JPH08211533A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE: To enhance sensitivity to infrared rays and to reduce fog by chemically sensitizing a specified silver halide emulsion with bromine ions and spectrally sensitizing it with a specified compound. CONSTITUTION: The silver halide emulsion having a chlorine content of 50-90mol% is chemically sensitized in the presence of bromine ions in an amount of 1-5mol% based on the silver and spectrally sensitized with the compound represented by the formula in which each of R1 and R2 is, independently, an alkyl or alkoxy group; D is a nonmetallic atomic group necessary to form a 6-membered ring; each of Z1 and Z2 is a nonmetallic atomic group necessary to complete a 5- or 6-membered N-contg. heterocyclic ring; X<-> is an acid anion; and (n) is 1 or 2 and when it is 1, an intramolecular salt is formed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic emulsion used in a silver halide photographic light-sensitive material which has been spectrally sensitized in the infrared region. In particular, the sensitivity and fog in the infrared spectral region are improved. And a silver halide light-sensitive material.

[0002]

2. Description of the Related Art As one of the exposure methods for a photographic light-sensitive material, an original image is scanned, and a silver halide photographic light-sensitive material is exposed on the basis of the image signal to expose a negative image or positive image There is known an image forming method using a so-called scanner method for forming an image. There are various types of recording apparatuses that use the scanner-type image forming method, and conventionally, glow lamps, xenon lamps, mercury lamps, tungsten lamps, light-emitting diodes, and the like have been used as the recording light sources of these scanner-type recording apparatuses. But,
Each of these light sources has a practical drawback that the output is weak and the life is short. To compensate for these drawbacks, there is a scanner that uses a coherent laser light source such as a Ne-He laser, an argon laser, or a He-Cd laser as a light source of a scanner system. According to these, high output can be obtained, but the device is large and expensive, a modulator is required, and since visible light is used, the safelight of the photosensitive material is limited, and the handleability is improved. There are drawbacks such as being inferior to. On the other hand, semiconductor lasers are small, inexpensive, easy to modulate, have a longer life than the above lasers, and emit light in the infrared region, so a bright safelight is used when using a photosensitive material that is photosensitive in the infrared region. Therefore, there is an advantage that handling workability is improved. However, since there is no light-sensitive material having high sensitivity in the infrared region and low fog, the characteristics of the semiconductor laser having excellent performance as described above cannot be utilized. As one of the manufacturing techniques for photographic light-sensitive materials, there is a technique in which a certain cyanine dye is added to a silver halide photographic emulsion to extend its light-sensitive wavelength range to a longer wavelength side, that is, a spectral sensitization technique. It is known that this spectral sensitization is also applied to the infrared region. For spectral sensitization in the infrared region, sensitizing dyes having absorption for infrared light are used, and these are described in, for example, “The Theory of the Phot” by Mees.
ographic Process, 3rd edition (published by MacMillan, 1966)
P.198-p.201 of. In this case, it is desirable that the spectral sensitivity, that is, the sensitivity to light in the infrared region, is high. Therefore, many sensitizing dyes have been developed conventionally. For example, U.S. Patents 2,095,854 and 2,095,856
No., No. 2,955,939, No. 3,482,978, No. 3,552,
974, 3,573,921, 3,582,344 etc.

[0003]

However, even if the sensitizing dyes described in these are used, the sensitivity and fog cannot be said to be sufficient. That is, in the methods described in these patents, the infrared sensitivity is increased, and in some cases, a slight decrease in fog is observed, but it is still insufficient, resulting in an increase in sensitivity in a higher infrared region and a decrease in fog. Means are desired.
An object of the present invention is to provide a silver halide photographic light-sensitive material having high sensitivity to infrared light and less fog.

[0004]

The above object of the present invention is to provide a silver halide emulsion having a chlorine content of 50 mol% to 90 mol% in a silver halide emulsion containing 1 mol% to 5 mol% of bromine ions with respect to silver. A silver halide light-sensitive material using a silver halide emulsion which has been chemically sensitized in the presence of mol% and which has been spectrally sensitized with at least one compound represented by the following general formula [I]. Can be achieved by

[0005]

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[In the formula, R ₁ and R ₂ may be the same or different and each represents an alkyl group or an alkoxy group. D represents a nonmetallic atomic group necessary for completing a 6-membered ring nucleus. Z ₁ and Z ₂ each represent a nonmetallic group necessary for completing a 5- or 6-membered nitrogen-containing heterocycle. X ^- represents an acid anion. n represents 1 or 2, and when n is 1, it forms an inner salt. Hereinafter, the present invention will be described in detail.

The silver halide used in the present invention is silver chlorobromide,
Silver chloroiodobromide, preferably in the case of silver chloroiodobromide, the silver iodide content is 0 to 3 mol%, preferably 0 to 1 mol%.
The silver chloride content is 50 to 90 mol%, preferably 60 to 80 mol%. In the case of silver chlorobromide, the silver chloride content is 50 to 90 mol%, preferably 60 to 80 mol%. The crystal structure of silver halide grains may be uniform or the halogen composition may be different between the inside and the outside. The (100) plane / (11) of the silver halide grains used in the present invention
1) The surface ratio is preferably 3 or more, particularly preferably 5 or more. The silver halide grains having a (100) face / (111) face ratio of 3 or more according to the present invention can be prepared by various methods. The most common method is to keep the pAg value during grain formation at a constant value of 8.1 or less, and to simultaneously add the silver nitrate aqueous solution and the alkali halide aqueous solution at a rate faster than the dissolution rate of the particles and at a rate that does not cause re-nucleation. Is. More preferably, the pAg value is 7.6 or less.
The method of reacting the aqueous solution of silver nitrate and the aqueous solution of alkali halide includes a single jet method and a double jet method, and a double jet method having a uniform particle shape and a narrow particle diameter is preferable. The silver halide emulsion used in the present invention can be prepared by a neutral method or an acidic method, but is preferably prepared in an acidic region. The silver halide emulsion grains of the present invention have an average grain size of about 0.05 μm to 1.0 μm (measured by, for example, a projection photographing method and a number average method), preferably 0.2
To 0.7 μm emulsion grains are desirable. The silver halide emulsion of the present invention may contain iridium. In order to contain iridium ions, it is common to add an aqueous solution iridium compound (for example, hexachloroiridium (IV) salt) in the form of an aqueous solution when preparing a silver halide emulsion. It may be added in the form of the same aqueous solution as the halide for grain formation, may be added before grain formation, during grain formation, or after grain formation until chemical sensitization, but is particularly preferable. Is addition at the time of grain formation. Iridium ions are preferably used in an amount of 1 × 10 ^-8 to 1 × 10 ^-5 mol per mol of silver halide.
More preferably, it is 1 × 10 ⁻⁷ to 1 × 10 ⁻⁶ mol. In the present invention, it is preferable to use a water-soluble rhodium salt, typically, rhodium chloride, rhodium trichloride, rhodium ammonium chloride and the like. Furthermore, these complex salts can also be used. The addition time of the rhodium salt is limited before the completion of the first ripening at the time of emulsion production, and is preferably added during grain formation, and the addition amount is 1 × 10 ^-8 to 1 × 10 ⁻ per mol of silver. A range of ⁶ moles is preferred.
In order to control the growth of grains during the formation of the silver halide grains, examples of the silver halide solvent include, for example, ammonia, rodancali, rhodanammon, and thioether compounds (e.g., U.S. Pat.Nos. 3,271,157 and 3,574,628).
No., No. 3,704,130, No. 4,297,439, No. 4,276,
374) and thione compounds (for example, JP-A-53-144319).
No. 53-82,408, No. 55-77,737, etc.), amine compounds (for example, JP-A No. 54-100,717, etc.) and the like can be used. In addition to the silver halide solvent, a compound that is adsorbed on the grain surface to control the crystal habit, such as a cyanine sensitizing dye, a tetrazaindene compound, or a mercapto compound can be used as a grain forming agent.

The emulsion used in the present invention can be chemically sensitized by a commonly used method such as sulfur sensitization (US Pat. No. 1,572).
No. 4,944, No. 2,278,947, No. 3,021,215, No.
3,635,717), reduction sensitization (US Pat. No. 2,518,698)
Issue, Research Disclosur
e) Vol.176 (1978.12) 17643, item 3, etc.), sensitization with thioether compounds (for example, US Pat. No. 2,521,926).
No. 3,021,215, No. 3,046,133, No. 3,165,
No. 552, No. 3,625,697, No. 3,635,717, No. 4,
No. 198,240) or their various sensitization methods are applied. More specific chemical sensitizers include sodium thiosulfate and allyl thiocarbamide.
amide), thiourea, thiosulfate, sulfur sensitizers such as thioether and cystine; reduction sensitizers such as tin chloride, phenylhydrazine and reductone. Further, the emulsion used in the present invention is gold sensitized (for example, US Pat. Nos. 2,540,085 and 2,399,083).
No.) is preferably used. Specific gold sensitizers include potassium chloroaurate, aurasthiosulfate and potassium chloroparadate. These gold compounds may be added before or after the sulfur sensitizer. It can also be added at the same time as the sulfur sensitizer. The amount of the gold sensitizer used in the present invention is preferably 1 × 10 ⁻⁷ to 1 × 10 ⁻³ mol, and more preferably 1 × 10 ⁻⁶ to 1 × 10 ^−4, per mol of silver halide. It is particularly preferred to use it in a molar ratio.

The above silver halide emulsion grains are chemically sensitized in the presence of 1 mol% to 5 mol% of bromine ions with respect to silver halide. Preferably the bromide ion is 2 mol%
To 4 mol% or less. The bromine ion used in the present invention is a water-soluble bromide, and various compounds capable of dissociating into bromine ion in water are used. For example, bromide salts such as salts of potassium, sodium, ammonium, lithium and the like are used. Preferred are potassium bromide and sodium bromide. The amount of bromine ions used is 1 mol% or more and 5 mol% or less, and preferably 2 mol% or more and 4 mol% or less with respect to silver halide. The bromine ion may be added at any time during the chemical sensitization of the silver halide grains, but preferably immediately before the chemical sensitizer is added. A silver halide emulsion chemically sensitized in the presence of the above bromine ion is represented by the general formula [I]
Spectral sensitization with an infrared sensitizing dye represented by.

[0010]

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In the formula, R ₁ and R ₂ may be the same or different and each is an alkyl group (preferably having 1 to 8 carbon atoms, for example, methyl group, ethyl group, propyl group,
Butyl group, pentyl group, heptyl group, etc., substituted alkyl group (as a substituent, for example, carboxy group, sulfo group, cyano group, halogen atom (eg fluorine atom, chlorine atom,
Bromine atom, etc., hydroxy group, alkoxycarbonyl group (having 8 or less carbon atoms, for example, methoxycarbonyl group,
Ethoxycarbonyl group, benzyloxycarbonyl group, etc.), alkoxy group (7 or less carbon atoms, for example, methoxy group, ethoxy group, propoxy group, butoxy group, benzyloxy group, etc.), aryloxy group (eg phenoxy group, p-tolyloxy group) Groups), acyloxy groups (having 3 or less carbon atoms, for example, acetyloxy group, propionyloxy group, etc.), acyl groups (having 8 or less carbon atoms, for example, acetyl group, propionyl group, benzoyl group, mesyl group, etc.), carbamoyl group (Eg carbamoyl group,
N, N-dimethylcarbamoyl group, morpholinocarbamoyl group, piperidinocarbamoyl group, etc.), sulfamoyl group (eg, sulfamoyl group, N, N-dimethylsulfamoyl group, morpholinosulfonyl group, etc.). D represents a group of non-metal atoms necessary for completing a 6-membered ring nucleus, and the 6-membered ring nucleus has 1, 2 or more suitable groups such as an alkyl group having 1 to 4 carbon atoms ( For example, a methyl group,
Ethyl group, propyl group, isopropyl group, butyl group, etc.), halogen atom (for example, chlorine atom, bromine atom, etc.), or alkoxy group (having 1 to 4 carbon atoms, for example, methoxy group, ethoxy group, propoxy group, isopropoxy group) , Butoxy group, etc.) and the like. Z ₁ and Z ₂ each represent a non-metal atom group necessary for completing a 5- or 6-membered nitrogen-containing heterocycle, for example, a thiazole nucleus (for example, benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole,
6-bromobenzothiazole, 5-iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-
Ethoxybenzothiazole, 5-carboxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5
-Phenethylbenzothiazole, 5-fluorobenzothiazole, 5-trifluoromethylbenzothiazole,
5,6-Dimethylbenzothiazole, 5-hydroxy-6
-Methylbenzothiazole, tetrahydrobenzothiazole, 4-phenylbenzothiazole, naphtho [2,1-
d] thiazole, naphtho [1,2-d] thiazole, naphtho [2,3-d] thiazole, 5-methoxynaphtho [1,2
-D] thiazole, 7-ethoxynaphtho [2,1-d] thiazole, 8-methoxynaphtho [2,1-d] thiazole, 5-methoxynaphtho [2,3-d] thiazole, etc.], selenazole nucleus [eg Benzoselenazole, 5
-Chlorobenzoselenazole, 5-methoxybenzoselenazole, 5-methylbenzoselenazole, 5-hydroxybenzoselenazole, naphtho [2,1-d] selenazole, naphtho [1,2-d] selenazole, etc.], oxazole Nuclear [benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-bromobenzoxazole, 5-fluorobenzoxazole, 5-phenylbenzoxazole, 5-methoxybenzoxazole, 5-trifluoromethylbenzoxazole, 5 -Hydroxybenzoxazole, 5-carboxybenzoxazole, 6-methylbenzoxazole, 6-chlorobenzoxazole, 6-methoxybenzoxazole, 6-hydroxybenzoxazole, 4,6-dimethylbenzene Oxazole, 5-ethoxy benzoxazole, naphtho [2,1-d] oxazole, naphtho [1, 2 -d] oxazole, naphtho [2,3 -
d] oxazole etc.], quinoline nucleus [eg 2-quinoline, 3-methyl-2-quinoline, 5-ethyl-2-quinoline, 6-methyl-2-quinoline, 8-fluoro-2]
-Quinoline, 6-methoxy-2-quinoline, 6-hydroxy-2-quinoline, 8-chloro-2-quinoline, 8-
Fluoro-4-quinoline, etc.], 3,3-dialkylindolenine nucleus (for example, 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-chloroindolenin, etc.), imidazole nuclei (eg 1-methylbenzimidazole, 1
-Ethylbenzimidazole, 1-Methyl-5-chlorobenzimidazole, 1-Ethyl-5-chlorobenzimidazole, 1-Methyl-5,6-dichlorobenzimidazole, 1-Ethyl-5,6-dichlorobenzimidazole , 1-methyl-5-methoxybenzimidazole, 1
-Methyl-5-cyanobenzimidazole, 1-ethyl-5-cyanobenzimidazole, 1-methyl-5-fluorobenzimidazole, 1-ethyl-5-fluorobenzimidazole, 1-phenyl-5,6-dichlorobenzo Imidazole, 1-allyl-5,6-dichlorobenzimidazole, 1-allyl-5-chlorobenzimidazole, 1-phenylbenzimidazole, 1-phenyl-5-chlorobenzimidazole, 1-methyl-5-trifluoromethyl Benzimidazole, 1-ethyl-5
-Trifluoromethylbenzimidazole, 1-ethylnaphtho [1,2-d] imidazole, etc.), pyridine nucleus (eg, pyridine, 5-methyl-2-pyridine, 3-methyl-4-pyridine, etc.) and the like. . Of these, a thiazole nucleus and an oxazole nucleus are advantageously used. More preferably, a benzothiazole nucleus, a naphthothiazole nucleus, a naphthoxazole nucleus or a benzoxazole nucleus is advantageously used. X ^- represents an acid anion. n represents 1 or 2. Specific examples of the compound represented by the general formula [I] used in the present invention are shown below. However, the present invention is not limited to these specific examples.

[0012]

[Chemical 4]

[0013]

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[0014]

[Chemical 6]

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

The infrared sensitizing dye used in the present invention can be directly dispersed in an emulsion. Further, these may be first dissolved in a suitable solvent such as methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine or a mixed solvent thereof, and added to the emulsion in the form of a solution. Also, ultrasonic waves can be used for dissolution. As a method of adding the infrared sensitizing dye, as described in U.S. Pat.No. 3,469,987, the dye is dissolved in a volatile organic solvent, and the solution is dispersed in a hydrophilic colloid. The method of adding the dispersion to the emulsion, as described in JP-B-46-24185, the water-insoluble dye is dispersed in a water-soluble solvent without being dissolved,
A method of adding this dispersion to an emulsion; US Pat. No. 3,822,13
As described in No. 5, the dye is dissolved in a surfactant,
A method of adding the solution to an emulsion; a method of dissolving using a compound for red-shifting, as described in JP-A-51-74624, and adding the solution to the emulsion; JP-A-50-80826.
A method in which a dye as described in No. 1 is dissolved in an acid containing substantially no water and the solution is added to the emulsion is used.
In addition, the method described in US Pat. Nos. 2,912,343, 3,342,605, 2,996,287, and 3,429,835 and the like can be used for addition to the emulsion.

Various compounds can be added to the photographic emulsion of the present invention in order to prevent the deterioration of sensitivity and the generation of fog during the manufacturing process, storage or processing of the light-sensitive material. The compounds are nitrobenzimidazole, ammonium chloroplatinate, 4-hydroxy-6-methyl-1,3,
An extremely large number of compounds such as many heterocyclic compounds such as 3a, 7-tetraazaindene and 1-phenyl-5-mercaptotetrazole, mercury-containing compounds, 3-mercapto compounds and metal salts can be used. An example of a compound that can be used is
“The Theory of the Photographic Process” by K. Mees
(3rd ed., 1966) pp. 344 to 349 with the original references. Other compounds include, for example, U.S. Pat.
Thiazolium salts described in 131,038 and 2,694,716; US Pat. Nos. 2,886,437 and 2,444,
Azaindenes described in 605 etc .; Urazols described in US Pat. No. 3,287,135 etc .; Sulfocatechols described in US Pat. No. 3,236,652 etc .; Described in UK Patent No. 623,448 etc. Oximes; US Pat. Nos. 2,403,927 and 3,266,897
No. 3,397,987, etc., mercaptotetrazoles, nitrones; nitroindazoles; US Pat. No. 2,839,405, etc., polyvalent metal salts; US Pat. No. 3,220,839, etc. The listed thiuronium salt
ts); Palladium, platinum and gold salts described in US Pat. Nos. 2,566,263 and 2,597,915.

Silver halide photographic emulsions include developing agents such as hydroquinones; catechols; aminophenols; 3-pyrazolidones; ascorbic acid and its derivatives; reductones and phenylenediamines, or a combination of developing agents. Can be included. Developing agents can be incorporated in the silver halide emulsion layers and / or other photographic layers (eg protective layers, interlayers, filter layers, antihalation layers, back layers, etc.). The developing agent is dissolved in a suitable solvent or is disclosed in US Pat. No. 2,592,368.
And in the form of dispersions as described in French Patent 1,505,778. Examples of the development accelerator include U.S. Pat. Nos. 3,288,612, 3,333,959 and 3,345,17.
The compounds described in No. 5, No. 3,708,303, British Patent No. 1,098,748, West German Patent Nos. 1,141,531, and No. 1,183,784 can be used.

The photographic emulsion of the present invention may contain an inorganic or organic hardener. For example, chrome salt (chrome alum,
Chromium acetate, etc., aldehydes (formaldehyde,
Glyoxal, glitalaldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), 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.), mucohalogenic acids (mucochloric acid, mucophenoxycycloric acid etc.), iso Oxazoles, dialdehyde starch, 2-
Chlor-6-hydroxytriazinylated gelatin and the like can be used alone or in combination. Specific examples thereof include U.S. Patents 1,870,354, 2,080,019 and 2,72.
6,162, 2,870,013, 2,983,611, 2,992,
109, 3,047,394, 3,057,723, 3,103,43
No. 7, No. 3,321,313, No. 3,325,287, No. 3,362,827
No. 3,539,644, No. 3,543,292, and British Patent 676,62.
No. 8, No. 826,544, No. 1,270,578, German Patent 872,
No. 153, No. 1,090,427, Japanese Patent Publication No. 34-7,133, No. 46-
There is a description in 1872.

A photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material produced by using the present invention may be coated with a coating aid, an antistatic agent, an improvement in slipperiness, an emulsion dispersion, an adhesion prevention and an improvement in photographic characteristics (for example, development acceleration). , Contrast enhancement, sensitization), and various other surfactants may be included. For example, saponin (steroidal), alkylene oxide derivative (eg polyethylene glycol, polyethylene glycol /
Polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or amides, silicone polyethylene oxide adducts), glycidol derivatives ( Non-ionic surfactants such as alkenyl succinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols, alkyl esters of sugars; alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkyls Naphthalene sulfonate, alkyl sulfates, alkyl phosphates, N-acyl-N-alk Acidity such as carboxy group, sulfo group, phospho group, sulfate ester group, phosphate ester group such as taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc. Anionic surfactants containing groups; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric acid esters, alkylbetaines, amine oxides; alkylamine salts, aliphatic or aromatic fourth groups Cationic surfactants such as quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocyclic rings can be used.

For the purpose of improving the sharpness of the legs of the characteristic curve and obtaining a high quality halftone dot or line image, etc., a polyalkylene oxide compound (for example, an alkylene oxide having 2 to 4 carbon atoms, such as ethylene oxide, propylene) is used. −
1,2-oxide, butylene-1,2-oxide, etc.,
Preferably, a polyalkylene oxide consisting of at least 10 units of ethylene oxide and a condensate or two kinds of a compound having at least one active hydrogen atom such as water, an aliphatic alcohol, an aromatic alcohol, a fatty acid, an organic amine or a hexitol derivative. The above block copolymers of polyalkylene oxide, etc.) can be used. Examples of specific compounds include JP-A-50-156423.
The polyalkylene oxide compounds described in JP-A-52-108130 and JP-A-53-3217 can be used. These polyalkylene oxide compounds may be used alone or in combination of two or more.

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, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol. , Polyvinyl alcohol partial acetal, poly-
N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole,
A wide variety of synthetic hydrophilic polymeric substances such as polyvinylpyrazole and other single or copolymers can be used. As the gelatin, acid-treated gelatin may be used in addition to lime-treated gelatin, and gelatin hydrolyzate and gelatin enzyme-decomposed product may also be used. As the gelatin derivative, various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleinimide compounds, polyalkylene oxides, epoxy compounds are added to gelatin. What is obtained by reaction is used. Specific examples thereof are U.S. Patents 2,614,928, 3,132,945 and 3,186,846.
No. 3,312,553, British Patent 861,414, No. 1,033,18
No. 9, 1,005,784, and JP-A No. 42-26845. As the gelatin-grafted polymer, a single (homo) or copolymer of a vinyl monomer such as acrylic acid, methacrylic acid, derivatives thereof such as esters and amides, acrylonitrile and styrene is grafted onto gelatin. Can be used. In particular, a graft polymer with a polymer having a certain degree of compatibility with gelatin, for example, a polymer such as acrylic acid, methacrylic acid, allylamide, methacrylamide, or hydroxyalkyl methacrylate is preferable.
Examples of these are U.S. Patents 2,763,625, 2,831,767,
There is a description in No. 2,956,884. A typical synthetic hydrophilic polymer is, for example, West German Patent Application (OLS) 2,312,70.
No. 8, U.S. Patents 3,620,751 and 3,879,205, JP
No. 43-7651.

The photographic emulsion of the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. For example, alkyl (meth) acrylate, alkoxyacryl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene, etc., alone or in combination, or with acrylic acid. , Methacrylic acid,
A polymer containing a combination of α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid as a monomer component can be used. For example, U.S. Patents 2,376,005, 2,739,137, 2,853,457,
No. 3,062,674, No. 3,411,911,
Same 3,488,708, same 3,525,620, same 3,607,290, same
3,635,715, 3,645,740, British patent 1,186,699
No. 1,307,373 can be used.

Any photographic developing method may be applied to the light-sensitive material of the present invention. Examples of the developing agent used in the developing solution include a dihydroxybenzene-based developing agent, a 1-phenyl-3-pyrazolidone-based developing agent, a p-aminophenol-based developing agent, and the like, which may be used alone or in combination (for example, 1-phenyl-3 -Pyrazolidones and dihydroxybenzenes or p-aminophenols and dihydroxybenzenes) can be used. Further, the light-sensitive material of the present invention may be processed with a so-called infectious developer using a sulfite ion buffer such as carbonyl bisulfite and hydroquinone. In the above, examples of the dihydroxybenzene-based developing agent include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, and 2,5-dimethylhydroquinone, and 1-phenyl-3-pyrazolidone. As a developing agent, 1-phenyl-3-pyrazolidone, 4,4-dimethyl-1-phenyl-3-pyrazolidone, 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone, 4,4-dihydroxymethyl -1-Phenyl-3-pyrazolidone and the like, and p-aminophenol, N-methyl-p-aminophenol, and the like are used as the p-aminophenol-based developing agent. A compound that gives a free sulfite ion as a preservative to the developer, for example, sodium sulfite, potassium sulfite, potassium metabisulfite,
Sodium bisulfite and the like are added. In the case of an infectious developer, formaldehyde sodium bisulfite which gives almost no free sulfite ion in the developer may be used. As the alkaline agent of the developer used in the present invention, potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, sodium acetate, potassium tertiary phosphate, diethanolamine, triethanolamine and the like are used. The pH of the developer is usually set to 9 or higher, preferably 9.7 or higher. The developer may contain an organic compound known as an antifoggant or a development control agent. Examples thereof include azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, Aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole) and the like; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes, for example Triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetrazaindenes), pentaazaindenes, etc. Benzenethiosulfonate, benzene sulfinic acid, benzenesulfonic acid amide, and the like 2-mercaptobenzimidazole-5-sodium sulfonate.

The developer which can be used in the present invention may contain the same polyalkylene oxide as described above as a development inhibitor. For example, polyethylene oxide having a molecular weight of 1,000 to 10,000 can be contained in the range of 0.1 to 10 g / l. It is preferable to add nitrilotriacetic acid, ethylenediaminetetraacetic acid, triethylenetetraaminehexaacetic acid, diethylenetetraaminepentaacetic acid, etc. as a water softening agent to the developer which can be used in the present invention. 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 fixing solution may contain a complex of ethylenediaminetetraacetic acid and a trivalent iron ion as a sulfiding agent. Although the treatment temperature and the treatment time are appropriately set, a treatment temperature of 18 ° C to 50 ° C is usually suitable.

[0026]

The present invention will be described in more detail with reference to the following examples. Example 1 [Preparation of silver halide emulsion] A silver halide emulsion was prepared according to the following formulation. Preparation of silver halide grains-1 liquid water 1.0 liter gelatin 35 g sodium chloride 3.5 g 3,6 dithiooctane-1,8-diol 33 mg-2 liquid water 200 ml silver nitrate 32.5 g-3 liquid water 200 ml sodium chloride a g Potassium bromide b g Potassium hexachloroiridate (0.002% aqueous solution) 36 ml Sodium hexachlororhodate (0.001% aqueous solution) 3 ml-4 liquid water 600 ml Silver nitrate 217 g-5 liquid water 600 ml Sodium chloride c g Potassium bromide d g K ₄ Fe (CN) ₆ 10 mg At the same time, 2 and 3 solutions were added to 1 solution kept at 42 ° C and pH 3.5 for 12 minutes at the same time with stirring, then 4 solutions and 5 solutions were added to 20
Added over minutes. Then, it was washed with water by a flocculation method according to a conventional method. According to the above method, as shown in Table 1, a, b, c and d were changed to prepare silver halide grains having different chlorine and bromine ratios. Further, 30 g of gelatin was added and pH was adjusted to 6.5, potassium bromide was added as shown in Table 1, and further 2 mg of sodium benzenethiosulfonate, 14 mg of sodium thiosulfate and 15 mg of sodium chloroaurate were added, Chemical sensitization was performed so that the maximum sensitivity was obtained at 55 ° C. Further, 50 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added as a stabilizer.

[0027]

[Table 1]

Using the silver halide emulsion shown in Table 1, 30 mg of a sensitizing dye was added as shown in Table 2 to perform dye sensitization. Further, 6 g of hydroquinone and polyacrylate latex were used at a gelatin binder ratio of 25% and a hardness. 2-bis (vinylsulfonyl acetamide) ethane as a film agent was added 1.25 g, 3.8 g / m ² coated silver amount in the polyester support was coated to the coating of gelatin 1.6 g / m ^2. At this time, 0.5 g / m ^{2 of} gelatin was used as a protective layer on the upper side of the emulsion layer, 50 mg / m ² of a silica matting agent having a particle size of 2.5 μm was used as a matting agent, and the particle size was
10 μm of colloidal silica was used at 60 mg / m ² and sodium dodecylbenzenesulfonate was used as a coating aid, and the coating was performed at the same time as the emulsion layer.

[0029]

[Chemical 7]

<Evaluation of Photographic Performance> The obtained sample was tested at 780 nm.
Through an interference filter with continuous peak and continuous wedge,
The film was exposed to xenon flash light with a light emission time of 10 ^-6 sec and developed using an automatic processor FG-710NH manufactured by Fuji Photo Film Co., Ltd. at the temperature and time shown below. Development 38 ° C for 12 seconds Fixing 38 ° C for 10 seconds Washing with water 26 ° C for 10 seconds Squeeze for 3 seconds Drying for 10 seconds Total 45 seconds The developing solution and fixing solution used have the following composition. [Developer Solution Formulation] Hydroquinone 25.0 g 4-Methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone 0.5 g Potassium sulfite 90.0 g Disodium ethylenediaminetetraacetate 2.0 g Potassium bromide 5.0 g 5-Methylbenzotriazole 0.2 g 2 -Mercaptobenzimidazole-5-sulfonic acid 0.3 g Sodium carbonate 20 g Water added 1 liter (sodium hydroxide is added to adjust pH = 10.6) [Fixer formulation] Ammonium thiosulfate 210 g Sodium sulfite (anhydrous) 20 g Ethylenediaminetetraacetic acid disodium 0.1 g Glacial acetic acid 15 g Water was added to 1 liter (adjusted to pH = 4.8 with ammonia water) The measurement results of the obtained sample are shown in Table 2. Relative sensitivity is defined as the reciprocal of the logarithm of the exposure that gives a density of 3.0,
The sensitivity of o.10 is expressed as 100, and fog is fog x 10
It was shown by the value of.

[0031]

[Table 2]

<Results> From the results of Table 2, the present invention has high sensitivity and low fog, and the effects of the present invention can be seen.

Example 2 Using the emulsion used in Example 1, except that the sensitizing dye was changed to that shown in Table 4, the same emulsion layer composition as in Example 1 was used. The antihalation layer was simultaneously coated on the polyester film.

[0034]

[Table 3]

[0035]

[Table 4]

[0036]

[Table 5]

The sample polyester film used in this example has a back upper layer and a back lower layer having the following compositions.

[0038]

[Table 6]

[0039]

[Table 7]

[0040]

Embedded image

The same processing as in Example 1 was carried out to evaluate the photographic performance, and the relative sensitivity and fog are shown in Table 4.

[0042]

[Table 8]

[0043]

[Chemical 9]

<Results> From the results shown in Table 4, the present invention has high sensitivity and low fog.

[0045]

From the above examples, the present invention can provide a silver halide photographic light-sensitive material having high sensitivity to infrared laser light and low fog.

[Procedure amendment]

[Submission date] March 23, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0030

[Correction method] Change

[Correction content]

<Evaluation of Photographic Performance> The obtained sample was tested at 780 nm.
Through an interference filter with continuous peak and continuous wedge,
The film was exposed to xenon flash light with a light emission time of 10 ^-6 sec and developed using an automatic processor FG-710NH manufactured by Fuji Photo Film Co., Ltd. at the temperature and time shown below. Development 38 ° C for 12 seconds Fixing 38 ° C for 10 seconds Washing with water 26 ° C for 10 seconds Squeeze for 3 seconds Drying for 10 seconds Total 45 seconds The developing solution and fixing solution used have the following composition. [Developer Solution Formulation] Hydroquinone 25.0 g 4-Methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone 0.5 g Potassium sulfite 90.0 g Disodium ethylenediaminetetraacetate 2.0 g Potassium bromide 5.0 g 5-Methylbenzotriazole 0.2 g 2 -Mercaptobenzimidazole-5-sulfonic acid 0.3 g Sodium carbonate 20 g Water added 1 liter (sodium hydroxide is added to adjust pH = 10.6) [Fixer formulation] Ammonium thiosulfate 210 g Sodium sulfite (anhydrous) 20 g Ethylenediaminetetraacetic acid disodium 0.1 g Glacial acetic acid 15 g Water was added to 1 liter (adjusted to pH = 4.8 with ammonia water) The measurement results of the obtained sample are shown in Table 2. Relative sensitivity is defined as the reciprocal of the logarithm of the exposure dose that gives a density of 3.0, and
The sensitivity of o.10 is expressed as 100, and the fog is fog x 100.
It was shown by the value of.

Claims (1)

[Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on a support,
The silver halide emulsion has a chlorine content of 50 mol% to 90 mol%. The silver halide emulsion contains bromine ions in an amount of 1 mol% to 5 mol% with respect to silver during chemical sensitization. A silver halide light-sensitive material dye-sensitized with at least one compound represented by formula [I]. Embedded image [In the formula, R ₁ and R ₂ may be the same or different and each represents an alkyl group or an alkoxy group. D represents a nonmetallic atomic group necessary for completing a 6-membered ring nucleus.
Z ₁ and Z ₂ each represent a nonmetallic group necessary for completing a 5- or 6-membered nitrogen-containing heterocycle. X ^- represents an acid anion. n
Represents 1 or 2, and when n is 1, forms an inner salt. ]