JP2665608B2 - Silver halide photographic light-sensitive material and processing method thereof - Google Patents

Description

The present invention relates to a silver halide photographic light-sensitive material which is spectrally sensitized in the infrared region, and in particular, a high contrast silver halide which is spectrally sensitized in the infrared region. The present invention relates to a photographic light-sensitive material and a processing method thereof.

(Prior Art) One of the exposure methods of a photographic light-sensitive material is to scan an original image and expose the silver halide photographic light-sensitive material on the basis of the image signal to expose a negative or positive image corresponding to the image of the original image. There is known an image forming method by a so-called Scanner method for forming an image.

There are various recording apparatuses in which the image forming method of the Scanner system is practically used, and a glow lamp, a xenon lamp, a mercury lamp, a tungsten lamp, a light emitting diode and the like have been conventionally used as a light source for recording of these Scanner system recording apparatuses. However, each of these light sources has a practical drawback that the output is weak and the life is short. There is a scanner that uses a coherent laser light source such as a Ne-He laser, an argon laser, and a He-Cd laser as a light source of a scanner system as a supplement to these drawbacks. These are capable of obtaining high output, but are large in size, expensive, require a modulator, and use visible light, which limits safelight of the photosensitive material, resulting in poor handling. There are drawbacks such as.

On the other hand, semiconductor lasers are small, inexpensive, and ready for modulation. They have a longer life than the above lasers and emit light in the infrared region. Since it can be used, it has an advantage that the handling workability is improved.

However, if the semiconductor laser is used as it is without shaping the laser beam, the energy distribution is broad and it is difficult to obtain a good halftone dot image or line image. Conventionally, a special developer called a lith developer has been used to obtain a good halftone dot or line image when the exposure energy distribution is broad. The squirrel developer contains only hydroquinone as a developing agent, and a sulfite which is a preservative is used in the form of an adduct with formaldehyde so as not to impair the infectious developing property, and the concentration of free sulfite ion is extremely low (usually 0.1 mol / or less). Therefore, the lith developer has a serious drawback that it is extremely susceptible to air oxidation and cannot be stored for more than 3 days.

As a method of obtaining a high-contrast photographic property using a stable developing solution, U.S. Patent Nos. 4,224,401 and 4,168,977.
No. 4,166,742, 4,311,781, 4,272,60
There is a method using a hydrazine derivative described in No. 6, No. 4,211,857, No. 4,243,739 and the like. According to this method, photographic characteristics with high contrast and high sensitivity can be obtained, and since it is permissible to add a high concentration of sulfite to the developing solution, the stability of the developing solution against air oxidation is not improved in the lith developer. Greatly improved compared to.

(Problems to be Solved by the Invention) However, the system using the hydrazine derivative and the cationic dye has a problem that a failure called black spot in this field is likely to occur, which is not preferable in the photomechanical process.

Here, the black spots are spot-like black spots (black peppers) that occur in non-image areas (for example, between the dots), and are commonly used as preservatives because the developer becomes tired over time. It occurs remarkably when the amount of sulfite ions present decreases or when the pH of the developing solution becomes high, impairing photographic quality.

Furthermore, a sensitizing material having a maximum sensitization at a wavelength longer than 750 nm, high sensitivity and sufficiently high contrast has not been obtained yet. Various techniques of infrared sensitization are known, but even if an attempt is made to obtain a high-contrast infrared light-sensitive material simply by combining the above-mentioned known hydrazine derivatives, the sensitivity becomes low and black spots increase. It has a harmful effect such as a failure or a decrease in Dmax.

(Object of the invention) Therefore, the object of the present invention is to use a stable developer, γ is extremely high to exceed 10 and has practical Dmax and high sensitivity and photographic characteristics with few black spots, and sensitivity to infrared light. To provide a sufficiently high silver halide photographic light-sensitive material.

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a silver halide photographic light-sensitive material in which at least one silver halide photographic emulsion layer is coated on a support, and silver halide grains in the silver halide emulsion. Is a cubic monodisperse grain containing at least one group 8 metal atom, and the sensitization maximum of the silver halide emulsion is 750 nm.
A silver halide photographic light-sensitive material characterized by being sensitized to a longer wavelength and further containing at least one hydrazine derivative represented by the following general formula (I), and a general formula (I) In the formula, B ₁ represents an aliphatic group or an aromatic group, B ₂ represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a carbamoyl group or an oxycarbonyl group, G ₁ is Carbonyl group, sulfonyl group, sulfoxy group, Or an iminomethylene group, D ₁ and D ₂ are both hydrogen atoms or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group. Represents a group.

In a silver halide photographic light-sensitive material in which at least one silver halide photographic emulsion layer is coated on a support, the silver halide grains in the silver halide emulsion contain at least one Group 8 metal atom. The silver halide emulsion has a maximum sensitization wavelength sensitized to longer than 750 nm and further contains a hydrazine derivative represented by the general formula (I). The silver halide photographic light-sensitive material contains at least 0.2 g / benzotriazole compound represented by the following general formula (II), and has a pH value of
Was processed with a developing solution of 11 or more in order to achieve a silver halide photographic light-sensitive material.

General formula (II) However, W is a hydrogen atom, a halogen atom (for example, a chlorine atom,
Bromine atom, etc.), alkyl group (eg, methyl group, ethyl group, propyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, etc.), hydroxy group, sulfo group, carboxy group.

(Specific Configuration of the Invention) The specific configuration of the present invention will be described in detail.

The silver halide emulsion used in the present invention may have any composition such as silver chloride, silver chlorobromide, silver iodobromide and silver iodochlorobromide, but the content of silver iodide is 10 mol% or less. Is preferred, and particularly preferably 0.05 to 5 mol%.

The average grain size of silver halide used in the present invention is preferably fine grains (for example, 0.7 μ or less), and particularly 0.5 μ
The following are preferred.

The silver halide grains in the present invention are substantially [100]
It is a cubic particle composed of planes. The term "consisting essentially of [100] planes" is more specifically 50% or more, more preferably 80% or more, and particularly preferably 95% of the grains contained in the silver halide emulsion. It is meant that the above number of grains consists of cubes and / or grains whose [100] faces occupy 60% or more of the surface area of the grains.

The grain size distribution of the silver halide grains used in the present invention is
It is preferably monodisperse.

Monodisperse here means the coefficient of variation defined below.
It means a silver halide emulsion having a grain size distribution of 40% or less, particularly preferably 20% or less.

Where the coefficient of variation is Is defined as

The photographic emulsion used in the present invention is P. Glafkides Chimie.
et Physique Photo-graphique (published by Paul Montel, 196
7 years), Photographic Emulsion Chemistry by GF Duffin
(Thy Focal Press, 1966), VLZelikman et al
By Making and Coating Photographic Emulsion (The Fo
cal Press, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a method of reacting a soluble silver salt and a soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. Good.

A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. PA in the liquid phase in which silver halide is formed as a form of simultaneous mixing method.
How to keep g constant, that is, so-called controlled
The double jet method can also be used.

According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

Further, in order to make the particle size uniform, British Patent 1,
No. 535,016, Japanese Examined Patent Publication Nos. 48-36890 and 52-16364, a method of changing the addition rate of silver nitrate or an alkali halide according to the grain growth rate, and US Pat.
It is preferable to use the method of changing the concentration of the aqueous solution as described in 4,242,445 and JP-A-55-158124 to grow the growth rapidly within a range not exceeding the critical saturation.

The silver halide grains may have a so-called core / shell type structure in which the inside and the surface have different halogen compositions. Particularly in the case of silver iodobromide, it is preferable that the silver iodide ratio of the core is higher than that of shell by 0.5 mol% or more,
Further, it is more preferable that it is higher than 2 mol%.

Metals contained in Group VIII in the periodic table used in the present invention, iron, cobalt, nickel, ruthenium,
Examples of compounds containing rhodium, palladium, osmium, iridium and platinum, which are preferably used in the present invention, include iron sulfate (II) FeSO ₄ -5H ₂ O; iron chloride (III) FeCl ₃ ; hexacyanoiron ( II) Potassium K ₄ F
_{e (CN) 6 · 3H 2} O; potassium hexacyanoferrate (III) K ₃ F
e (CN) ₆ ; Cobalt chloride (II) CoCl ₂ ; Cobalt nitrate (I
_{I) Co (NO 3) 2} · 6H 2 O; hexacyanocobaltate (III) potassium K ₃ Co (CN) _6; chloride nickel _{(II) NiCl 2; 6H 2} O nitrate nickel _{(II) Ni (NO 3)} 2・ 6H ₂ O; Ruthenium (III) chloride RuCl ₃ ; Potassium hexachlororuthenium (IV) ・ K ₂ RuCl ₆ ; Rhodium (III) chloride RhCl ₃・ 4H ₂ O; Ammonium hexachlororhodium (III) (NH) ₃ RhCl ₆ ; Palladium (II) chloride PdCl ₂ ; Palladium (II) nitrate Pd (NO
₃ ) ₂ ; Palladium (II) bromide PdBr ₂ ; Potassium hexachloropalladium (IV) K ₂ PdCl ₆ ; Potassium tetrathiopalladium (II) ・ K ₂ Pd (CNS) ₄ ; Osmium chloride (I
I) UsCl ₂ ; Iridium (III) chloride IrCl ₃ ; Iridium chloride (IV) IrCl ₄ ; Iridium bromide (III) IrBr ₃ .4H ₂ O; Iridium bromide (IV) IrBr ₄ ; Hexachloroiridium (II)
I) Potassium K ₃ IrCl ₆ ; Hexachloroiridium (IV)
Potassium acid K ₂ IrCl ₆ ; Ammonium hexachloroplatinate (IV) ₂ (NH ₄ ) ₂ PtCl ₆ ; Potassium hexachloroplatinate (IV)
K ₂ PtCl ₆ ; ammonium hexabromoplatinate (IV) (N
H ₄ ) ₂ PtBr ₆ ;. These Group VIII metal compounds are used alone or in combination of two or more compounds in an amount corresponding to 10 ⁻⁹ mol to 10 ⁻³ mol per mol of silver halide. Particularly, the combination of two or three of iridium salt, rhodium salt and iron salt is advantageously carried out. Addition of these compounds can be appropriately carried out at the time of producing the silver halide emulsion and at each stage before coating the emulsion. Further, in the above-mentioned method for producing silver halide grains, it may be added at any stage of nucleation or growth, and further during chemical ripening of the silver halide emulsion.
In particular, it is preferably incorporated in silver halide grains.

The silver halide emulsion of the present invention is preferably gold-sensitized and sulfur-sensitized.

Examples of the gold sensitizer used in the present invention include various gold salts such as potassium chloroaurite, potassium aurithothiocyanate, potassium chloroaurate, and aurik trichloride. Specific example is U.S. Pat.
3 and 2642361.

As the sulfur sensitizer used in the present invention, various sulfur compounds such as thiosulfates, thioureas, thiazoles, and rhodanines can be used in addition to the sulfur compounds contained in gelatin. Specific examples are U.S. Pat.
944, 2,278,947, 2,410,689, 2,728,668
No. 3,501,313, and No. 3,656,955. Preferred sulfur compounds are thiosulfates and thiourea compounds.

The addition amount of the sulfur sensitizer and the gold sensitizer is preferably 10 ^-2 to 10 ^-7 mol per mol of silver, more preferably 1 x 10 ^-3 to
It is 1 × 10 ⁻⁵ mol.

The molar ratio of the sulfur sensitizer to the gold sensitizer is 1: 3 to 3: 1 and preferably 1: 2 to 2: 1.

 In the present invention, a reduction sensitization method can be used.

As the reduction sensitizer, a primary tin salt, amines, formamidine sulfinic acid, a silane compound or the like can be used.

The silver halide emulsion of the present invention is infrared-sensitized so as to have a maximum 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 dye represented by the following general formula (IIIa) or (IIIb) is used. Is particularly preferable.

The infrared sensitizing dye represented by formula (IIIa) or (IIIb) is described in detail below.

General formula (III a) In formula (IIIa), R ₁ and R ₂ may be the same or different and each represents an alkyl group. R ₃
Represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group, a benzyl group or a phenethyl group. V represents a hydrogen atom, a lower alkyl group, an alkoxy group, a halogen atom or a substituted alkyl group. Z ₁ represents a non-metal atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle.
X ₁ represents an acid anion. m, p and q each independently represent 1 or 2.

 However, q is 1 when the dye forms an inner salt.

R ₁ and R _{2 in} formula (IIIa) may be the same or different and each represents an alkyl group (including a substituted alkyl group). Preferably, it has 1 to 8 carbon atoms. For example methyl, ethyl, propyl, butyl, pentyl, heptyl, octyl.

Examples of the substituent include a carboxyl group, a sulfo group, a cyano group, a halogen atom (for example, a fluorine atom, a chlorine atom,
Bromine atom), hydroxyl group, alkoxycarbonyl group (preferably having 8 or less carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl, etc.), alkoxy group (preferably having 7 or less carbon atoms, for example, methoxy, ethoxy, propoxy). , Butoxy, benzyloxy), aryloxy groups (eg phenoxy, p-tolyloxy), acyloxy groups (preferably having 3 or less carbon atoms, eg acetyloxy, propionyloxy), acyl groups (preferably having 8 or less carbon atoms, eg Acetyl, propionyl, benzoyl, mesyl), carbamoyl group (eg carbamoyl, N, N-dimethylcarbamoyl, morpholinocarbamoyl, piperidinocarbamoyl), sulfamoyl group (eg sulfamoyl, N, N-dimethyl) Rufamoyl, morpholinosulfonyl), an alkyl group substituted with an aryl group (eg, phenyl, p-hydroxyphenyl, p-carboxyphenyl, p-sulfophenyl, α-naphthyl) (preferably having 6 or less carbon atoms in the alkyl moiety). ) Is mentioned. However, two or more of these substituents may be combined and substituted with an alkyl group.

R ₃ is a hydrogen atom, a lower alkyl group (preferably having 1 to 4 carbon atoms, for example, methyl, ethyl, propyl, butyl), a lower alkoxy group (preferably having 1 to 4 carbon atoms).
4, for example methoxy, ethoxy, propoxy, butoxy), phenyl, benzyl or phenethyl groups. Particularly, a lower alkyl group and a benzyl group are advantageously used.

V is a hydrogen atom, a lower alkyl group (preferably having 1 to 4 carbon atoms, such as methyl, ethyl, propyl), an alkoxy group (preferably having 1 to 4 carbon atoms, such as methoxy, ethoxy, butoxy), a halogen atom (eg, It represents a fluorine atom, a chlorine atom) or a substituted alkyl group (preferably having 1 to 4 carbon atoms, for example, trifluoromethyl, carboxymethyl).

Z ₁ represents a group of non-metal atoms necessary for completing a 5- or 6-membered nitrogen-containing heterocycle, for example, a thiazole nucleus [eg, benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzo]. Thiazole,
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], selenazole nucleus [eg benzoselenazole, 5-chlorobenzoselenazole, 5-methoxybenzoselenazole, 5 -Methylbenzoselenazole, 5-hydroxybenzoselenazole, naphtho [2,1-d] selenazole, naphtho [1,2-
d] selenazole], 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, 6-hydroxybenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 5-ethoxybenzoxazole, naphtho [2,1- d] oxazole, naphtho [1,2-d] oxazole, naphtho [2,3-
d] oxazole], 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], 3,3-dialkylindolenine nucleus (eg, 3,3- Dimethylindolenine, 3,3-diethylindolenine, 3,3-dimethyl-5-cyanoindolenine, 3,3-dimethyl-5-methoxyindolenine,
3,3-Dimethyl-5-methylindolenine, 3,3-dimethyl-5-chloroindolenine), imidazole nucleus (e.g., 1-methylbenzimidazole, 1-ethylbenzimidazole, 1-methyl-5-chlorobenzo) Imidazole, 1-ethyl-5-chlorobenzimidazole, 1
-Methyl-5,6-dichlorobenzimidazole, 1-ethyl-5,6-dichlorobenzimidazole, 1-ethyl-5-methoxybenzimidazole, 1-methyl-5-
Cyanobenzimidazole, 1-ethyl-5-cyanobenzimidazole, 1-methyl-5-fluorobenzimidazole, 1-ethyl-5-fluorobenzimidazole, 1-phenyl-5,6-dichlorobenzimidazole, 1-allyl -5,6-dichlorobenzimidazole,
1-allyl-5-chlorobenzimidazole, 1-phenylbenzimidazole, 1-phenyl-5-chlorobenzimidazole, 1-methyl-5-trifluoromethylbenzimidazole, 1-ethyl-5-trifluoromethylbenzimidazole , 1-ethylnaphtho [1,2-
d] imidazole), pyridine nucleus (eg pyridine, 5
-Methyl-2-pyridine, 3-methyl-4-pyridine)
Can be mentioned. 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. m, p and q each independently represent 1 or 2.

 However, q is 1 when the dye forms an inner salt.

X ₁ is an acid anion (for example, chloride, bromide, iodide, tetrafluoroborate, hexafluorophosphate, methylsulfate, ethylsulfate, benzenesulfate, 4-methylbenzenesulfonate,
4-chlorobenzene sulfonate, 4-nitrobenzene sulfonate, trifluoromethane sulfonate, perchlorate).

General formula (III b) In the formula, R ₁ ′ and R ₂ ′ may be the same or different and each represents an alkyl group. R ₃ ′ and R ₄ ′ each independently represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group, a benzyl group or a phenethyl group. R ₅ ′ and R ₆ ′ each represent a hydrogen atom, or
R ₅ ′ and R ₆ ′ combine to form a divalent alkylene group.
R ₇ 'is a hydrogen atom, a lower alkyl group, a lower alkoxy group,
Phenyl group, benzyl group, or Represents Provided that W ₁ ′ and W ₂ ′ each independently represent an alkyl group or an aryl group, and W ₁ ′ and W ₂ ′ are connected to each other to form a 5- or 6-membered nitrogen-containing heterocycle. You can also Further, R ₃ ′ and R ₇ ′ or R ₄ ′ and R ₇ ′ may be linked to each other to form a divalent alkylene group. Z'and
Z ₁ ′ each independently represents a group of non-metal atoms necessary for completing a 5- or 6-membered nitrogen-containing heterocycle. X ₁ represents an acid anion, and m ′ represents 1 or 2.

However, m'is 1 when the dye forms an intramolecular salt.

The alkyl groups of the general formula (III b) R ₁ ′ and R ₂ ′ include substituted alkyl groups, specific examples of which are those of the general formula (III a)
_The same as described in ₁ and R ₂ .

Specific examples of R ₃ ′ and R ₄ ′ in the general formula (III b) are represented by the general formula (I
It is the same as described in R ₃ of II a).

R ₅ ′ and R ₆ ′ each represent a hydrogen atom, or
R ₅ 'and R ₆ ' combine to form a divalent alkylene group (eg ethylene or trimethylene). The alkylene group is one, two or more suitable groups such as an alkyl group (preferably having 1 to 4 carbon atoms, eg, methyl, ethyl, propyl, isopropyl, butyl), a halogen atom (eg, chlorine atom, bromine). Atom) or an alkoxy group (preferably having 1 to 4 carbon atoms, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy) and the like.

R ₇ 'is a hydrogen atom, a lower alkyl group (preferably having from 1 to 4 carbon atoms, such as methyl, ethyl, propyl, etc.),
A lower alkoxy group (preferably having 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy, butoxy, etc.),
Phenyl, benzyl group, or Represents Here, W ₁ ′ and W ₂ ′ are each independently an alkyl group (including a substituted alkyl group. Preferably, the alkyl moiety has 1 to 18 carbon atoms, more preferably 1 to 4, for example, methyl, ethyl, propyl, butyl, Benzyl, phenylethyl), or an aryl group (including a substituted phenyl group, for example, phenyl, naphthyl, tolyl, p-chlorophenyl, etc.), wherein W ₁ ′ and W ₂ ′ are linked to each other to include a 5- or 6-membered group. It is also possible to form a nitrogen heterocycle. However,
R ₃ ′ and R ₇ ′ or R ₄ ′ and R ₇ ′ are linked to form a divalent alkylene group (synonymous with the divalent alkylene group formed by linking R ₅ ′ and R ₆ ′ above). It can also be formed.

Specific examples of the 5- or 6-membered nitrogen-containing heterocycle formed by Z ′ and Z ₁ ′ are the same as the ring described for Z ₁ in the general formula (IIIa).

Specific examples of the acid anion of X ₁ ′ are the same as the acid anion described in X ₁ of the general formula (IIIa).

m'represents 0 or 1, and is 1 when the dye forms an intramolecular salt.

Specific examples of the infrared sensitizing dye represented by formula (IIIa) or (IIIb) are shown below. However, the present invention is not limited to these infrared sensitizing dyes.

The infrared sensitizing dye represented by the general formula (IIIa) is disclosed in JP-A-59-59
In the method shown in -292242, the infrared sensitizing dye represented by the general formula (IIIb) is, for example, U.S. Pat.
It can be synthesized by a method such as 56,227.

The sensitizing dye of the general formula (IIIa) is particularly preferable because it has excellent sensitizing properties in the infrared region.

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 ₁₃ is a hydrogen atom,
It represents an alkyl group (having 8 or less carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, etc.) and an alkenyl group (eg, an allyl group). 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-toluenesulfonic acid, etc.) and Z ₃ are preferably thiazolium. 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 / 1 ~ 1/300
Is preferably used, and particularly, the range of 1/2 to 1/50 is preferably used.

The compound represented by the general formula (IV) used in the present invention can be directly dispersed in an emulsion, and a suitable solvent (for example, water, methyl alcohol, ethyl alcohol, propanol, methyl cellosolve, acetone, etc.).
Alternatively, these solvents can be dissolved in a mixed solvent containing a plurality of solvents and added to the emulsion. Other sensitizing dyes can be added to the emulsion in the form of a solution or a dispersion in a colloid according to the method of addition.

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.

The combination of the present invention may further include a compound of the following general formula (V).

General formula (V) Here, A represents a divalent aromatic residue. R ₂₁ , R ₂₂ , R
₂₃ and R ₂₄ are each a hydrogen atom, a hydroxy 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, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted It represents a substituted arylamino group, a substituted or unsubstituted aralkylamino group, an aryl group, or a mercapto group.

However, at least one of A, R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ has a sulfo group. W ₃ and W ₄ is -CH =, or -N
Represents =. However, at least one of W ₃ and W ₄ represents -N =.

 The general formula (V) will be described in more detail.

Wherein, -A- represents a divalent aromatic residue, which -SO ₃ M group [wherein M represents a cation [such as sodium, potassium, etc.) to give a hydrogen atom or a water-soluble. ] May be included.

As -A-, those selected from the following -A ₁ -or -A _2- are useful. However, when R ₂₁ , R ₂₂ , R ₂₃ or R ₂₄ is --SO
_{When 3} M is not included, -A- is selected from the group of -A _1- .

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

R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ are each a hydrogen atom, a hydroxy group, a lower alkyl group (the number of carbon atoms is preferably 1 to 8, for example, methyl group, ethyl group, n-propyl group, n
-Butyl group), an alkoxy group (preferably having a carbon number of 1 to 8, 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, p-
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 benzothiazolitho group) Ruthio 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) Group, dimethylamino group, diethylamino group, dodecylamino group, cyclohexylamino group, β-hydroxyethylamino group, di- (β-hydroxyethyl) amino group, β-sulfoethylamino group), arylamino group, or substituted aryl Amino groups (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
-Carboxyarinino group, p-carboxyanilino group,
o-chloroanilino group, m-chloroanilino group, p-chloroanilino group, p-aminoanilino group, o-anisino group, m-anisidino group, p-anisino group, o-acetaminoanilino group, hydroxyanilino group, di- Sulfophenylamino group, naphthylamino group, sulfonaphthylamino group, etc.), heterocyclylamino group (eg, 2-benzothiazolylamino group, 2-pyridyl-amino group, etc.), substituted or unsubstituted aralkylamino group (eg, Benzylamino group, o-anisylamino group, m-anisylamino group, p-anisylamino group, etc.), aryl group (eg, phenyl group, etc.), and mercapto group. R
₂₁ , R ₂₂ , R ₂₃ , and R ₂₄ may be the same or different from each other. -A- is -A ₂ - when selected from the group of, R _21, R
_At least one of ₂₂ , R ₂₃ and R ₂₄ needs to have at least one sulfo group (which may be a free acid group or may form a salt). W ₃ and W ₄ represents -CH = or -N =, at least one is -N =.

Next, specific examples of the compound included in the general formula (V) will be given. However, the compound is not limited to these compounds.

(V-1) 4,4'-bis [4,6-di (benzothiazolyl-2-thio) pyrimidin-2-ylamino] stilbene-2,2'-disulfonic acid disodium salt (V-2) 4,4 '-Bis [4,6-di (benzothiazolyl-2-amino) pyrimidin-2-ylamino)] stilbene-2,2'-disulfonic acid disodium salt (V-3) 4,4'-bis [4,6 -Di (naphthyl-2-oxy) pyrimidin-2-ylamino] stilbene-2,
2'-Disulfonic acid disodium salt (V-4) 4,4'-bis [4,6-di (naphthyl-2-oxy) pyrimidin-2-ylamino] bibenzyl-2,
2'-Disulfonic acid disodium salt (V-5) 4,4'-bis (4,6-dianilinopyrimidin-2-ylamino) stilbene-2,2'-disulfonic acid disodium salt (V-6) 4 , 4'-Bis [4-chloro-6- (2-naphthyloxy) pyrimidin-2-ylamino] biphenyl-2,2'-disulfonic acid disodium salt (V-7) 4,4'-bis [4, 6-Di (1-phenyltetrazolyl-5-thio) pyrimidin-2-ylamino] stilbene-2,2'-disulfonic acid disodium salt (V-8) 4,4'-bis [4,6- Di (benzimidazolyl-2-thio) pyrimidin-2-ylamino] stilbene-2,2'-disulfonic acid disodium salt (V-9) 4,4'-bis [4,6-diphenoxypyrimidin-2-ylamino ) Stilbene-2,2'-disulfonic acid disodium salt (V-10 4,4'-bis [4,6-diphenylthiopyrimidin-2-ylamino) stilbene-2,2'-disulfonic acid disodium salt (V-11) 4,4'-bis [4,6-dimercapto Pyrimidin-2-ylamino) biphenyl-2,2'-disulfonic acid disodium salt (V-12) 4,4'-bis [4,6-dianilino-triazin-2-ylamino) stilbene-2,2'-disulfone Acid disodium salt (V-13) 4,4'-bis (4-anilino-6-hydroxy-triazin-2-ylamino) stilbene-2,
2'-Disulfonic acid disodium salt (V-14) 4,4'-bis [4-naphthylamino-6-
Anilino-triazin-2-ylamino) stilbene-
2,2'-Disulfonic acid disodium salt (V-15) 4,4'-bis [2,6-di (2-naphthoxy)]
Pyrimidin-4-ylamino] stilbene-2,2′-disulfonic acid (V-16) 4,4′-bis [2,6-di (2-naphthylamino) pyrimidin-4-ylamino] stilbene-2,2 ′
-Disulfonic acid disodium salt (V-17) 4,4'-bis [2,6-dianilinopyrimidin-4-ylamino) stilbene-2,2'-disulfonic acid disodium salt (V-18) 4,4 ′ -Bis [2-naphthylamino) -6
-Anilinopyrimidin-4-ylamino] stilbene-
2,2'-Disulfonic acid (V-19) 4,4'-bis [2,6-diphenoxypyrimidin-4-ylamino] stilbene-2,2'-disulfonic acid ditriethylammonium salt (V-20) 4,4'-bis [2,3-di (benzimidazolyl-2-thio) pyrimidin-4-ylamino] stilbene-2,2'-disulfonic acid disodium salt The compound represented by the general formula (V) is known. Alternatively, it can be easily produced according to a known method.

The compound represented by the general formula (V) used in the present invention may be a mixture of two or more kinds thereof. The compounds of general formula (V) are advantageously used in an amount of about 0.01 to 5 grams per mole of silver halide in the emulsion.

The ratio (weight ratio) between the infrared sensitizing dye and the compound represented by the general formula (V) is preferably such that the dye / the compound represented by the general formula (V) = 1/1 to 1/200. Especially 1 /
A range of 2 to 1/50 is advantageously used.

The compound represented by the general formula (V) used in the present invention can be directly dispersed in an emulsion, and can also be dispersed in a suitable solvent (eg methyl alcohol, ethyl alcohol, methyl cellosolve, water, etc.) or a mixed solvent thereof. It is also possible to add it to the emulsion by dissolving it in. Other sensitizing dyes can be added to the emulsion in the form of a solution or a dispersion in a colloid according to the method of addition. In addition, JP-A-
It can be dispersed and added to the emulsion by the method described in JP-A-80119.

The infrared sensitizing dye represented by formula (IIIa) or (IIIb) according to the present invention can be used in combination with other sensitizing dyes. For example, U.S. Pat.
2,688,545, 3,397,060, 3,615,635, 3,628,964, British Patents 1,242,588, 1,293,86
No. 2, Japanese Patent Publication No. 43-4936, No. 44-14030, No. 43-10773
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.
And sensitizing dyes described in JP-A No. 3,635,721 and the like can be used.

The hydrazine derivative used in the present invention is represented by the general formula (I).

General formula (I) In the formula, B ₁ represents an aliphatic group or an aromatic group, B ₂ represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a carbamoyl group or an oxycarbonyl group, G ₁ is Carbonyl group, sulfonyl group, sulfoxy group, Or an iminomethylene group, D ₁ and D ₂ are both hydrogen atoms or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group. Represents a group.

In the general formula (I), the aliphatic group represented by B ₁ preferably has 1 to 30 carbon atoms, particularly 1 to 20 carbon atoms.
Is a linear, branched or cyclic alkyl group. Here, the branched alkyl group may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. Further, this alkyl group may have a substituent such as an aryl group, an alkoxy group, a sulfoxy group, a sulfonamide group, a carbonamide group or the like.

The aromatic group represented by B ₁ in the general formula (I) is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group.
Here, the unsaturated heterocyclic group may be bonded to a monocyclic or bicyclic aryl group to form a heteroaryl group.

For example, there are a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, a benzothiazole ring, and among others, a ring containing a benzene ring is preferable.

Particularly preferred as B ₁ is an aryl group.

The aryl group or unsaturated heterocyclic group of B ₁ may be substituted, and typical examples of the substituent include a linear, branched or cyclic alkyl group (preferably having 1 to 20 carbon atoms), an aralkyl group. (Preferably an alkyl moiety having 1 to 3 carbon atoms having 1 to 3 rings), an alkoxy group (preferably having 1 to 20 carbon atoms), a substituted amino group (preferably having 1 to 20 carbon atoms) Substituted amino group), acylamino group (preferably having 2 to 30 carbon atoms), sulfonamide group (preferably having 1 to 30 carbon atoms), ureido group (preferably having 1 to 30 carbon atoms) Things to have) and so on.

The alkyl group represented by B ₂ in the general formula (I) is preferably an alkyl group having 1 to 4 carbon atoms,
It may have a substituent such as a halogen atom, a cyano group, a carboxy group, a sulfo group, an alkoxy group and a phenyl group.

The aryl group represented by B ₂ is preferably a monocyclic or bicyclic aryl group, and includes, for example, a benzene ring. This aryl group may be substituted with, for example, a halogen atom, an alkyl group, a cyano group, a carboxyl group, a sulfo group or the like.

The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, and may be substituted with a halogen atom, an aryl group, or the like.

The aryloxy group is preferably a monocyclic one, and the substituent includes a halogen atom and the like.

The amino group is an unsubstituted aquino group and has 1 to 10 carbon atoms.
Are preferred, and may be substituted with an alkyl group, a halogen atom, a cyano group, a nitro group, a carboxy group, or the like. The carbamoyl group is preferably an unsubstituted carbamoyl group, an alkylcarbamoyl group having 1 to 10 carbon atoms or an arylcarbamoyl group, and may be substituted with an alkyl group, a halogen atom, a cyano group, a carboxy group or the like.

The oxycarbonyl group is preferably an alkoxycarbonyl group having 1 to 10 carbon atoms or an aryloxycarbonyl group, and may be substituted with an alkyl group, a halogen atom, a cyano group, a nitro group or the like.

Preferred among the groups represented by B ₂ are hydrogen atom, alkyl group (for example, methyl group, trifluoromethyl group, 3-hydroxypropyl group, 3-methanesulfonamidopropyl group) when G ₁ is a carbonyl group. Group), aralkyl group (eg, o-hydroxybenzyl group), aryl group (eg, phenyl group, 3,5-dichlorophenyl group, o-methanesulfonamidophenyl group,
4-methanesulfonylphenyl group) and the like, and a hydrogen atom is particularly preferable.

When G ₁ is a sulfonyl group, B ₂ is an alkyl group (eg, methyl group) or an aralkyl group (eg, o).
-Hydroxyphenylmethyl group, etc.), aryl group (eg, phenyl group, etc.) or substituted amino group (eg,
Dimethylamino group) and the like are preferable.

When G ₁ is a sulfoxy group, preferred B ₂ is a cyanobenzyl group, a methylthiobenzyl group, etc., and G ₁ is In the case of, B ₂ is preferably a methoxy group, an ethoxy group, a butoxy group, a phenoxy group or a phenyl group, and particularly,
A phenoxy group is preferred.

When G ₁ is an N-substituted or unsubstituted iminomethylene group,
Preferred B ₂ is a methyl group, an ethyl group, or a substituted or unsubstituted phenyl group.

As the substituent for B _2, the substituents enumerated for B ₁ can be applied, and for example, an acyl group, an acyloxy group, an alkyl or aryloxycarbonyl group, an alkenyl group, an alkynyl group, a nitro group and the like can also be applied.

A carbonyl group is most preferable as G in the general formula (I).

Also, B ₂ splits the G ₁ -B ₂ part from the rest of the molecule,
It may be one that causes a cyclization reaction to form a cyclic structure containing an atom of the B ₂ moiety, and specifically, one that can be represented by the general formula (a).

In the general formula (a) -B ₃ -Z ₁ formula, Z ₁ is nucleophilically attacked to G _1, is a group capable of splitting the G ₁ -B ₃ -Z ₁ moiety from the remainder molecule, B ₃ Is one obtained by removing one hydrogen atom from B ₂ , and Z ₃₃ nucleophilically attacks G ₁ .
G ₁ , B ₃ , and Z ₃₃ can form a cyclic structure.

More specifically, Z ₃₃ easily undergoes a nucleophilic reaction with G ₁ when the hydrazine compound of the general formula (I) produces the next reaction intermediate due to oxidation or the like, and B ₁ -N = N-G ₁ -B _3- Z ₃₃ B ₁ —N═N is a group capable of being split from G ₁ and specifically includes OH, SH or NHB ₄ (B ₄ is a hydrogen atom, an alkyl group, an aryl group, —COB ₅ , or —SO ₂ B ₅ , B ₅ may represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, etc.), or a functional group that directly reacts with G ₁ such as COOH (wherein , OH, SH, NHB ₄ —COOH may be temporarily protected so as to generate these groups by hydrolysis of alkali etc.), or (B ₆ and B ₇ represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group) and react with G ₁ by reacting with a nucleophile such as a hydroxide ion or a sulfite ion. It may be a functional group that enables

The ring formed by G ₁ , B ₃ and Z ₃₃ is preferably a 5-membered or 6-membered ring. Among the compounds represented by the general formula (a), preferred compounds include those represented by the general formulas (b) and (c).

General formula (b) In the formula, R _b ^{1 to} R _b ⁴ are hydrogen atoms, alkyl groups, (preferably having 1 to 12 carbon atoms) alkenyl groups (preferably having 2 to 12 carbon atoms) aryl groups (preferably having 6 to 12 carbon atoms) 12
The same) or different. B is an atom necessary for completing a 5-membered ring or 6-membered ring which may have a substituent, m and n are 0 or 1, and (n +
m) is 1 or 2.

As the 5- or 6-membered ring formed by B, for example,
Examples thereof include a cyclohexane ring, a cycloheptene ring, a benzene ring, a naphthalene ring, a pyridine ring and a quinoline ring.

Z ₃₃ has the same meaning as in formula (a).

General formula (c) In the formula, R _c ¹ and R _c ² represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a halogen atom, and may be the same or different.

R _c ³ represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group.

 p represents 0 or 1, and q represents 1 to 4.

R _c ¹ , R _c ² and R _c ³ may combine with each other to form a ring as long as Z ₃₃ can undergo an intramolecular nucleophilic attack on G ₁ .

R _c ¹ and R _c ² are preferably a hydrogen atom, a halogen atom or an alkyl group, and R _c ³ is preferably an alkyl group or an aryl group.

q preferably represents 1 to 3, and when q is 1, p is 1
Or 2, when q is 2, p represents 0 or 1, when q is 3, p represents 0 or 1, and when q is 2 or 3, CR
_c ¹ R _c ² may be the same or different.

Z ₃₃ has the same meaning as in formula (a).

D ₁ and D ₂ are a hydrogen atom, an alkylsulfonyl group having 20 or less carbon atoms and an arylsulfonyl group (preferably a phenylsulfonyl group or a phenylsulfonyl group substituted so that the sum of the substituent constants of the hamet is −0.5 or more). Group), an acyl group having 20 or less carbon atoms (preferably a benzoyl group, or a benzoyl group substituted so that the sum of the substituent constants of Hamet is −0.5 or more, or a straight-chain, branched or cyclic unsubstituted or Substituted aliphatic acyl group (eg, a substituent includes a halogen atom, an ether group, a sulfonamide group, a carbonamide group, a hydroxyl group, a carboxy group, and a sulfonic acid group). D ₁ and D ₂ are most preferably a hydrogen atom. preferable.

B ₁ or B _{2 in} the general formula (I) may have a ballast group incorporated therein which is commonly used in a non-moving photographic additive such as a coupler. The ballast group is a group having a carbon number of 8 or more and relatively inert to photographic properties, and includes, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group and an alkylphenoxy group. You can choose from.

B ₁ or B _{2 in} the general formula (I) may be one in which a group that enhances adsorption to the surface of the silver halide grain is incorporated. Examples of the adsorptive group include thiourea group, heterocyclic thioamide group, mercaptoheterocyclic group, and triazole group, which are disclosed in U.S. Pat. Nos. 4,385,108, 4,459,347, and Japanese Patent Laid-Open No. 59-347.
-195,233, 59-200,231, 59-201,045, 5
9-201,046, 59-201,047, 59-201,048,
59-201,049, JP-A-61-170,733, 61-270,744
No. 62-948, Japanese Patent Application No. 62-67,508, No. 62-67,501
And the groups described in Nos. 62-67,510.

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

Examples of the hydrazine derivative used in the present invention include RESEARCH DISCLOSURE Item 23516 (1983
November, p. 346) and references cited therein,
U.S. Pat.Nos. 4,080,207, 4,269,929, 4,276,364
No., No. 4,278,748, No. 4,385,108, No. 4,458,347,
4,560,638, 4,478,928, UK Patent 2,011,391B,
JP-A-60-179734, JP-A-61-170,733, JP-A-61-27
0,744, 62-948, EP217,310, Japanese Patent Application No. 61-175,2
34, 61-251,482, 61-268,249, 61-276,
No. 283, No. 62-67,508, No. 62-67,529, No. 62-67,51
0, 62-58,513, 62-130,819, 62-143,46
Nos. 9 and 62-166,117 can be used.

In the present invention, when the hydrazine derivative represented by the general formula (I) is contained in the photographic light-sensitive material, it is preferably contained in the silver halide emulsion layer, but other non-photosensitive hydrophilic colloid layers (eg, Protective layer, intermediate layer, filter layer, anti-halation layer, etc.). Specifically, when the compound to be used is water-soluble, as an aqueous solution, and when it is poorly water-soluble, an organic solvent that can be mixed with water such as alcohols, esters, and ketones is used as a solution to prepare a hydrophilic colloid solution. Can be added to. When it is added to the silver halide emulsion layer, it may be added at any time from the start of chemical ripening to before coating, but it is preferably added after the completion of chemical ripening and before coating. In particular, it is preferable to add it to the coating solution prepared for coating.

The content of the compound represented by formula (I) of the present invention is the grain size of the silver halide emulsion, the halogen composition, the method and degree of chemical sensitization, the relationship between the layer containing the compound and the silver halide emulsion, and the fog. It is desirable to select an optimal amount depending on the kind of the preventive compound, etc., and a test method for the selection is well known to those skilled in the art. Usually, it is preferably contained in an amount of 1 × 10 ^-6 mol to 1 × 10 ^-1 mol, and particularly preferably 1 × 10 ^-5 to 1 × 10 ^-2 mol per mol of silver halide.

The compounds described in JP-A Nos. 60-140340 and 61-167939 can be added to the photographic light-sensitive material of the present invention for the purpose of enhancing the sensitivity and enhancing the contrast. These may be used alone or in combination of two or more.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fog during the manufacturing process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles, nitrobenzotriazoles. , Etc .; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetrazaine Dens), pentaazaindenes, etc .; many compounds known as antifoggants or stabilizers such as benzenethiosulphonic acid, benzenesulphonic acid, benzenesulphonic acid amide, etc. It can be obtained.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other hydrophilic colloid layers. For example, chromium salts (such as chrome myoban), aldehydes (such as formaldehyde), N-methylol compounds (such as dimethylol urea), dioxane derivatives, active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-
Propanol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids (mucochloric acid, mucofenoxiclic acid, etc.), etc. can be used alone or in combination. .

In the photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the present invention, coating aid, antistatic, swelling property improving, emulsion dispersion, adhesion preventing and photographic property improving (for example, development acceleration, hardening, sensitization). Various surfactants may be included for various purposes such as.

For example, saponin (steroidal), alkylene oxide derivative (for example, polyethylene glycol, polyethylene glycol / polypropylene glycol condensate, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, poly Alkylene glycol alkyl amines or amides, polyethylene oxide adducts of silicones), glycidol derivatives (eg, alkenyl succinic acid polyglycerides, alkyl phenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Ionic surfactants; alkyl carboxylates, alkyl sulphonates, alkyl benzenes Phuphonate, alkylnaphthalene sulfonate, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxy Anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups such as ethylene alkyl phosphates;
Amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfuric acid or phosphoric acid esters, alkyl betaines,
Amphoteric surfactants such as amine oxides; alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and phosphonium or sulfonium containing an aliphatic or heterocyclic ring. Cationic surfactants such as salts can be used.

The photographic light-sensitive material of the present invention may contain a matting agent such as silica, magnesium oxide and polymethyl methacrylate for the purpose of preventing adhesion to the photographic emulsion layer and other hydrophilic colloid layers.

The light-sensitive material of the present invention may contain a dispersion of a water-soluble or sparingly-soluble synthetic polymer for the purpose of improving the dimensional stability of the salt. For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide,
Vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene, etc., alone or in combination, or with these, acrylic acid, methacrylic acid,
A polymer having a combination of α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrene sulfonic acid as a monomer component can be used.

As the support of the light-sensitive material of the present invention, cellulose triacetate, cellulose diacetate, nitrocellulose, polystyrene, polyethylene terephthalate and the like can be used, but polyethylene terephthalate film is most preferable.

These supports may be subjected to corona treatment by a known method, or may be subjected to undercoating processing by a known method, if necessary.

In addition, a waterproof layer containing a polyvinylidene chloride-based polymer may be provided in order to enhance so-called dimensional stability, which changes in dimension due to changes in temperature and humidity.

Suitable development accelerators or nucleation infectious development accelerators for use in the present invention are disclosed in JP-A-53-77616 and JP-A-54-377.
32, 53-137, 133, 60-140, 340, 60-14959, and the like, as well as various compounds containing an N or S atom are effective.

The silver halide emulsion layer and other layers of the photographic light-sensitive material of the present invention preferably contain a compound having an acid group. Examples of the compound having an acid group include salicylic acid, acetic acid, organic acids such as ascorbic acid and acrylic acid, maleic acid,
Examples thereof include polymers or copolymers having an acid monomer such as phthalic acid as a repeating unit. Regarding these compounds, JP-A Nos. 61-223834 and 61-228437 have been used.
No. 62-25745, No. 62-55642 and Japanese Patent Application No. 61-6274.
The record of the specification No. 0 can be referred to. Among these compounds, ascorbic acid is particularly preferable as the low molecular weight compound, and an acid monomer such as acrylic acid is used as the high molecular compound and a crosslinkable monomer having two or more unsaturated groups such as divinylbenzene. It is a water dispersible latex of the copolymer.

In order to obtain ultra-high contrast and high sensitivity photographic characteristics using the silver halide light-sensitive material of the present invention, it is necessary to use a conventional infectious developer or a highly alkaline developer close to pH 13 described in U.S. Patent No. 2,419,975. And a stable developer can be used.

That is, the silver halide light-sensitive material of the present invention contains sulfite ions as a preservative in an amount of 0.15 mol / or more and has a pH of 11.0.
It is possible to obtain a sufficiently high-contrast negative image with a developing solution having a pH of -12.3, particularly pH 11.0-12.0.

There is no particular limitation on the developing agent used in the developing solution used in the present invention, but it is preferable to contain dihydroxybenzenes from the viewpoint of easily obtaining good halftone dot quality, and dihydroxybenzenes and 1-phenyl-3- A combination of pyrazolidones or a combination of dihydroxybenzenes and p-aminophenols may be used.

Examples of the dihydroxybenzene developing agent used in the present invention include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone,
There are 2,5-dimethylhydroquinone and the like, but hydroquinone is particularly preferable.

Examples of the developing agent for 1-phenyl-3-prazolidone or a derivative thereof used in the present invention include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-4-pyrazolidone and 1-phenyl-4-methyl-4. -Hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-
Methyl-3-pyrazolidone, 1-p-aminophenyl-
4,4-Dimethyl-3-pyrazolidone, 1-p-tolyl-
Examples include 4,4-dimethyl-3-pyrazolidone.

Examples of the p-aminophenol-based developing agent used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol and N- (4-hydroxyphenyl). Glycine, 2-methyl-p-aminophenol, p-benzylaminophenol, etc. are available, but among them N-methyl-p
-Aminophenol is preferred.

The developing agent is preferably used usually in an amount of 0.05 mol / -0.8 mol /. When a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is used in an amount of 0.05 mol / to 0.5 mol / and the latter is used in an amount of 0.06 mol / or less. preferable.

Examples of the sulfite preservative used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite.
Sulfite is preferably 0.4 mol / mol or more, particularly preferably 0.5 mol / mol or more. Further, the upper limit is preferably 2.5 mol / up.

Alkaline agents used to set the pH include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium triphosphate, potassium triphosphate, etc.
Contains pH regulators and buffers. The pH of the developer is set between 10.5-12.3.

The benztriazole compound used in the present invention is represented by the following general formula (II).

General formula (II) In the general formula (II), W is a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), an alkyl group (preferably having 1 to 20 carbon atoms), an alkoxy group (preferably having 1 to 20 carbon atoms). ), A hydroxy group, a sulfo group, and a carboxy group.

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

These compounds are preferably added in an amount of 0.2 g or more per developer.

As additives used in addition to the above components, compounds such as boric acid and borax, development inhibitors such as sodium bromide, potassium bromide and potassium iodide: ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve An organic solvent such as hexylene glycol, ethanol, or methanol: 1-phenyl-5-mercaptotetrazole, an antifoggant such as an indazole compound such as 5-nitroindazole, or a black pepper inhibitor may be included. Further, if necessary, it may contain a toning agent, a surfactant, an antifoaming agent, a water softener, a film hardener, an amino compound described in JP-A-56-106244.

The developer of the present invention contains a silver stain preventing agent as disclosed in JP-A-56-24,3.
The compounds described in No. 47 can be used. The compounds described in Japanese Patent Application No. 60-109,743 can be used as a dissolution aid added to the developing solution. Further, as the pH buffer used in the developing solution, the compounds described in JP-A-60-93,433 or the compounds described in Japanese Patent Application No. 61-28708 can be used.

As the fixing agent, those having a generally used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as a fixing agent can be used. The fixing solution may contain water-soluble aluminum (for example, aluminum sulfate, light vane, etc.) as a hardening agent. Here, the amount of the water-soluble aluminum salt is usually 0.4 to 2.0 g-Al /. Furthermore, a trivalent iron compound can be used as a complex with ethylenediaminetetraacetic acid as an oxidizing agent.

The development temperature is usually selected between 18 ° C and 50 ° C, more preferably 25 ° C to 43 ° C.

(Examples) Hereinafter, the present invention will be specifically described with reference to Examples.
The present invention is not limited thereby.

Example 1. Preparation of Emulsion A In a gelatin aqueous solution kept at 50 ° C., 4 × 10 ⁻⁷ per mol of Ag
In the presence of a molar amount of potassium iridium (III) hexachloride and ammonia, an aqueous solution of silver nitrate and an aqueous solution of potassium iodide and potassium bromide were added simultaneously for 60 minutes, and the pAg was kept at 7.8 during that period to obtain an average particle size of 0.28μ, and an average particle size of 0.28μ. A cubic monodisperse emulsion having a silver iodide content of 1 mol% was prepared. Further, this emulsion was washed with water according to a conventional method to remove soluble salts, and then gelatin was added. Subsequently, an aqueous solution of 0.1 mol% potassium iodide per mol of silver was added to carry out conversion of the grain surface to prepare Emulsion A.

Preparation of Emulsion B The same as Emulsion A except that pAg during grain formation was kept at 8.9, and finally the average grain size was 0.28 μm and the average silver iodide content was 1.1.
Emulsion B was prepared with mol% (including conversion) octahedral monodisperse grains.

Preparation of Emulsion C In the same manner as Emulsion A except that iridium (III) hexachloride was not added to the aqueous gelatin solution kept at 50 ° C,
A cubic monodisperse emulsion having an average grain size of 0.28 μm and an average silver iodide content of 1.1 mol% (including conversion) was obtained.

Preparation of coating sample To 1 kg of the above emulsion, 60 ml of a 0.05% solution of the infrared sensitizing dye represented by IIIb-6 was added to perform sensitization in the infrared region. In order to supersensitize and stabilize this emulsion, 4,4'-bis-
(4,6-Dinaphthoxy-pyrimidin-2-ylamino)
70 ml of a 0.5% methanol solution of stilbene disulfonic acid disodium salt and 90 ml of a 0.5% methanol solution of 2,5-dimethyl-3-allyl-benzothiazole iodo salt were added.

Furthermore, 4-hydroxy-6-methyl-1, as a stabilizer,
3,3a, 7-Tetrazaindene was added, and I-5 and I-19 as hydrazine derivatives were added in the amounts shown in Table 1, hydroquinone 100 mg / m ² , polyethyl acrylate latex as a plasticizer and a gelatin binder ratio. 25%, 8-bis (vinylsulfonylacetamide) ethane as a hardener 8
6.2 mg / m ^{2 was} added and coated on a polyester support so as to give silver of 3.7 g / m ² . Gelatin was 2.5 g / m ² .

0.6g / m ² of gelatin on this, particle size of 3 ~ as matting agent
4μ polymethylmethacrylate 60mg / m ² , particle size 10 ~ 20m
μ colloidal silica 70 mg / m ² , silicone oil 100 mg
/ m ² was added, and dodecylbenzenesulfonic acid sodium salt as a coating aid, and a protective layer upper layer containing a fluorine-based surfactant having the following structural formula and Gelatin 0.7g / m ² , polyethyl acrylate latex 2
25 mg / m ² , dye of the above structural formula 20 mg / m ² , dye 10 mg / m
² and the lower layer of the protective layer to which sodium dodecylbenzenesulfonate was added as a coating aid were simultaneously coated to prepare a sample.

The base used in this example has a back layer and a back protective layer having the following compositions. (The swelling ratio of the backing layer is 11
It is 0%. ) (Back layer) Gelatin 3.0g / m ² Sodium dodecylbenzenesulfonate 80mg Dye a 80mg 〃 b 30mg 〃 c 100mg 1,3-divinylsulfonyl-2-propanol 60mg / m ² Polyvinyl-benzenesulfonate potassium 30g / m ² (Back protection layer) Gelatin 0.75g / m ² Polymethylmethacrylate (particle size 4.7μ) 30mg / m ² Sodium dodecylbenzenesulfonate 20mg / m ² Fluorine-based surfactant (the above compound) 2mg / m ² Silicone oil 100mg / m ² Evaluation of photographic performance The obtained sample was exposed to xenon flash light with an emission time of 10 ^-6 sec through an interference filter having a peak at 780 nm and a continuous wedge, and a developer-1 and a fixer of the following composition As an example, using GR-F1 (manufactured by Fuji Photo Film Co., Ltd.), an automatic processor FG-360F (manufactured by Fuji Photo Film Co., Ltd.) (water washing tank capacity 6) was used to develop, fix, wash, and dry at 38 ° C. 20 ″.
Sensitometry was performed.

The reciprocal of the exposure dose giving a density of 3.0 was taken as the sensitivity, and the relative sensitivity is shown in Table 1.

Also, the slope of the straight line connecting the points of density 0.1 and 3.0 in the characteristic curve is defined as the gradation, and the sensitivity at the exposure amount increased from the exposure amount giving density 0.1 to the natural logarithm by 0.5 is Dmax. Shown in the table.

As is clear from Table 1, Sample 2, which corresponds to the present invention, is superior in sensitivity, gradation and Dmax to others.

Example 2. Preparation of emulsion D A mixed aqueous solution of potassium bromide and sodium chloride containing potassium iridium (III) chloride 6 and (NH ₄ ) ₃ RhCl ₆ and an aqueous solution of silver nitrate were stirred in an aqueous gelatin solution at 50 ° C. for 12 hours. A constant flow rate was added for a minute, and a mixed aqueous solution of potassium bromide and sodium chloride and an aqueous solution of silver nitrate were added for 20 minutes, and finally 1 mol of iridium (III) hexachloride was added per 1 mol of silver.
A monodisperse cubic silver chlorobromide emulsion containing x10 ^-7 mol and (NH ₄ ) ₃ RhCl ₆ 1 x10 ^-7 mol and having a silver bromide content of 30 mol% and an average grain size of 0.28 μm was obtained. This emulsion was washed with water and desalted in a conventional manner, followed by addition of gelatin, followed by addition of 0.1 mol% potassium iodide aqueous solution per mol of silver to carry out conversion of the grain surface, and further deoxyribonucleic acid per mol of silver. 127 m
g, 5 mg of sodium thiosulfate, and 8 mg of chloroauric acid, and add 6
Emulsion D was prepared by heating at 0 ° C. for 75 minutes for chemical sensitization and adding 150 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene as a stabilizer.

Preparation of Emulsion E Emulsion D except that a mixed aqueous solution of potassium bromide and sodium chloride containing potassium iridium (III) chloride and an aqueous solution of silver nitrate were added to a gelatin aqueous solution at a constant flow rate for 12 minutes at 50 ° C. with stirring. Emulsion E was prepared in the same manner as in.

Preparation of emulsion F First, while stirring a mixed aqueous solution of potassium bromide and sodium chloride and an aqueous solution of silver nitrate in an aqueous gelatin solution,
Emulsion F was prepared in the same manner as Emulsion D, except that a constant flow rate was added at 50 ° C. for 12 minutes.

Preparation of coating sample 4-hydroxy-6-methyl-1,3,3 was added to the obtained emulsion.
A coated sample was prepared in the same manner as in Example 1 except that a, 7-tetrazaindene was not added. I-5, I at this time
The amount of -19 added is shown in Table 2.

Evaluation of Photographic Performance The obtained sample was exposed in the same manner as in Example 1 and then processed in the same manner as in Example 1 using the developer solutions-1 and -2 and the fixing solution having the following compositions, and evaluated. Done. The results are shown in Table 2.

Further, at this time, the results are shown in Table 2 with the density of the unexposed portion as fog.

As is clear from Table 2, it is understood that the treatments 1 and 3 corresponding to the present invention can achieve high sensitivity and high contrast with less fog.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location G03C 5/29 501 G03C 5/29 501

Claims (2)

(57) [Claims] 1. A silver halide photographic light-sensitive material in which at least one silver halide photographic emulsion layer is coated on a support, wherein the silver halide grains in the silver halide emulsion are the eighth silver halide grains.
A cubic monodisperse grain containing at least one group metal atom, the silver halide emulsion having a maximum sensitization wavelength sensitized to a wavelength longer than 750 nm, and a hydrazine derivative represented by the following general formula (I): A silver halide photographic light-sensitive material containing at least one kind. General formula (I) In the formula, B ₁ represents an aliphatic group or an aromatic group, B ₂ represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a carbamoyl group or an oxycarbonyl group, and G ₁ is Carbonyl group, sulfonyl group,
Sulfoxy group, Or an iminomethylene group, D ₁ and D ₂ are both hydrogen atoms or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group. Represents a group. 2. A silver halide photographic light-sensitive material in which at least one silver halide photographic emulsion layer is coated on a support, and the silver halide grains in the silver halide emulsion are the eighth silver halide grains.
It is a cubic monodisperse grain containing at least one group metal atom, and the silver halide emulsion is sensitized with a maximum sensitization wavelength longer than 750 nm. Further, the hydrazine derivative represented by the general formula (I) is And containing the benzotriazole compound represented by the following general formula (II) in an amount of 0.2 g / or more, and treating the silver halide photographic light-sensitive material with a developing solution having a pH of 11 or more. And a method for processing a silver halide photographic light-sensitive material. General formula (II) However, W represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxy group, a sulfo group, or a carboxy group.