (I). General formula (I) (In the formula, R ¹ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, R ² represents a hydrogen atom or a group capable of substituting it, R ³ And R ⁴ may be the same or different from each other, represent a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, R ⁵ represents a hydrogen atom, and R ⁶ and R ⁷ may be the same or different from each other. Of course, it represents a substituted or unsubstituted alkyl group, provided that at least one of the groups represented by R ¹ , R ² , R ³ , R ⁴ , R ⁶ or R ⁷ is a sulfo group or a salt thereof or a carboxyl group as a substituent. Group or a salt thereof.)