JPH0687134B2 - 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 specifically to a silver halide photographic light-sensitive material for printing plate making using a laser (LED) as a light source. It is about.

[Conventional technology]

In recent years, a scanner method has been widely used in the field of printing plate making, and the mainstream has changed to a dot generator method that directly forms dots or characters electrically. Conventionally, an argon laser having a high output has been used as the scanner light source of the dot generator method, but since this device is bulky and expensive, recently, a more compact and inexpensive helium-neon laser has been used. Light source (632.8n
m) Alternatively, a dot generator type scanner device using an LED light source (660 to 680 nm) has been developed by each company. Various characteristics are required for the photosensitive material used in this scanner. In other words, it has high spectral sensitivity for each wavelength, and since it is exposed at high illuminance for 10 ^-3 to 10 ^-7 seconds, it must have high sensitivity and high contrast even under such conditions. Is required. Further, in the field of facsimile, it is required to endure high-temperature rapid processing for prioritizing promptness, or from the viewpoint of work efficiency, safety against bright green safelight.

Iridium salts have been introduced into silver halide for the purpose of improving reciprocity law failure. JP-A-48-60918, JP-A-58-211753 and 61-29
837, 61-201233, and Japanese Examined Patent Publication No. 48-42172.

However, the silver halide emulsion in which the iridium salt is introduced improves the high-illuminance failure at the same time as often improves the low-illumination failure, so that there is a problem that the safety of the bright green safelight is remarkable and deteriorates. It was

For the purpose of solving the above problems, the photographic emulsion layer or other layers are often colored with a dye that absorbs light in a specific wavelength range. 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.

Many efforts have been made by those skilled in the art to find dyes that meet these conditions.

Of these, the oxonol dye having two pyrazolone nuclei has the property of being decolorized in a developer containing sulfite, and is used as a dye of a light-sensitive material as a useful dye because it rarely exerts a bad effect on a photographic emulsion. Came.

For example, those having a sulfoaryl group at the 1-position of pyrazolone are disclosed in Japanese Patent Publication Nos. 39-22069, 51-46607, and 55-10061,
Nos. 60-53304 and 51-1419, which have a sulfoalkyl group at the 1-position of pyrazolone, are disclosed in
49-99620, Japanese Examined Patent Publication No. 55-10059 and the like. However, although dyes belonging to these systems have little effect on photographic emulsions themselves, they can be spectrally sensitized to unnecessary areas or desorbed sensitizing dyes to emulsions that have been spectrally sensitized. It has a drawback of causing a decrease in sensitivity which is considered to be caused.

In addition, there are some that remain after the processing due to the speeding up of the developing processing that has recently been performed. In order to solve this, it has been proposed to use a dye having a high reactivity with sulfite ion, but in this case, the stability in the photographic film is not sufficient, and the density decreases with time, It has the drawback that the desired photographic effect cannot be obtained.

On the other hand, those having a sulfoaralkyl group at the 1-position of pyrazolone and further having a specific substituent at the 3-position of pyrazolone are described in JP-A Nos. 50-145125, 50-147712 and 52-20830. However, they have the drawbacks of poor decolorization and poor residual color.

(Problems to be Solved by the Invention) The first object of the present invention is He, which has excellent safelight safety.
-To provide a silver halide photographic light-sensitive material for He light source or LED light source.

Secondly, it is to provide a silver halide photographic light-sensitive material excellent in decolorization even in a rapid development process.

Thirdly, to provide a silver halide photographic light-sensitive material having high sensitivity to a light source of high illuminance.

(Structure of the Invention) The above object of the present invention is to provide a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, wherein the emulsion layer is 1 × 10 ⁻ per mol of silver. Contains ⁶ mol or less of iridium salt and has a silver iodide content of 0.1 to 4.0
A silver halide photographic light-sensitive material characterized by comprising a compound represented by the following general formula (I) in the emulsion layer or other hydrophilic colloid layer, which comprises mol% of silver halide grains. .

In the formula, R ₁ and R ₂ are each an alkyl group, an aryl group, a cyano group,
--COOR ₅ , --CONR ₅ R ₆ , --COR ₇ , --SO ₂ R ₇ , --SO ₂ NR ₅ R ₆ or --NR ₆ SO ₂ R ₇ (wherein R ₅ and R ₆ are hydrogen atoms, alkyl groups or Represents an aryl group, R ₇ represents an alkyl group or an aryl group, R ₅ and R ₆ or R ₆ and R ₇ may combine to form a 5- or 6-membered ring), R ₃ and R ₄ each represents a hydrogen atom or a methyl group, Q _1, Q ₂ each represent a phenyl group or substituted phenyl group, X _1, X ₂ is a bond or -O- or -NR ₈ - (R ₈ is a hydrogen atom, Represents an alkyl group having 5 or less carbon atoms or a substituted alkyl group having 5 or less carbon atoms,
Y ₁ and Y ₂ each represent a sulfo group or a carboxyl group,
L ₁ , L ₂ and L ₃ each represent a methine group. n is 0, 1 or 2
Where m1 = m2 = 1 and p1 and p2 are 0, 1 and
Represents 2, 3, or 4, and q1 and q2 represent 1, 2 or 3, respectively. Next, the dye represented by formula (I) will be described in detail.

The alkyl group represented by R ₁ , R ₂ , R ₅ , R ₆ and R ₇ is an alkyl group having 1 to 8 carbon atoms (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-). Butyl, n-amyl, n-hexyl, n-octyl, isoamyl) are preferable, and substituents [for example, halogen atom such as fluorine, chlorine, bromine, phenyl group, hydroxyl group, cyano group, alkoxy group (for example, methoxy, ethoxy, hydroxy). Ethoxy), aryloxy groups (eg phenoxy, p-methoxyphenoxy), carboxyl groups, sulfo groups, amino groups, substituted amino groups (eg dimethylamino, diethylamino)].

The alkyl group represented by R ₃ and R ₄ is preferably an alkyl group having 4 or less carbon atoms (eg, methyl, ethyl, n-propyl).

The aryl group represented by R ₁ , R ₂ , R ₅ , R ₆ and R ₇ is preferably a phenyl group or a naphthyl group, and a substituent (for example, a halogen atom such as fluorine, chlorine or bromine, a sulfo group, a carboxyl group, It may have a hydroxyl group, a cyano group, an alkyl group having 1 to 4 carbon atoms (eg methyl, ethyl, n-propyl), an alkoxy group (eg methoxy, ethoxy), an aryloxy group (eg phenoxy)].

The aryl group represented by Q ₁ and Q ₂ is a phenyl group,
A naphthyl group is preferable, a sulfo group, a substituent other than a carboxyl group [for example, an alkyl group having 1 to 4 carbon atoms (for example, methyl, ethyl), an alkoxy group (for example, methoxy, ethoxy, a halogen atom (for example, fluorine, chlorine, bromine), Carbamoyl (eg methylcarbamoyl, ethylcarbamoyl), sulfamoyl (eg ethylsulfamoyl), cyano group, nitro group, alkylsulfonyl group (eg methanesulfonyl), arylsulfonyl group (eg benzenesulfonyl), amino group (eg dimethylamino, Diethylamino), acylamino group (eg acetylamino), sulfonamide group (eg methanesulfonamide), hydroxyl group].

Examples of the divalent linking group represented by X ₁ and X ₂ include —O.
_{-, - NR 8 -, -} NR 8 CO -, - SO 2 -, - NR 8 SO 2 - can be exemplified, R ₈ is a hydrogen atom, C 5 or lower alkyl groups (e.g. methyl carbon, ethyl, n -Propyl, n-butyl, n-amyl, isobutyl) or a substituted alkyl group having 5 or less carbon atoms, [as a substituent, an alkoxy group having 3 or less carbon atoms (eg, methoxy, ethoxy), a sulfo group, a carboxyl group, cyano Group, hydroxyl group, amino group (eg dimethylamino, diethylamino), carbamoyl group (eg hydroxyethylaminocarbonyl, ethylaminocarbonyl) or sulfamoyl group (eg ethylaminosulfonyl).

Examples of the 5- or 6-membered ring formed by connecting R ₅ and R ₆ or R ₆ and R ₇ include a piperidine ring, a morpholine ring, a pyrrolidine ring and a pyrrolidone ring.

The methine group represented by L ₁ , L ₂ and L ₃ may have a substituent (for example, methyl, ethyl, cyano, phenyl, chlorine atom, sulfoethyl).

In the above general formula (I), the sulfo group, the carboxyl group and the enol moiety of the pyrazolone ring are in a free form or a salt form (for example, Na salt, K salt, (C ₂ H ₅ ) ₃ NH salt, pyridinium salt, ammonium salt). May be formed.

In the above general formula (I), preferred is that R ₃ and R ₄ represent a hydrogen atom or a methyl group, and Q ₁ and Q ₂ are a phenyl group or a substituted phenyl group [an alkyl group having 4 or less carbon atoms as a substituent, a carbon atom An alkoxy group having a number of 4 or less, a halogen atom (for example, fluorine, chlorine, bromine), a dialkylamino group having a number of 6 or less, and a hydroxyl group are preferable. ], X ₁ , X ₂ represent a bond or —O— or —NR ₈ — (R ₈ is as defined above). More preferably, m ₁ = m ₂ = 1 under the above conditions, and particularly preferably m ₁ = m ₂ = 1 and R ₁ and R ₂ are an alkyl group, an aryl group, a cyano group, or --COOR. ₅ , -CONR ₅ R ₆ -COR ₇ , -SO
_{2 R 7, -SO 2 NR 5} R 6 or _{-NR 6 SO 2 R 7 (R} 5, R 6, R 7 are as defined above.) Is representative of the.

Specific examples of the dye represented by formula (I) are shown below, but the invention is not limited thereto.

The dye represented by formula (I) is described in JP-A-50-145125,
Nos. 50-147712, 59-111640, 62-273527, Japanese Patent Application Nos. 62-79483 and 62-110333, or can be synthesized by a similar method.

For the non-photosensitive hydrophilic colloid layer of the present invention, the above dye is dissolved in an appropriate solvent [eg, water, alcohol (eg, methanol, ethanol, propanol, etc.), acetone, methyl cellosolve, etc., or a mixed solvent thereof]. It is added to the coating solution.

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

The amount of the specific dye is generally ^{10 -2 g / m 2 ~2g /} m 2, particularly from ^{10 -2 g / m 2 ~1g /} m 2 is preferred.

In the photographic emulsion layer of the photographic light-sensitive material used in the present invention, silver iodobromide and silver iodochlorobromide are used as silver halides.

The content of silver iodide is 0.1 to 4.0 mol%, particularly preferably 0.5.
~ 3.0 mol%.

The average grain size of the silver halide grains is not particularly limited, but 3
μm or less is preferable, and particularly preferably 0.2 μm or more and 2 μm
It is the following.

The shape of the silver halide grains used in the present invention may be any of a cube, an octahedron, a tetradecahedron, a plate and a sphere, and may be a mixture of these various shapes. , Tetradecahedral and tabular grains are preferred.

The particle size distribution may be either polydisperse or monodisperse, but is preferably monodisperse with a coefficient of variation of 20% or less, and further 15%.
The following monodispersion is preferable.

Where the coefficient of variation is Is defined as

The photographic emulsion used in the present invention is described by P. Glafkides, Chimie et.
Physique Photographique (published by Paul Montel, 1967
), GFDuffin Photographic Emulsion Chemist
ry (The Focal Press, 1966), VLZelikman et
al. Making and Coating Photographic Emulsion
(Published by The Focal 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. PAg in the liquid phase in which silver halide is formed as a form of simultaneous mixing method.
Can also be used, that is, a so-called controlled 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.

In addition, in order to make the particle size uniform, British Patent 1,53
No. 5,016, Japanese 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.
As described in JP-A No. 2,445 and JP-A No. 55-158124, it is preferable to grow rapidly in a range not exceeding the critical saturation by using a method of changing the concentration of the aqueous solution.

In the case of tabular grains, it is preferable to use grains having a uniform particle size and / or thickness as described in Japanese Patent Publication No. 47-11,386, Japanese Patent Application No. 61-48950.

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 the silver iodide ratio of the shell by 0.5 mol% or more,
Further, it is more preferable that it is higher than 2 mol.

The silver halide used in the present invention is 1 × per mol of silver.
^Contains less than 10 ^-6 mol of iridium salt. The preferred range is
It is 1 × 10 ^-8 to 1 × 10 ^-6 mol, and it is preferably added before the physical ripening in the production process of the silver halide emulsion, particularly during grain formation.

The iridium salt used here is a water-soluble iridium salt or iridium complex salt, such as iridium trichloride, iridium tetrachloride, potassium hexachloroiridium (III), potassium hexachloroiridium (IV), ammonium hexachloroiridium (III), etc. There is.

The silver halide used in the present invention is, in addition to the above iridium salt, a cadmium salt, a zinc salt, a lead salt, a thallium salt, or a complex salt thereof, a rhodium salt or a complex salt thereof, iron in the process of silver halide grain formation or physical ripening. A salt, an iron complex salt or the like can coexist.

Silver halide emulsions are usually chemically sensitized. For chemical sensitization, for example, “Die Grundlagender P” edited by H. Frieser.
hotographishen Prozesse mit Silber-halogeniden "(A
kademischeVerlagsgesellschaft, 1968) 675 to 734 can be used.

That is, a sulfur sensitizing method using a compound containing sulfur capable of reacting with active gelatin or silver (eg, thiosulfates, thioureas, mercapto compounds, rhodanins); a reducing substance (eg, first tin salt) , Amines, hydrazine derivatives, formamidinesulfinic acid, silane compounds); reduction sensitization methods; precious metal compounds (eg, gold complex salts)
A noble metal sensitization method using a complex salt of a metal of Group VIII of the Periodic Table such as Pt, Ir, Pd) or the like can be used alone or in combination.

The silver halide photographic light-sensitive material of the present invention has the general formula (I)
In addition to the dye represented by, other dyes can be used in combination. Preferred dyes used in combination are JP-A-59-154439, 59-208548, 59-211034, and 60-6434.
6, but some of them are listed below.

The silver halide photographic light-sensitive material of the present invention is spectrally sensitized with respect to the wavelength of a laser light source or an LED light source. Preferred sensitizing dyes are JP-B-43-4933, JP-B-48-42172, and 55-39.
818, JP-A-50-62425 and JP-A-54-18726 are described in detail, but some of them are listed below.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance that does not substantially absorb visible light and exhibits supersensitization may be included in the emulsion.

Useful sensitizing dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization are described in Research Disclosure (Resear
ch Disclosure) Volume 176 17643 (December 1978) Page 23 I
It is described in J of V.

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, mercaptoadiazoles, 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 .; added many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. It is possible.

In the photographic emulsion layer of the photographic light-sensitive material of the present invention, for the purpose of increasing sensitivity, increasing contrast, or promoting development, for example, polyalkylene oxide or its derivative such as ether, ester, amine, thioether compound, thiomorpholine, quaternary compound. Ammonium salt compound, urethane derivative,
Urea derivatives, imidazole derivatives, and developing agents such as dihydroxybenzenes and 3-pyrazolidones may be included. Among them, dihydroxybenzenes (hydroquinone, 2-methylhydroquinone, catechol, etc.) and 3
-Pyrazolidones (1-phenyl-3-pyrazolidone,
1-phenyl-4-methyl-4-hydroxymethyl-3
-Pyrazolidone, etc.) is preferred, and is usually used at 5 g / m ² or less. 0.01 to 1 g for dihydroxybenzenes
/ m ² is more preferable, and in the case of 3-pyrazolidones, 0.0
1 to 0.2 g / m ² is more preferable.

The photographic emulsion and the non-photosensitive hydrophilic colloid of the present invention may contain an inorganic or courageous hardener. For example, active vinyl compounds (1,3,5-triacryloyl-hexahydro-
s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis- [β- (vinylsulfonyl) propionamide], etc., active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.) ), Mucohalogen acids (such as mucochloric acid), N-carbamoylpyridinium salts (such as (1-morpholino) carbonyl-3-pyridinio) methanesulfonate) and haloamidinium salts (1- (1-chloro-1-pyridinomethylene)) Pyrrolidinium, 2-naphthalene sulfonate, etc.) can be used alone or in combination. Among them, JP-A-53-41220, 53-57257, 59-162546,
Active vinyl compounds described in the same 60-80846 and US Patent 3,
The active halides described in 325,287 are preferred.

For a photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material produced by using the present invention, a coating aid, an antistatic agent, an improvement in smoothness, an emulsion dispersion, an adhesion prevention and an improvement in photographic characteristics (for example,
Various surfactants may be included for various purposes such as development acceleration, contrast enhancement, and sensitization.

For example, saponins (steroids), alkylene oxide derivatives (eg polyethylene glycol, polyethylene glycol / polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycols). Nonionic surfactants such as alkyl amines or amides, polyethylene oxide adducts of silicones), glycidol derivatives (eg alkenyl succinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Agents: alkyl carboxylates, alkyl sulfonates, alkyl benzene sulfonates Acid salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, Nacyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates Anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups such as esters; amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphate esters , Alkylbetaines, amine oxides and other amphoteric surfactants; alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and aliphatic or heterocyclic compounds Phos containing a ring Cationic surfactants such as chloride or sulfonium salts may be used.

In order to prevent static electricity, it is preferable to use the fluorine-containing surfactants described in JP-A-60-80849.

The photographic light-sensitive material of the present invention may contain a matting agent such as silica, magnesium oxide or polymethylmethacrylate in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of preventing adhesion.

The light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of dimensional stability. For example, a polymer having a monomer component of alkyl (meth) acrylate, alkoxyacryl (meth) acrylate, glycidyl (meth) acrylate, or a combination thereof, or a combination thereof with acrylic acid, methacrylic acid, or the like is used. be able to.

Gelatin is advantageously used as the binder or protective colloid of the photographic emulsion, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sodium alginate,
Sugar derivatives such as starch derivatives, polyvinyl alcohol, polyvinyl alcohol partial acetals, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, polyvinyl pyrazole, etc. Synthetic hydrophilic polymeric substances can be used.

As the gelatin, in addition to coal-treated gelatin, acid-treated gelatin may be used, and gelatin hydrolyzate and gelatin enzyme hydrolyzate may also be used.

The silver halide emulsion layer used in the present invention may contain a polymer latex such as an alkyl acrylate.

As the support of the light-sensitive material of the present invention, cellulose triacetate, cellulose diacetate, nitrocellulose,
Polystyrene, polyethylene terephthalate paper, baryta coated paper, polyolefin coated paper and the like can be used.

For the photographic processing of the light-sensitive material of the present invention, any known method can be used. A known treatment liquid 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.

The developing solution used for black-and-white photographic processing may contain a known developing agent. As developing agents, dihydroxybenzenes (for example, hydroquinone), 3-
Pyrazolidones (eg 1-phenyl-3-pyrazolidone), aminophenols (eg N-methyl-p
-Aminophenol), 1-phenyl-3-pyrazolines, ascorbic acid, and heterocyclic compounds such as 1,2,3,4-tetrahydroquinoline ring and indrene ring described in U.S. Pat. No. 4,067,872. Can be used alone or in combination. The developer generally contains other known preservatives, alkali agents, pH buffers, antifoggants, and the like, and if necessary, dissolution aids, color tones, development accelerators, surfactants, defoamers, A water softener, a film hardening agent, a viscosity imparting agent and the like may be contained.

As the fixer, one having a commonly 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 a water-soluble aluminum salt as a hardening agent.

The light-sensitive material of the present invention is preferably processed using an automatic developing machine, which enables rapid processing and the like. At this time, the developing process is 30 to 45 ° C. for 5 to 60 seconds, and the fixing process is
30-45 ℃, 5-30 seconds, 30-45 ℃, 5-
It is preferable to carry out the condition for 30 seconds. Also in this case,
As the fixing bath, it is preferable to use an acidic hardening fixing bath containing a polyvalent metal.

〔Example〕

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto.

(Example 1) Emulsions A to C were prepared by the following method.

[Emulsion A]: A mixed aqueous solution of potassium iodide and potassium bromide and an aqueous solution of silver nitrate were added to an aqueous gelatin solution containing 1,8-dihydroxy-3,6-dithiaoctane under vigorous stirring at 75 ° C. for 15 minutes with pAg. It was added while controlling so as to be 7.7, to obtain monodisperse cubic silver iodobromide having an average particle size of 0.28 μm and an iodide content of 6 mol%. Using this silver iodobromide emulsion as a core, an aqueous solution of potassium bromide containing 10 ^-7 mol of K ₃ IrCl ₆ per 1 mol of Ag and an aqueous solution of silver nitrate were added to give a pAg of 7.4, and monodispersed with an average particle size of 0.45 μ. Cubic core / shell silver iodobromide emulsion (average silver iodide content 1.5 mol%, dispersion coefficient 11
%) Was obtained. This emulsion was desalted according to a conventional method, and then 3 mg of sodium thiosulfate and 4 mg of chloroauric acid were added per 1 mol of silver, and chemical sensitization was performed at 65 ° C. for 70 minutes. As a stabilizer, 30 ml of a 1% solution of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added per mol of silver.

[Emulsion B]: A monodisperse cubic core / shell silver iodobromide emulsion (average silver iodide content: 2 mol%, having an average grain size of 0.45 μm) was prepared in the same manner as in A except that K ₃ IrCl ₆ was not contained. Coefficient of dispersion 12
%) [Emulsion C]: A mixed aqueous solution of potassium iodide and potassium bromide containing 1 × 10 ⁻⁷ mol of K ₃ IrCl ₆ per 1 mol of silver, and a silver nitrate aqueous solution were mixed with 1,8-dihydroxy-3,6- 40 ° C at 75 ° C under vigorous stirring in an aqueous gelatin solution containing dithiaotan.
The content was controlled and pAg = 7.4 to prepare a monodisperse cubic silver iodobromide emulsion having an average grain size of 0.45 μm (average silver iodide content: 1.5 mol%, dispersion coefficient: 9%).
This emulsion was desalted and chemically sensitized in the same manner as Emulsion A, and a stabilizer was added.

In the above emulsion, 3,3'-di (3-sulfopropyl) -5,5'-dichloro-9-ethyl-naphtho [1,2-d] thiacarbocyanine sodium salt and 3,3'-di (3-sulfopropyl) -5,5'- 3 ′
-Di (3-sulfopropyl) -9-ethyl-naphtho [1,
50 mg of 2-d] thiacarbocyanine sodium salt was added per mol of silver halide, and the compound of the general formula [I] and the comparative compound were added as shown in Table 1. Further, for the prevention of fogging, 1-phenyl-5-mercaptotetrazole is 50 mg per 1 mol of silver, polyethyl acrylate latex is 25% as a plasticizer for gelatin binder, and 2-bis (vinylsulfonylacetamide) ethane is 120 mg / m as a hardening agent. ² addition, 4.5g / m silver on polyester support
^It was applied so that it became ² . The gelatin was 4.7 g / m ² .

1.5 g / m ² of gelatin as a protective layer, 60 mg / m ^{2 of} polymethylmethacrylate having a particle size of 3 to 4 μm as a matting agent,
Hydroquinone 150 mg / m ² as an antifoggant, dodecylbenzene sulfonic acid sodium salt as a coating aid,
A layer to which a fluorine-containing surfactant having the following structural formula was added was simultaneously applied.

The sample thus obtained was subjected to wedge exposure with an emitting diode light having an emission maximum at 660 nm, and a developing solution 1 having the following composition and LF-308 (manufactured by Fuji Photo Film Co., Ltd.) as a fixing solution were used. Made, processor FG-360F
It was developed at 35 ° C. for 30 seconds, fixed, washed with water, and dried for evaluation.
The sensitivity and safelight safety residual color were evaluated as follows.

1) Sensitivity: Relative value of the reciprocal of exposure amount that gives a density of 1.5 2) Safelight Safety: 20W bulb green safelight (Fuji Safelight Filter No. 4) Leave at 1m distance for 3 minutes, then develop The increase in fog density was measured.

3) Residual color property: A sample subjected to development processing, fixing, washing with water and drying was prepared by the above method, and the tint of the unexposed portion was visually evaluated. "5" represents the best quality and "1" represents the worst quality.

As is clear from Table 1, samples 2 to 4, 12, and 13 of the present invention
Shows good performance in both sensitivity safelight safety and residual color.

[Developer formulation]

Water 720 ml Ethylenediaminetetraacetic acid disodium salt 4 g Sodium hydroxide 44 g Sodium sulfite 45 g Sodium carbonate 26.4 g Boric acid 1.6 g Potassium bromide 1 g Hydroquinone 36 g Diethylene glycol 39 g 5-Methyl-benzotriazole 0.2 g Pyrazone 0.7 g Add water 1 (Comparative compound)

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Shigeru Ono 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Fuji Photo Film Co., Ltd. Examiner Toshiyasu Kimura (56) Reference JP-A-63-139949 (JP, A) JP-A-SHO 61-201233 (JP, A) JP 56-147142 (JP, A) JP 60-162247 (JP, A) JP 50-145125 (JP, A) JP 50-147712 (JP, A) A) JP-A-61-93448 (JP, A)

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, said emulsion layer containing 1 × 10 ⁻⁶ mol or less of iridium salt per mol of silver, and It is composed of silver halide grains having a silver iodide content of 0.1 to 4.0 mol%, and at least one of the emulsion layer and the other hydrophilic colloid layer contains a compound represented by the following general formula (I). A characteristic silver halide photographic light-sensitive material. General formula (I) In the formula, R ₁ and R ₂ are each an alkyl group, an aryl group, a cyano group,
--COOR ₅ , --CONR ₅ R ₆ , --COR ₇ , --SO ₂ R ₇ , --SO ₂ NR ₅ R ₆ or --NR ₆ SO ₂ R ₇ (wherein R ₅ and R ₆ are hydrogen atoms, alkyl groups or Represents an aryl group, R ₇ represents an alkyl group or an aryl group, R ₅ and R ₆ or R ₆ and R ₇ may combine to form a 5- or 6-membered ring), R ₃ and R ₄ each represents a hydrogen atom or a methyl group, Q ₁ and Q ₂ each represent a phenyl group or a substituted phenyl group, and X ₁ and X ₂ are a bond or —O— or —
NR ₈ - (R ₈ is a hydrogen atom, an alkyl group or a substituted alkyl group having 5 or less carbon atoms having a carbon number of 5 or less) represents,
Y ₁ and Y ₂ each represent a sulfo group or a carboxyl group,
L ₁ , L ₂ and L ₃ each represent a methine group. n is 0, 1 or 2
Where m1 = m2 = 1 and p1 and p2 are 0, 1 and
Represents 2, 3, or 4, and q1 and q2 represent 1, 2 or 3, respectively.