JPH0950091A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material capable of obtaining an image high in sensitivity and small in fluctuation of performances caused by the change of humidity at the time of exposure and stable in finish. SOLUTION: This photographic sensitive material contains a mercaptoazole derivative capable of obtaining a betaine structure in the molecule, preferably, a compound represented by the formula in which M1 is an H or metal atom or a tetrammonium group; Q1 is a nonmetallic atomic group necessary to form a single or condensed ring by combining with a C atom and an N atom; (n) is 0, 1, or 2; each of R1 and R2 is, independently an alkyl group or each may combined with each other to form a ring; and R3 is an H atom or an alkyl or aryl group, and L is bivalent group.

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 light-sensitive material capable of obtaining a stable finish with little change in performance due to changes in humidity during exposure.

[0002]

2. Description of the Related Art Silver halide photographic light-sensitive materials, particularly silver halide color photographic light-sensitive materials, are widely used today because of their high sensitivity, excellent gradation and sharpness.

However, the development processing of the silver halide color photographic light-sensitive material is a so-called wet processing, and it takes time to prepare the processing solution, it becomes dirty, a waste solution containing various chemicals is discharged, and a dark room is required. There are drawbacks such as a long time from the start of the operation until the first print is obtained. To compensate for these disadvantages and take advantage of the advantages of the silver halide color photographic light-sensitive material described above, until now, skilled engineers have concentrated on developing color negatives to producing color prints in only a few large developing laboratories. The scheme has been taken.

However, although the essence of wet processing has not changed in recent years, improvements in equipment such as printers and automatic processors, improvements in developing solutions, improvements in silver halide color photographic light-sensitive materials and their packaging forms have been accumulated. Therefore, a so-called minilab, which is capable of consistently performing color negative development to color print production in a small space such as at a photo shop, is rapidly becoming popular. However, there is a strong demand for further shortening of development processing time and high robustness against environmental conditions.

In recent years, the development processing time has been remarkably shortened by employing a silver halide emulsion containing a high concentration of silver chloride. However, it cannot be said that the resistance to fluctuations due to development processing conditions or environmental conditions during exposure is sufficient. In particular, fluctuation due to humidity conditions during exposure is one of the serious problems. In addition, this problem is especially 400 nm to 650
It was also found to be significant when using emulsions spectrally sensitized to nm. For example, when a specific sensitizing dye is contained so as to have a spectral sensitivity of 650 nm or more, even if a silver halide emulsion containing a high concentration of silver chloride is used, the humidity conditions at the time of exposure as described above will There were no problems with different finishes.

Japanese Patent Publication No. 55-12581 and Japanese Patent Publication No. 62-
2014440, JP-A-62-260241, JP-A-1-291250, and JP-A-4-253053 disclose techniques for improving latent image stability by containing a specific thiazolium compound. These techniques describe the stability of the resulting latent image for a relatively long time,
Nothing is said about the efficiency involved in the latent image formation process of electrons during exposure.

Japanese Unexamined Patent Publication No. 4-368935 discloses a technique for improving the sensitivity fluctuation due to the humidity change at the time of exposure by incorporating an adsorptive reducing compound. However, since this technique tends to lower the sensitivity of the light-sensitive material, there has been a strong demand for a technique that improves sensitivity fluctuation due to humidity change during exposure while maintaining sensitivity.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide photographic light-sensitive material which has high sensitivity, has little performance fluctuation due to humidity change during exposure, and can provide a stable finish.

[0009]

The inventors of the present invention have made intensive studies on silver halide photographic emulsions used in silver halide photographic light-sensitive materials, and have found that the above object of the present invention can be achieved by the following constitution. The present invention has been completed.

(1). A silver halide photographic light-sensitive material containing a mercaptoazole compound capable of having a betaine structure in the molecule.

(2). A silver halide photographic light-sensitive material comprising a compound represented by the following general formula (1).

[0012]

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[In the formula, M ₁ represents a hydrogen atom, a metal atom, or a quaternary ammonium group. Q ₁ represents a group of non-metal atoms necessary for bonding to a carbon atom and a nitrogen atom to form a monocyclic ring or a condensed heterocycle with them. L represents a divalent group, and n represents an integer of 0 to 2. R ₁ and R ₂ represent an alkyl group, R ₁ and R ₂ may be the same or different,
Also, they may be bonded to each other to form a ring. R ₃ represents a hydrogen atom, an alkyl group, or an aryl group. ] (3). A silver halide photographic light-sensitive material comprising a compound represented by the following general formula (2) or general formula (3).

[0014]

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[In the formula, M ₂ represents a hydrogen atom, a metal atom, or a quaternary ammonium group. Q ₂ represents a group of non-metal atoms necessary for bonding to a carbon atom and a nitrogen atom to form a monocyclic ring or a condensed heterocycle with them. R ₄ and R ₅ represent an alkyl group, R ₄ and R ₅ may be the same or different, and may combine with each other to form a ring. R ₆ represents a hydrogen atom, an alkyl group, or an aryl group. (4). A silver halide emulsion layer (referred to as YL) each containing at least one yellow coupler on a support;
Silver halide emulsion layer containing magenta coupler (ML
, And a silver halide emulsion layer containing a cyan coupler (referred to as CL), and YL, ML, and CL each have a betaine structure in the molecule in a multilayer color light-sensitive material having different spectral sensitization. Multi-layer color light-sensitive material having a layer containing a mercaptoazole compound.

(5). On the support, a silver halide emulsion layer containing at least one yellow coupler (Y
L), a silver halide emulsion layer containing magenta coupler (referred to as ML) and a silver halide emulsion layer containing cyan coupler (referred to as CL), and Y
A multilayer color light-sensitive material, wherein L, ML and CL each have a different spectral sensitization, and a layer containing a compound represented by the above formula (1).

(6). On the support, a silver halide emulsion layer containing at least one yellow coupler (Y
L), a silver halide emulsion layer containing magenta coupler (referred to as ML) and a silver halide emulsion layer containing cyan coupler (referred to as CL), and Y
A multilayer color light-sensitive material in which L, ML, and CL each have a different spectral sensitization, and a layer containing a compound represented by the general formula (2) or (3).

(7). In a silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer on a support, at least one of the silver halide emulsion layers contains silver halide grains having a silver chloride content of 90 mol% or more. The silver halide photographic light-sensitive material as described in (1), which further comprises:

(8). The silver halide photographic light-sensitive material according to (1), wherein at least one of the silver halide emulsion layers contains silver halide grains having a silver chloride content of 95 mol% or more.

(9). In a silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer on a support, at least one of the silver halide emulsion layers contains silver halide grains having a silver chloride content of 90 mol% or more. The silver halide photographic light-sensitive material as described in (2), which contains.

(10). The silver halide photographic light-sensitive material described in (2), wherein at least one of the silver halide emulsion layers contains silver halide grains having a silver chloride content of 95 mol% or more.

(11). In a silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer on a support, at least one of the silver halide emulsion layers contains silver halide grains having a silver chloride content of 90 mol% or more. The silver halide photographic light-sensitive material as described in (3), which further comprises:

(12). The silver halide photographic light-sensitive material as described in (3), wherein at least one of the silver halide emulsion layers contains silver halide grains having a silver chloride content of 95 mol% or more.

The present invention will be described in detail below.

The mercaptoazole compound capable of having a betaine structure in the molecule of the present invention will be described.

The mercaptoazole compound capable of having a betaine structure in the molecule means a zwitterionic compound, and specifically, the substituent is a basic group (eg, amino group, nitrogen-containing heterocyclic group, guanidino). Group, an amidino group, and the like). In other words, it can be expressed as a compound having an isoelectric point.

Next, the compound represented by the general formula (1) of the present invention will be described.

In the above general formula (1), the cation represented by M ₁ is preferably an alkali metal cation (eg Na ⁺ , K ⁺ etc.), an alkaline earth metal cation (eg Ca ⁺⁺ , Mg ^{+). +} Etc.) and ammonium cations (for example, ammonium cation, triethylammonium cation, pyridinium cation, etc.).

As the metal atom represented by M ₁ , Li, N
Examples thereof include a, K, Mg, Ca, Zn and Ag.

Examples of the quaternary ammonium group represented by M ₁ include NH ₄ , N (CH ₃ ) ₄ , N (C ₄ H ₉ ) ₄ and N (C
_{H 3) 3 C 12 H 25} , N (CH 3) 3 C 16 H 33, N (CH 3) 3
Such as CH ₂ C ₆ H ₅ and the like.

Preferred heterocycles formed by Q ₁ are imidazole ring, pyrazole ring, triazole ring, tetrazole ring, oxazole ring, thiazole ring,
Selenazole ring, tellurazole ring, oxadiazole ring, thiadiazole ring, pyridine ring, pyrimidine ring,
Examples thereof include a benzimidazole ring, a benzoxazole ring, and a benzothiazole ring in which an aromatic ring is condensed. Another preferable example is a tetrazaindene ring.

Preferred divalent groups represented by L are:
Examples thereof include an alkylene group, an arylene group, a heteroarylene group, an ether group, a thioether group, an imino group, an ester group, an amide group and a sulfonyl group, and these groups are combined to form one divalent group. Good.

Examples of the alkyl group represented by R ₁ , R ₂ and R ₃ include methyl, ethyl, propyl, i-propyl, butyl, t-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl and dodecyl. Each group of is mentioned. These alkyl groups further include a halogen atom (for example, each atom of chlorine, bromine, fluorine, etc.), an alkoxy group (for example, each group of methoxy, ethoxy, 1,1-dimethylethoxy, hexyloxy, dodecyloxy, etc.), aryloxy. Group (for example, each group such as phenoxy and naphthyloxy), aryl group (for example, each group such as phenyl and naphthyl), alkoxycarbonyl group (for example, each group such as methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, 2-ethylhexylcarbonyl), Aryloxycarbonyl group (for example, phenoxycarbonyl, naphthyloxycarbonyl, and other groups), heterocyclic group (for example, 2-pyridyl, 3-pyridyl, 4-pyridyl,
Morpholyl, piperidyl, piperazil, selenazolyl,
Each of sulforanyl, piperidinyl, tetrazolyl, thiazolyl, oxazolyl, imidazolyl, thienyl, pyrrolyl, pyrazinyl, pyrimidinyl, pyridazinyl, pyrimidyl, pyrazolyl, furyl, etc.), amino group (for example, amino, N, N-dimethylamino, anilino, etc.) Group), a hydroxyl group, a cyano group, a sulfo group, a carboxyl group, a sulfonamide group (eg, methylsulfonylamino, ethylsulfonylamino, butylsulfonylamino, octylsulfonylamino, phenylsulfonylamino, etc.) Good.

Examples of the aryl group represented by R ₃ include a phenyl group and a naphthyl group.

Next, the compounds represented by the general formulas (2) and (3) of the present invention will be described.

In the above general formulas (2) and (3), the cation represented by M ₂ is preferably an alkali metal cation (eg Na ⁺ , K ⁺ etc.), an alkaline earth metal cation (eg Ca ⁺⁺ , Mg ^++, etc.) and ammonium cations (eg, ammonium cation, triethylammonium cation, pyridinium cation, etc.) can be mentioned.

As the metal atom represented by M ₂ , Li, N
Examples thereof include a, K, Mg, Ca, Zn and Ag.

Examples of the quaternary ammonium group represented by M ₂ are NH ₄ , N (CH ₃ ) ₄ , N (C ₄ H ₉ ) ₄ and N (C
_{H 3) 3 C 12 H 25} , N (CH 3) 3 C 16 H 33, N (CH 3) 3
Such as CH ₂ C ₆ H ₅ and the like.

Preferred heterocycles formed by Q ₂ are imidazole ring, pyrazole ring, triazole ring, tetrazole ring, oxazole ring, thiazole ring,
Selenazole ring, tellurazole ring, oxadiazole ring, thiadiazole ring, pyridine ring, pyrimidine ring,
Examples thereof include a benzimidazole ring, a benzoxazole ring, and a benzothiazole ring in which an aromatic ring is condensed. Another preferable example is a tetrazaindene ring.

Examples of the alkyl group represented by R ₄ , R ₅ and R ₆ are, for example, methyl, ethyl, propyl, i-propyl, butyl, t-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, dodecyl and the like. Each group of is mentioned. These alkyl groups further include a halogen atom (for example, each atom of chlorine, bromine, fluorine, etc.), an alkoxy group (for example, each group of methoxy, ethoxy, 1,1-dimethylethoxy, hexyloxy, dodecyloxy, etc.), aryloxy. Group (for example, each group such as phenoxy and naphthyloxy), aryl group (for example, each group such as phenyl and naphthyl), alkoxycarbonyl group (for example, each group such as methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, 2-ethylhexylcarbonyl), Aryloxycarbonyl group (for example, phenoxycarbonyl, naphthyloxycarbonyl, and other groups), heterocyclic group (for example, 2-pyridyl, 3-pyridyl, 4-pyridyl,
Morpholyl, piperidyl, piperazil, selenazolyl,
Each of sulforanyl, piperidinyl, tetrazolyl, thiazolyl, oxazolyl, imidazolyl, thienyl, pyrrolyl, pyrazinyl, pyrimidinyl, pyridazinyl, pyrimidyl, pyrazolyl, furyl, etc.), amino group (for example, amino, N, N-dimethylamino, anilino, etc.) Group), a hydroxyl group, a cyano group, a sulfo group, a carboxyl group, a sulfonamide group (eg, methylsulfonylamino, ethylsulfonylamino, butylsulfonylamino, octylsulfonylamino, phenylsulfonylamino, etc.) Good.

Examples of the aryl group represented by R ₆ include phenyl and naphthyl groups.

Specific examples of the compounds represented by the general formulas (1), (2) and (3) of the present invention are shown below, but the present invention is not limited thereto.

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[0044]

[Chemical 6]

[0045]

[Chemical 7]

[0046]

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[0047]

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Specific examples of the method for synthesizing the compounds represented by the general formulas (1), (2) and (3) of the present invention are shown below.

(Synthesis of Exemplified Compound 1-1) 6.81 g of 4-dimethylaminananiline was dissolved in 10 ml of benzene,
After 3.3 ml of carbon disulfide was added dropwise, the reaction solution was ice-cooled and 7.0 ml of triethylamine was added dropwise over about 10 minutes. The reaction solution gradually solidified, allowed to stand at room temperature for 3 hours, 30 ml of diethyl ether was added, and the mixture was stirred for 10 minutes and then the crystals were filtered to obtain Intermediate 1.

The crystals were dissolved in 50 ml of chloroform, and 7.0 ml of triethylamine was further added. The reaction solution was ice-cooled to about 3 ° C. and then ethyl chloroformate 5.1 m
1 was added dropwise while being careful not to let the reaction liquid exceed 5 ° C. After the dropping, the mixture was stirred under ice cooling for 15 minutes and then at room temperature for 1.5 hours to complete the reaction. The precipitated triethylamine hydrochloride was filtered off and washed twice with 5 ml of dilute hydrochloric acid,
It was washed with water three more times. The organic phase obtained was dried over anhydrous magnesium sulfate, the solvent was distilled under reduced pressure, and the product was recrystallized from 12 ml of methanol to obtain 6.25 g of intermediate 2 as a pale yellow crystal (yield 70.2%). Obtained. (Note that the structure was identified by ¹ HNMR, IR, and FD mass spectra. Melting point: 69.5 to 70.0 ° C) Intermediate 2, 6.20 g, sodium azide 5.60 g,
180 ml of water and 18 ml of ethanol were mixed and heated under reflux for about 3 hours. The reaction solution was cooled to room temperature, the insoluble material was filtered off, and concentrated hydrochloric acid was added to adjust the pH to 4. The precipitated crystals were filtered and further methanol / ethanol = 80 ml
By recrystallizing in a mixed solvent of / 25 ml, 6.0 g (yield 78.0) of Exemplified Compound 1-1 as pale yellow needle crystals.
%)Obtained. (The structure was identified by ¹ HNMR, IR, and FD mass spectrum. Melting point 169 to 171 ° C) Other compounds can be synthesized in the same manner as above.

In the present invention, the silver halide emulsion is a conventional silver halide emulsion such as silver chloride, silver bromide, silver iodochloride, silver iodobromide chlorobromide and silver chloroiodobromide as silver halide. Any used can be used. A preferable composition of the silver halide photographic emulsion is substantially no silver iodide-containing silver chlorobromide containing 90 mol% or more of silver chloride, and more preferably 95 mol% or more. From the viewpoint of rapid processing and processing stability, a silver halide emulsion containing 97 mol% or more of silver chloride is more preferable, and a silver halide emulsion containing 98 to 100 mol% of silver chloride is particularly preferable.

To obtain the silver halide emulsion according to the present invention, a silver halide emulsion having a portion containing a high concentration of silver bromide is particularly preferably used. In this case, the portion containing a high concentration of silver bromide may be epitaxy-bonded to silver halide emulsion grains, a so-called core-shell emulsion, or may be formed only partially without forming a complete layer. May simply have regions with different compositions. Further, the composition may change continuously or discontinuously. It is particularly preferable that the portion where silver bromide exists at a high concentration is the top of crystal grains on the surface of silver halide grains.

In order to obtain the silver halide emulsion according to the present invention, it is advantageous to contain a heavy metal ion. Heavy metal ions that can be used for such purposes include iron,
Iridium, platinum, palladium, nickel, rhodium,
Examples include Group 8 to 10 metals such as osmium, ruthenium, and cobalt; Group 12 transition metals such as cadmium, zinc, and mercury; and ions of lead, rhenium, molybdenum, tungsten, gallium, and chromium. Among them, metal ions of iron, iridium, platinum, ruthenium, gallium and osmium are preferred.

These metal ions can be added to the silver halide emulsion in the form of a salt or a complex salt.

When the heavy metal ion forms a complex, its ligands are cyanide ion, thiocyanate ion, cyanate ion, chloride ion, bromide ion, iodide ion, nitrate ion, carbonyl and ammonia. Etc. can be mentioned. Among them, cyanide ion, thiocyanate ion, isothiocyanate ion, chloride ion, bromide ion and the like are preferable.

In order to add a heavy metal ion to the silver halide emulsion according to the present invention, the heavy metal compound is added to the physical layer before the formation of silver halide grains, during the formation of silver halide grains and after the formation of silver halide grains. It may be added at any place during each step during aging. In order to obtain a silver halide emulsion satisfying the above-mentioned conditions, a heavy metal compound can be dissolved together with a halide salt and continuously added during the whole or part of the grain forming process.

The amount of the heavy metal ion added to the silver halide emulsion is 1 × 10 ^-9 per mol of silver halide.
Mol or more and 1 × 10 ^-2 mol or less, particularly preferably 1 × 10 ⁻² mol or less.
It is preferably at least 10 ^-8 mol and not more than 5 10 ^-5 mol.

The silver halide grains according to the present invention may have any shape. One preferred example is
It is a cube having a (100) plane as a crystal surface. U.S. Pat. Nos. 4,183,756 and 4,225,666;
JP-A-55-26589, JP-B-55-42737, and The Journal of Photographic Science (J. Photogr. Sci.) 21, 39.
(1973), etc., particles having an octahedral, tetradecahedral, dodecahedral shape or the like can be prepared and used. Further, particles having a twin plane may be used.

As the silver halide grains according to the present invention, grains having a single shape are preferably used, but it is particularly preferable to add two or more kinds of monodispersed silver halide emulsions to the same layer.

The grain size of the silver halide grains according to the present invention is not particularly limited, but in view of other photographic properties such as rapid processability and sensitivity, it is preferably 0.1 to 1.2 μm.
m, and more preferably 0.2 to 1.0 μm.

The particle size can be measured using the projected area of the particle or the approximate diameter. If the particles are of substantially uniform shape, the particle size distribution can be fairly accurately expressed as a diameter or projected area.

The grain size distribution of the silver halide grains of the present invention is preferably monodisperse silver halide grains having a coefficient of variation of 0.22 or less, more preferably 0.15 or less, and a coefficient of variation of 0 is particularly preferred. It is to add two or more kinds of monodisperse emulsions of 0.15 or less to the same layer. Here, the coefficient of variation is a coefficient representing the width of the particle size distribution, and is defined by the following equation.

Coefficient of variation = S / R (where, S is the standard deviation of the particle size distribution, and R is the average particle size.) The particle size here is the diameter of a spherical silver halide particle. In the case of a particle having a shape other than a cube or a sphere, it represents a diameter when the projected image is converted into a circular image having the same area.

As the apparatus and method for preparing a silver halide emulsion, various methods known in the art can be used.

The silver halide emulsion according to the present invention may be obtained by any of the acidic method, the neutral method and the ammonia method. The particles may be grown at one time or may be grown after seed particles have been made. The method of producing the seed particles and the method of growing them may be the same or different.

The method of reacting the soluble silver salt with the soluble halide salt may be any of a forward mixing method, a back mixing method, a simultaneous mixing method, a combination thereof, etc., but a method obtained by the simultaneous mixing method. Is preferred. Further, as one type of the double jet method, a pAg controlled double jet method described in JP-A-54-48521 can be used.

Further, JP-A-57-92523 and 57-57
No.-92524, etc., a device for supplying an aqueous solution of a water-soluble silver salt and a water-soluble halide salt from an addition device arranged in a reaction mother liquor, and a water-soluble silver salt and a water-soluble solution described in German Patent Publication No. 292,164. Apparatus for continuously changing the concentration of an aqueous halide salt solution, JP-B-56-50
The reaction mother liquor was taken out of the reactor described in No. 1776, etc.,
An apparatus that forms grains while keeping the distance between silver halide grains constant by concentrating by ultrafiltration may be used.

If necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound or a compound such as a sensitizing dye may be added at the time of forming silver halide grains or after the completion of grain formation.

The silver halide emulsion according to the present invention can be used in combination with a sensitizing method using a gold compound and a sensitizing method using a chalcogen sensitizer.

As the chalcogen sensitizer applied to the silver halide emulsion according to the present invention, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer and the like can be used, and the sulfur sensitizer is preferable. Thiosulfates as sulfur sensitizers,
Allyl thiocarbamide thiourea, allyl isothiocyanate, cystine, p-toluene thiosulfonate, rhodanine, inorganic sulfur and the like can be mentioned.

The addition amount of the sulfur sensitizer according to the present invention is preferably changed depending on the type of silver halide emulsion to be applied and the magnitude of expected effect, but 5 × 10 5 per mol of silver halide. ^{-10 to} 5 × 10 ^-5 mol range,
Preferably, it is in the range of 5 × 10 ^{−8 to} 3 × 10 ⁻⁵ mol.

The gold sensitizer according to the present invention may be added in the form of various gold complexes other than chloroauric acid, gold sulfide and the like. Examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, and mercaptotriazole. The amount of the gold compound used varies depending on the type of silver halide emulsion, the type of compound used, the ripening conditions, etc., but is usually 1 × 10 ⁻⁴ mol to 1 × 10 ⁻⁸ mol per mol of silver halide.
It is preferably molar. More preferably, 1 × 10 ⁻⁵
Mol to 1 × 10 ⁻⁸ mol.

A reduction sensitization method may be used as the chemical sensitization method of the silver halide emulsion according to the present invention.

The compound represented by the general formula (1) of the present invention is preferably contained in the silver halide emulsion layer or its adjacent layer, and the addition amount thereof is preferably 2 × 1.
0 ^{−5 to} 0.2 g / m ² , more preferably 1 × 10 ⁻⁴ to
0.1 g / m ² , particularly preferably 2 × 10 ^{−4 to} 0.05
g / m ² .

The method of adding the compound represented by the general formula (1) of the present invention to a silver halide photographic emulsion may be a conventional addition method of a photographic emulsion additive. For example methanol,
It can be dissolved in ethanol, methyl cellosolve, acetone, water, a mixed solvent thereof or the like and added as a solution. In addition, solid dispersion, emulsion dispersion, ultrasonic dispersion,
You may add as a dispersion liquid created by oil protection dispersion etc.

The compound represented by the general formula (1) of the present invention may be added at any stage from the step of producing a photographic emulsion or after the production of a photographic emulsion and immediately before the coating step.
The preferred addition time in the present invention is from the end of silver halide grain formation to the end of the coating solution adjusting step.

The addition amount of the compound represented by the general formula (1) of the present invention to the silver halide photographic emulsion is preferably 1 × 10 ^{−6 to} 0.1 mol, and more preferably 1 mol per mol of silver halide. It is 5 × 10 ^{−6 to} 0.01 mol.

In the silver halide photographic light-sensitive material of the present invention, dyes having absorption in various wavelength regions can be used for the purpose of preventing irradiation and halation. For this purpose, any of the known compounds can be used. In particular, as dyes having absorption in the visible region,
JP-A-3-251840, A described on page 308
The dyes of I-1 to 11 and the dyes described in JP-A-6-3770 are preferably used. Examples of the infrared-absorbing dye include general formulas (I) described in the lower left column of page 2 of JP-A-1-280750. The compounds represented by (II) and (III) have preferable spectral characteristics, do not affect the photographic characteristics of the silver halide photographic emulsion, and do not cause contamination due to residual color. Specific examples of preferred compounds include Exemplified Compounds (1) to (45) listed on page 3, lower left column to page 5, lower left column of the same publication.

The amount of these dyes added is 680 nm of an untreated sample of a light-sensitive material for the purpose of improving sharpness.
Is preferable to make the spectral reflection density 0.7 or more, more preferably 0.8 or more.

It is preferable to add a fluorescent whitening agent to the light-sensitive material according to the present invention because the whiteness can be improved. Examples of the compounds preferably used include the compounds represented by the general formula II described in JP-A-2-232652.

When the silver halide photographic light-sensitive material of the present invention is used as a color photographic light-sensitive material, it is combined with a yellow coupler, a magenta coupler and a cyan coupler and spectrally sensitized to a specific region of an arbitrary wavelength range. It has a layer containing an emulsion. The silver halide emulsion contains one kind or a combination of two or more kinds of sensitizing dyes.

As the spectral sensitizing dye used in the silver halide emulsion according to the present invention, any known compound can be used.
BS-1 to 8 described on page 28 of JP-A-251840 can be preferably used alone or in combination. As the green photosensitive sensitizing dye, GS-1 to GS-5 described on page 28 of the same publication are preferably used. RS-1 to 8 described on page 29 of the same publication are preferably used as red-sensitive sensitizing dyes. Further, for red, green and blue photosensitive sensitizing dyes, the supersensitizers SS-1 to SS-9 described in JP-A-4-285950, pages 8 to 9 and JP-A-5-66515.
Compounds S-1 to S-1 described on pages 15 to 17
It is preferable to use 7 in combination.

The sensitizing dye may be added at any time from the formation of silver halide grains to the end of chemical sensitization.

The sensitizing dye may be added by dissolving it in a water-miscible organic solvent such as methanol, ethanol, fluorinated alcohol, acetone or dimethylformamide or water and adding it as a solution, or as a solid dispersion. Although it may be added, it is preferably added as a solid dispersion.

The coupler used in the silver halide photographic light-sensitive material according to the present invention forms a coupling product having a spectral absorption maximum wavelength in the wavelength region longer than 340 nm through a coupling reaction with an oxidant of a color developing agent. Any compound that can be used can be used, but as a typical example, a yellow dye-forming coupler having a spectral absorption maximum wavelength in the wavelength range of 350 to 500 nm, a wavelength range of 500
Typical examples are magenta dye-forming couplers having a spectral absorption maximum wavelength in the range of -600 nm and cyan dye-forming couplers having a spectral absorption maximum wavelength in the wavelength range of 600 to 750 nm.

Cyan couplers that can be preferably used in the silver halide photographic light-sensitive material of the present invention include:
Couplers represented by general formulas (C-I) and (C-II) described in the lower left column of page 5 of JP-A-4-114154 can be exemplified. Specific compounds are described in the same specification on page 5, lower right column to page 6, lower left column, CC-1 to CC.
-9 may be mentioned.

As magenta couplers which can be preferably used in the silver halide photographic light-sensitive material according to the present invention, the general formulas (MI) and (M) described in the upper right column of page 4 of JP-A-4-114154 can be used. -II) can be mentioned. Specific compounds are listed in the lower left column of page 4 to the upper right column of page 5 in the same publication, MC-1 to MC-1.
There can be mentioned those described as MC-11. More preferred of the magenta coupler,
The general formula (M-
Among them, the couplers represented by I), of which the RM of the general formula (M-I) is a tertiary alkyl group, are particularly preferable because of their excellent light resistance. MC-8 to MC-11 described in the upper column of page 5 of the publication are preferable because they are excellent in the reproduction of colors ranging from blue to purple and red, and are also excellent in the depiction of details.

In the silver halide photographic light-sensitive material of the present invention, known yellow couplers such as pivaloylacetanilide type yellow couplers and benzoylacetanilide type yellow couplers can be used.

Further, in the silver halide photographic light-sensitive material according to the present invention, in addition to the above-mentioned yellow coupler, JP-A No. 4-1 / 1992 is used.
No. 14,154, the general formula (Y-
The couplers represented by I) can be used. Specific compounds are described in YC in the lower left column on page 3 of the specification.
-1 to YC-9. Further, a coupler represented by the general formula [I] described in JP-A-6-67388 can also be used,
Specifically, Japanese Unexamined Patent Publication No. 4-114154, YC-8, YC-9 described in the lower left column of page 4, and No. 1 (1) to No. 13-14 of Japanese Unexamined Patent Publication No. 6-67388. Examples thereof include the compound represented by (47). Further, compounds represented by the general formula [Y-1] described in JP-A-4-81847, page 1 and JP-A-4-81847, can also be used.

When the oil-in-water type emulsion dispersion method is used to add the coupler or other organic compound used in the silver halide photographic light-sensitive material of the present invention, it is usually highly water-insoluble with a boiling point of 150 ° C. or higher. If necessary, a low boiling point and / or water-soluble organic solvent may be used in combination with the boiling point organic solvent to dissolve, and emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. As a dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser, or the like can be used. After or at the same time as the dispersion, a step of removing the low boiling organic solvent may be added. Examples of high boiling organic solvents that can be used to dissolve and disperse the coupler include dioctyl phthalate, diisodecyl phthalate, phthalates such as dibutyl phthalate, tricresyl phosphate, and phosphates such as trioctyl phthalate,
Is preferably used. The high-boiling organic solvent preferably has a dielectric constant of 3.5 to 7.0. Further, two or more kinds of high-boiling organic solvents can be used in combination. .

Further, instead of the method using a high-boiling point organic solvent or in combination with a high-boiling point organic solvent, a water-insoluble and organic-solvent-soluble polymer compound is optionally added to a low-boiling point and / or water-soluble organic solvent. It is also possible to employ a method in which the surfactant is dissolved in a hydrophilic binder such as an aqueous gelatin solution and the resulting mixture is emulsified by various dispersing means using a surfactant.
Examples of the water-insoluble and organic solvent-soluble polymer used at this time include poly (Nt-butylacrylamide).

Preferred compounds as the surfactant used for dispersing the photographic additives and adjusting the surface tension during coating are a hydrophobic group having 8 to 30 carbon atoms and a sulfonic acid group or a salt thereof in one molecule. The thing contained is mentioned. Specifically, A-1 to A described in JP-A No. 64-26854.
-11. Also, a surfactant in which a fluorine atom is substituted for an alkyl group is preferably used. These dispersions are usually added to a coating solution containing a silver halide emulsion, but it is preferable that the time from dispersion to addition to the coating solution and the time from addition to the coating solution and coating are short and 10 hours each. It is preferably within 3 hours, more preferably within 3 hours and within 20 minutes.

It is preferable to use an anti-fading agent in combination with each of the above couplers in order to prevent fading of the formed dye image due to light, heat, humidity and the like. Particularly preferred compounds include phenyl ether compounds represented by the general formulas I and II described in JP-A-2-66541, page 3, and phenolic compounds represented by the general formula IIIB described in JP-A-3-174150. An amine compound represented by the general formula A described in JP-A-64-90445, JP-A-62-1
The metal complexes represented by the general formulas XII, XIII, XIV and XV described in Japanese Patent No. 182741 are particularly preferable for magenta dyes. Further, compounds represented by the general formula I 'described in JP-A-1-19649 and compounds represented by the general formula II described in JP-A-5-11417 are particularly preferable for yellow and cyan dyes.

For the purpose of shifting the absorption wavelength of the coloring dye, the compound (d-11) described in JP-A-4-114154, page 9, lower left column, the compound (A'-, described in the same publication, page 10, lower left column). Compounds such as 1) can be used. In addition, a fluorescent dye-releasing compound described in U.S. Pat. No. 4,774,187 can also be used.

In the silver halide light-sensitive material of the present invention, a compound which reacts with an oxidized product of a developing agent is added to the layer between the light-sensitive layers to prevent color turbidity, or added to the silver halide emulsion layer. It is preferable to improve fog and the like. The compound for this purpose is preferably a hydroquinone derivative, more preferably a dialkylhydroquinone such as 2,5-di-t-octylhydroquinone. Particularly preferable compounds are the compounds represented by the general formula II described in JP-A-4-133056, and examples thereof include compounds II-1 to II-14 described on pages 13 to 14 and compound 1 described on page 17. .

It is preferable to add an ultraviolet absorber to the light-sensitive material of the present invention to prevent static fog and improve the light resistance of the dye image. Benzotriazoles are mentioned as preferable ultraviolet absorbers, and particularly preferable compounds are those represented by the general formula described in JP-A-1-250944.
Compounds represented by formula III-3, compounds represented by formula III described in JP-A-64-66646, JP-A-63-
UV-1L to UV-27L described in Japanese Patent No. 187240,
Examples thereof include compounds represented by the general formula described in JP-A-4-1633 and compounds represented by general formulas (I) and (II) described in JP-A-5-165144.

The silver halide photographic light-sensitive material of the present invention comprises
It is advantageous to use gelatin as the binder, but if necessary, other gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, proteins other than gelatin, sugar derivatives, cellulose derivatives, homopolymers or copolymers. A hydrophilic colloid such as a synthetic hydrophilic polymer substance can also be used.

As the hardener for these binders, it is preferable to use a vinyl sulfone type hardener or a chlorotriazine type hardener alone or in combination. JP-A-61-24
It is preferable to use the compounds described in JP-A Nos. 9054 and 61-245153. Further, it is preferable to add a preservative and an antifungal agent as described in JP-A-3-157646 to the colloid layer in order to prevent the growth of mold and bacteria which adversely affect photographic performance and image storability. It is preferable to add a slipping agent or matting agent described in JP-A-6-118543 or JP-A-2-73250 to the protective layer in order to improve the physical properties of the surface of the photosensitive material or the processed sample.

Any material may be used as the support for the silver halide photographic light-sensitive material of the present invention. Paper coated with polyethylene or polyethylene terephthalate, paper support made of natural pulp or synthetic pulp, A vinyl chloride sheet, polypropylene which may contain a white pigment, polyethylene terephthalate support, cellulose triacetate, baryta paper, etc. can be used. Of these, a support having a waterproof resin coating layer on both sides of the base paper is preferable. As the water resistant resin, polyethylene, polyethylene terephthalate or a copolymer thereof is preferable.

As the white pigment used for the support, inorganic and / or organic white pigments can be used, and preferably inorganic white pigments are used. For example, alkaline earth metal sulfates such as barium sulfate, alkaline earth metal carbonates such as calcium carbonate, finely divided silicic acid, silicas such as synthetic silicates, calcium silicate, alumina, alumina hydrate, oxidation Examples include titanium, zinc oxide, talc and clay. The white pigment is preferably barium sulfate or titanium oxide.

The amount of the white pigment contained in the water resistant resin layer on the surface of the support is 13% by weight in order to improve the sharpness.
The above is preferred, and more preferably 15% by weight.

The dispersity of the white pigment in the water resistant resin layer of the paper support according to the present invention can be measured by the method described in JP-A-2-28640. When measured by this method, the degree of dispersion of the white pigment is preferably 0.20 or less, more preferably 0.15 or less, as the coefficient of variation described in the above publication.

It is more preferable that the value of the center surface average roughness (SRa) of the support is 0.15 μm or less, and further 0.12 μm or less because the effect of good gloss can be obtained. In addition, trace amounts of ultramarine, oil-soluble dyes, etc. to adjust the spectral reflection density balance of the white background after treatment in the white pigment-containing water-resistant resin of the reflective support or in the applied hydrophilic colloid layer to improve whiteness It is preferable to add a bluing agent or a reddish agent.

In the silver halide photographic light-sensitive material of the present invention, the support surface is subjected to corona discharge, ultraviolet irradiation, flame treatment, etc., if necessary, and then directly or undercoat layer (adhesiveness of the support surface, charging It may be applied via one or more undercoat layers for improving anti-preventive property, dimensional stability, abrasion resistance, hardness, antihalation property, frictional property and / or other property). .

When coating a photographic light-sensitive material using a silver halide emulsion, a thickener may be used in order to improve coatability. Extrusion coating and curtain coating, in which two or more layers can be applied simultaneously, are particularly useful as a coating method.

To form a photographic image using the silver halide photographic light-sensitive material of the present invention, the image recorded on the negative is optically formed on the silver halide photographic light-sensitive material to be printed. The image may be printed on the CRT (cathode ray tube) after being converted into digital information, and then the image is formed on the silver halide photographic light-sensitive material to be printed. It may be printed, or may be printed by changing the intensity of the laser light based on digital information and scanning.

The present invention is preferably applied to a light-sensitive material in which a developing agent is not incorporated in the light-sensitive material, and is particularly preferably applied to a light-sensitive material for forming an image for direct viewing. For example, color paper, color reversal paper, a photosensitive material for forming a positive image, a photosensitive material for a display, and a photosensitive material for a color proof can be used. It is particularly preferable to apply the invention to a photosensitive material having a reflective support.

As the aromatic primary amine developing agent used in the present invention, known compounds can be used. The following compounds may be mentioned as examples of these compounds.

CD-1) N, N-diethyl-p-phenylenediamine CD-2) 2-amino-5-diethylaminotoluene CD-3) 2-amino-5- (N-ethyl-N-laurylamino) toluene CD-4) 4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline CD-5) 2-methyl-4- (N-ethyl-N- (β
-Hydroxyethyl) amino) aniline CD-6) 4-Amino-3-methyl-N-ethyl-N
-(Β- (Methanesulfonamido) ethyl) -aniline CD-7) N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide CD-8) N, N-dimethyl-p-phenylenediamine CD-9) 4-amino-3-methyl-N-ethyl-N
-Methoxyethylaniline CD-10) 4-amino-3-methyl-N-ethyl-N
-(Β-ethoxyethyl) aniline CD-11) 4-amino-3-methyl-N-ethyl-N
-(Γ-Hydroxypropyl) aniline In the present invention, the above color developer can be used in any pH range, but from the viewpoint of rapid processing, the pH is 9.5 to 13.0.
And more preferably pH 9.8-1.
It is used in the range of 2.0.

The processing temperature for color development according to the present invention is 35.
The temperature is preferably from 70 ° C to 70 ° C. The higher the temperature, the shorter the processing time is possible, which is preferable. However, from the viewpoint of the stability of the processing solution, the higher the temperature, the more preferable.

The color development time is conventionally about 3 minutes and 30 seconds, but in the present invention, it is preferably within 40 seconds, more preferably within 25 seconds.

To the color developing solution, known developing solution component compounds can be added in addition to the color developing agent. Usually, alkaline agents having a pH buffering action, chloride ions, development inhibitors such as benzotriazoles, preservatives,
A chelating agent or the like is used.

The silver halide photographic light-sensitive material of the present invention is subjected to bleaching treatment and fixing treatment after color development. The bleaching process may be performed simultaneously with the fixing process. After the fixing process,
Usually, a water washing process is performed. Further, as an alternative to the water washing treatment, a stabilization treatment may be performed. The developing apparatus used for the development processing of the silver halide photographic light-sensitive material of the present invention may be a roller transport type in which the light-sensitive material is conveyed across rollers arranged in a processing tank.
The endless belt method may be used in which the photosensitive material is fixed and conveyed on a belt, but the processing tank is formed in a slit shape and the processing solution is supplied to the processing tank and the processing solution is conveyed. A spray method for atomizing, a web method by contact with a carrier impregnated with a treatment liquid, a method with a viscous treatment liquid, and the like can also be used. When processing a large amount, it is usually a running process using an automatic developing machine, but at this time, the smaller the replenishing amount of the replenisher is, the more preferable, and the most preferable processing form from the environmental suitability is,
The replenishment method is to add the treatment agent in the form of tablets, and the method described in Kokai Giho 94-16935 is most preferable.

[0114]

EXAMPLES The present invention will be described below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 A paper support was prepared by laminating high density polyethylene on both sides of a paper pulp having a basis weight of 180 g / m ² . However, on the side to be coated with the emulsion layer, a molten polyethylene containing surface-treated anatase-type titanium oxide dispersed at a content of 15% by weight was laminated to produce a reflective support. After subjecting this reflective support to a corona discharge treatment, a gelatin undercoat layer was provided, and each layer having the following constitution was further applied to prepare a silver halide photographic material. The coating liquid was prepared as follows.

23.4 g of a yellow coupler (Y-1),
Dye image stabilizer (ST-1) 3.34 g, (ST-
2) 3.34 g, (ST-5) 3.34 g, stain inhibitor (HQ-1) 0.34 g, image stabilizer A 5.0 g,
60 ml of ethyl acetate was added to and dissolved in 3.33 g of the high boiling organic solvent (DBP) and 1.67 g of the high boiling organic solvent (DNP), and this solution was added with 7 m of 20% surfactant (SU-1).
A yellow coupler dispersion was prepared by emulsifying and dispersing in 220 ml of 10% gelatin aqueous solution containing 1 by using an ultrasonic homogenizer. This dispersion was mixed with a blue-sensitive silver halide emulsion prepared under the following conditions to prepare a first layer coating solution.

This dispersion was mixed with a silver halide emulsion (Em-B101) (containing 8.50 g of silver) prepared under the following conditions to prepare a coating solution for the first layer. The second layer coating liquid was also prepared in the same manner as the first layer coating liquid. Further, (H-1) was added to the second layer as a hardener. Surfactants (SU-2) and (SU-3) were added as coating aids to adjust the surface tension.

Sample 101 was prepared as described above.
The layer structure is shown in Table 1 below.

[0119]

[Table 1]

[0120]

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SU-1: sodium tri-i-propylnaphthalene sulfonate SU-2: di (2-ethylhexyl) sulfosuccinate sodium salt SU-3: di (2,3,3,4) sulfosuccinate , 4,
5,5, -Octafluoropentyl) sodium salt H-1: tetrakis (vinylsulfonylmethyl) methane HQ-1: 2,5-di-t-octylhydroquinone DBP: dibutylphthalate DNP: dinonylphthalate Image stabilizer A: Pt-octylphenol << Preparation of high silver chloride monodisperse emulsion (EMP-1) >> In a liter of a 2% gelatin aqueous solution kept at 40 ° C, the following (A
Solution) and (solution B) were added simultaneously over 30 minutes while controlling pAg = 7.3 and pH = 3.0, and the following (solution C) and (solution D) were further added at pAg = 8.0, pH = 5.5 and added simultaneously over 180 minutes. At this time, pAg was controlled by the method described in JP-A-59-45437.
H was controlled using sulfuric acid or an aqueous solution of sodium hydroxide.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added to 200 ml (Solution B) Silver nitrate 10 g Water was added to 200 ml (Solution C) Sodium chloride 102.7 g K ₂ IrCl ₆ 4 × 10 ^-8 mol K ₄ Fe (CN) ₆ 2 × 10 ^-5 mol Potassium bromide 1.0 g Water was added to 600 ml (D solution) Silver nitrate 300 g Water was added to 600 ml After addition was completed, Kao Atlas Demol N 5 was added. % Aqueous solution and magnesium sulfate 20% aqueous solution for desalting, and then mixed with gelatin aqueous solution to obtain an average particle size of 0.71μ.
m, coefficient of variation of particle size distribution 0.07, silver chloride content 99.
A 5 mol% monodispersed cubic emulsion EMP-1 was obtained.

<< Preparation of Silver Chlorobromide Monodisperse Emulsion (EMP-2) >> In the preparation of the high silver chloride monodisperse emulsion (EMP-1), (C solution) and (D solution) were replaced with the following (C2 solution). And (D
The average particle size is 0.71 μm,
Coefficient of variation of particle size distribution 0.07, content of silver chloride 90 mol%
To obtain a monodispersed cubic emulsion EMP-2.

(Solution C2) Sodium chloride 92.9 g K ₂ IrCl ₆ 4 × 10 ⁻⁸ mol / mol Ag K ₄ Fe (CN) ₆ 2 × 10 ₋₅ mol / mol Ag potassium bromide 21.0 g Water was added. 600 ml (D2 solution) Silver nitrate 300 g Water was added to 600 ml << Preparation of silver chlorobromide monodisperse emulsion (EMP-3) >> In preparation of high silver chloride monodisperse emulsion (EMP-1), (C liquid) and ( Monodisperse cube having average particle size of 0.71 μm, variation coefficient of particle size distribution of 0.07, and silver chloride content of 80 mol% in the same manner except that (D solution) is changed to (C3 solution) and (D3 solution) below. Emulsion EMP-3 was obtained.

(Solution C3) Sodium chloride 82.6 g K ₂ IrCl ₆ 4 × 10 ₋₈ mol / mol Ag K ₄ Fe (CN) ₆ 2 × 10 ⁻⁵ mol / mol Ag potassium bromide 42.0 g Water was added. 600 ml (D3 solution) Silver nitrate 300 g Water was added to 600 ml << Preparation of blue-sensitive silver halide emulsion >> EMP-1 and 2 above
In contrast, the following compounds were optimally chemically sensitized at 60 ° C. to obtain blue-sensitive silver halide emulsions (Em-B101) to
(Em-B102) was obtained. Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer STAB-4 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-2 1 * 10 < ^-4 > mol / mol AgX STAB-4: 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene The sensitizing dyes BS-1 and BS-2 are Japanese Patent Applications. Flat 5-98
The sensitizing dye obtained by the method described on page 87 of the No. 094 specification was added by an addition liquid in the form of solid fine particles.

<< Preparation of Green-Sensitive Silver Halide Emulsion >> Above E
MP-1 was optimally chemically sensitized at 55 ° C. using the following compound to obtain a green-sensitive silver halide emulsion (Em-G10
1) was obtained.

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer STAB-4 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX Here, the sensitizing dye GS-1 was added by an additive solution in which the sensitizing dye obtained by the method described on page 87 of Japanese Patent Application No. 5-98094 is present as solid fine particles.

<< Preparation of Red-Sensitive Silver Halide Emulsion >> Above E
The following compounds were optimally chemically sensitized to MP-1 to MP-3 at 60 ° C. to obtain a red-sensitive silver halide emulsion (Em-R
101) to (Em-R103) were obtained. Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-4 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-2 1 × 10 ⁻⁴ mol / mol AgX Further, SS-1 was added to the red photosensitive emulsion in an amount of 2.0 × 10 ⁻³ mol per mol of silver halide.

Here, the sensitizing dyes RS-1 and RS-2 were added by an additive solution in which the sensitizing dye obtained by the method described on page 87 of Japanese Patent Application No. 5-98094 is present as solid fine particles. .

<< Preparation of Infrared-Sensitive Silver Halide Emulsion >> The above compound EMP-1 was optimally chemically sensitized at 60 ° C. to obtain a red-sensitive silver halide emulsion (Em-IR).
101).

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-4 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye IRS-1 2 × 10 ⁻⁴ mol / mol AgX Here, the sensitizing dye IRS-1 was added by an addition liquid in which the sensitizing dye obtained by the method described on page 87 of Japanese Patent Application No. 5-98094 is present as solid fine particles.

[0132]

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[0133]

[Chemical 12]

In the preparation of Sample 101, the silver halide emulsion (Em-B101) was changed as shown in Table 2 below, and Table 2
Samples 102 to 120 were prepared in the same manner except that the compound shown in 1 was dissolved in ethanol and added. Samples 101 to 1
20 was kept in an atmosphere of 25 ° C.-30% RH and 25 ° C.-80% RH, and light wedge exposure was performed by an ordinary method at an exposure time of 0.5 seconds, and then development processing was performed in the following development processing step.

Treatment Step Treatment Temperature Time Replenishment Amount Color development 38.0 ± 0.3 ° C. 45 seconds 80 cc Bleach-fix 35.0 ± 0.5 ° C. 45 seconds 120 cc Stabilization 30-34 ° C. 60 seconds 150 cc Dry 60- 80 ° C., 30 seconds The composition of the development processing solution is shown below.

Color developer tank solution and replenisher tank solution replenisher pure water 800 ml 800 ml triethylenediamine 2 g 3 g diethylene glycol 10 g 10 g potassium bromide 0.01 g-potassium chloride 3.5 g-potassium sulfite 0.25 g 0.5 g N-ethyl -N- (β methanesulfonamidoethyl) -3-methyl-4-aminoaminoline sulfate 6.0 g 10.0 g N, N-diethylhydroxylamine 6.8 g 6.0 g triethanolamine 10.0 g 10.0 g diethylenetriamine Sodium pentaacetate 2.0g 2.0g Fluorescent brightener (4,4'-diaminostilbenedisulphonic acid derivative) 2.0g 2.5g Potassium carbonate 30g 30g Add water to make the total volume 1 liter. pH = 10.10, replenisher pH = 10.60.

Bleach-fixing solution Tank solution and replenishing solution Diethylenetriamine pentaacetate ammonium ferric dihydrate 65 g Diethylenetriamine pentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml 2-Amino-5-mercapto-1,3,4-thiadiazole 2 0.0 g Ammonium sulfite (40% aqueous solution) 27.5 ml Water is added to bring the total volume to 1 liter, and the pH is adjusted to 5.0 with potassium carbonate or glacial acetic acid.

Stabilizing liquid tank liquid and replenishing liquid o-phenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g Diethylene glycol 1.0 g Optical brightener (Tinopearl SFP) 2.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.8 g Bismuth chloride (45% aqueous solution) 0.65 g Magnesium sulfate heptahydrate 0.2 g PVP 1 0.0 g Ammonia water (25% ammonium hydroxide aqueous solution) 2.5 g Nitrilotriacetic acid trisodium salt 1.5 g Water is added to bring the total volume to 1 liter, and the pH is adjusted to 7.5 with sulfuric acid or ammonia water.

The blue density of the obtained sample was measured using a PDA-65 densitometer (manufactured by Konica Corporation). Sensitivity is defined based on the reciprocal of the exposure dose giving a density of 0.75,
Regarding the sensitivity of 30 ° C. and 30% RH, sample 101 is used in the case of a sample using a blue-sensitive silver halide emulsion, sample 109 is used in the case of a sample using a green-sensitive silver halide emulsion, and red-sensitive silver halide emulsion is used. 1) in the case of a sample using infrared sensitive silver halide emulsion and 1 in the case of sample using an infrared-sensitive silver halide emulsion.
It was expressed as a relative value as 00. Also, 25 ° C, 80% RH
Regarding the sensitivity of (1), the sensitivity of the same sample at 25 ° C. and 30% RH was set as 100 and expressed as a relative value. Table 2 shows the results.

[0140]

[Table 2]

As is clear from Table 2, the samples using the silver halide emulsion having the maximum spectral sensitivity at 400 to 650 nm without using the compound of the present invention show a large decrease in sensitivity when exposed to high humidity. It can be seen that the sample using the compound of the present invention has a maximum spectral sensitivity in the range of 400 to 650 nm, high sensitivity, and improved sensitivity reduction when exposed under high humidity.

Example 2 A paper support was prepared by laminating high-density polyethylene on both sides of a paper pulp having a basis weight of 180 g / m ² . However, on the side to be coated with the emulsion layer, a molten polyethylene containing surface-treated anatase-type titanium oxide dispersed at a content of 15% by weight was laminated to produce a reflective support. After subjecting this reflective support to a corona discharge treatment, a gelatin undercoat layer was provided, and each layer having the following constitution was further applied to prepare a silver halide photographic material. The coating solutions were prepared as shown in Tables 3 and 4 below.

Further, as a hardener (H-1), (H-2)
Was added. Surfactants (SU-
2) and (SU-3) were added to adjust the surface tension. Further, F-1 was added to each layer so that the total amount became 0.04 g / m ² .

[0144]

[Table 3]

[0145]

[Table 4]

PVP: Polyvinylpyrrolidone DOP: Dioctyl phthalate DIDP: Di-i-decyl phthalate H-2: 2,4-dichloro-6-hydroxy-s-triazine sodium HQ-2: 2,5-di-sec- Dodecylhydroquinone HQ-3: 2,5-di-sec-tetradecylhydroquinone HQ-4: 2-sec-dodecyl-5-sec-tetradecylhydroquinone HQ-5: 2,5-di (1,1-dimethyl-) 4-hexyloxycarbonyl) butyl hydroquinone

[0147]

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[0148]

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[0149]

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[0150]

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[0151]

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<< Preparation of blue-sensitive silver halide emulsion >> 40 ° C.
In 1 liter of a 2% gelatin aqueous solution kept at
Solution) and (solution B) were added simultaneously over 30 minutes while controlling pAg = 7.3 and pH = 3.0, and the following (solution C) and (solution D) were further added at pAg = 8.0, pH = 5.5 and added simultaneously over 180 minutes. At this time, pAg was controlled by the method described in JP-A-59-45437.
H was controlled using sulfuric acid or an aqueous solution of sodium hydroxide.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added to 200 ml (Solution B) Silver nitrate 10 g Water was added to 200 ml (Solution C) Sodium chloride 102.7 g K ₂ IrCl ₆ 4 × 10 ^-8 mol / mol Ag K ₄ Fe (CN) ₆ 2 × 10 ^-5 mol / mol Ag potassium bromide 1.0 g Water added 600 ml (solution D) Silver nitrate 300 g Water added 600 ml After addition, Kao Atlas Desalination was performed using a 5% aqueous solution of DEMOL N and a 20% aqueous solution of magnesium sulfate, and then mixed with a gelatin aqueous solution to obtain an average particle size of 0.71μ.
m, coefficient of variation of particle size distribution 0.07, silver chloride content 99.
A 5 mol% monodispersed cubic emulsion EMP-1 was obtained. Next, the addition times of (Solution A) and (Solution B) and (Solution C) and (D
The average particle size is 0.64 μm and the variation coefficient of the particle size distribution is 0.0, as in EMP-1 except that the addition time of the solution is changed.
7. Monodisperse cubic emulsion E having a silver chloride content of 99.5 mol%
MP-1B was obtained.

The EMP-1 was optimally chemically sensitized at 60 ° C. using the following compounds. Also EMP-1B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-1 and EMP-1B were mixed at a silver ratio of 1: 1 to obtain a blue-sensitive silver halide emulsion (Em-B).

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stable Agent STAB-3 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-2 1 × 10 ⁻⁴ mol / mol AgX << green sensitive silver halide emulsion Preparation >> (Solution A) and (Solution B)
The average particle diameter was 0.40 μm in the same manner as in EMP-1 except that the addition time of (C) and (C solution) and (D solution) were changed.
m, a coefficient of variation 0.08, and a monodispersed cubic emulsion EMP-2 having a silver chloride content of 99.5%. Next, average particle size 0.5
A monodisperse cubic emulsion EMP-2B having a thickness of 0 μm, a coefficient of variation of 0.08 and a silver chloride content of 99.5% was obtained.

The above EMP-2 was optimally chemically sensitized at 55 ° C. using the following compounds. Also EMP-2B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-2 and EMP-2B were mixed at a silver amount of 1: 1 to obtain a green-sensitive silver halide emulsion (Em-G).

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stable Agent STAB-3 3 × 10 ^-4 mol / mol AgX sensitizing dye GS-1 4 × 10 ^-4 mol / mol AgX << Preparation of red-sensitive silver halide emulsion >> (Solution A) and (Solution B)
The average particle diameter was 0.40 μm in the same manner as in EMP-1 except that the addition time of (C) and (C solution) and (D solution) were changed.
m, a coefficient of variation 0.08 and a monodisperse cubic emulsion EMP-3 having a silver chloride content of 99.5%. The average particle size is 0.38
A monodisperse cubic emulsion EMP-3B having a particle size of 0.08, a coefficient of variation of 0.08 and a silver chloride content of 99.5% was obtained.

The EMP-3 was optimally chemically sensitized at 60 ° C. using the following compounds. Also EMP-3B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-3 and EMP-3B were mixed in a silver amount of 1: 1 to obtain a red-sensitive silver halide emulsion (Em-R).

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stable Agent STAB-3 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-2 1 × 10 ⁻⁴ mol / mol AgX STAB-1: 1- ( 3-acetamidophenyl) -5-mercaptotetrazole STAB-2: 1-phenyl-5-mercaptotetrazole STAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole Also, for red-sensitive emulsions, SS -1 was added in an amount of 2.0 × 10 ^-3 mol per mol of silver halide.

In the preparation of these emulsions, the sensitizing dye was added in the same manner as in Example 1 with the addition liquid in which the sensitizing dye was present as solid fine particles.

In this way, the sample 201 was prepared.

Samples 202 to 209 were prepared in the same manner as in Sample 201, except that the compounds shown in Table 5 were added.

[0163]

[Table 5]

Samples 201 to 209 were exposed and developed in the same manner as in Example 1, and the obtained sample was measured for blue, green and red densities using a PDA-65 densitometer (manufactured by Konica Corporation). It evaluated similarly to 1. Table 6 shows the results.

[0165]

[Table 6]

As is clear from Table 6, the sample to which the compound of the present invention is added shows the same improvement effect even in the multi-layer structure.

Example 3 Samples 201, 204, 206 and 20 prepared in Example 2
8 is an automatic processor (Konica Corporation NPS-868J;
Exposure and development were carried out through Konica Color LV-400 which had been developed using ECOJET-P as a processing chemical. This automatic processor has been modified to measure the temperature and humidity in the exposed area. This automatic processor was installed in a room where the temperature and humidity could be set to a constant value, and the temperature of the room was kept constant, the humidity was varied, and printing was performed from a negative film of the same scene. When the print developed during this period was viewed, in Sample 201, a shift was seen in the cyan color direction when the humidity of the exposed portion increased. Sample 20 of the present invention
Nos. 4, 206, and 208 showed no change in print color regardless of the humidity of the exposed portion, and it was found that a stable print finish was obtained.

[0168]

According to the present invention, it is possible to provide a silver halide photographic light-sensitive material which is highly sensitive, has a small performance fluctuation due to a change in humidity during exposure, and can provide a stable finish.

Claims (12)

[Claims] 1. A silver halide photographic light-sensitive material comprising a mercaptoazole compound capable of having a betaine structure in the molecule. 2. A silver halide photographic light-sensitive material containing a compound represented by the following general formula (1). Embedded image [In the formula, M ₁ represents a hydrogen atom, a metal atom, or a quaternary ammonium group. Q ₁ represents a group of non-metal atoms necessary for bonding to a carbon atom and a nitrogen atom to form a monocyclic ring or a condensed heterocycle with them. L represents a divalent group, and n represents an integer of 0 to 2. R ₁ and R ₂ represent an alkyl group,
R ₁ and R ₂ may be the same or different and may be bonded to each other to form a ring. R ₃ represents a hydrogen atom, an alkyl group, or an aryl group. ] 3. A silver halide photographic light-sensitive material containing a compound represented by the following general formula (2) or general formula (3). Embedded image [In the formula, M ₂ represents a hydrogen atom, a metal atom, or a quaternary ammonium group. Q ₂ represents a group of non-metal atoms necessary for bonding to a carbon atom and a nitrogen atom to form a monocyclic ring or a condensed heterocycle with them. R ₄ and R ₅ represent an alkyl group, R ₄ and R ₅ may be the same or different, and may combine with each other to form a ring. R ₆ represents a hydrogen atom, an alkyl group, or an aryl group. ] 4. A support comprising on its support at least one silver halide emulsion layer containing yellow coupler (referred to as YL), a silver halide emulsion layer containing magenta coupler (referred to as ML) and a cyan coupler. YL, M with silver halide emulsion layer (CL)
A multilayer color light-sensitive material in which L and CL each have a different spectral sensitization, and a layer containing a mercaptoazole compound capable of having a betaine structure in the molecule. 5. A support comprising a silver halide emulsion layer (referred to as YL) each containing at least one yellow coupler, a silver halide emulsion layer containing magenta coupler (referred to as ML) and a cyan coupler. YL, M with silver halide emulsion layer (CL)
A multilayer color light-sensitive material in which L and CL each have a different spectral sensitization, and a layer containing a compound represented by the above formula (1). 6. A support comprising a silver halide emulsion layer (referred to as YL) each containing at least one layer of a yellow coupler, a silver halide emulsion layer containing a magenta coupler (referred to as ML) and a cyan coupler. YL, M with silver halide emulsion layer (CL)
A multilayer color light-sensitive material in which L and CL each have a different spectral sensitization, and a layer containing a compound represented by the general formula (2) or (3). 7. A silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer on a support, wherein at least one of the silver halide emulsion layers has a silver chloride content of 90 mol% or more. The silver halide photographic light-sensitive material according to claim 1, which contains silver halide grains. 8. The silver halide photographic light-sensitive material according to claim 1, wherein at least one of the silver halide emulsion layers contains silver halide grains having a silver chloride content of 95 mol% or more. 9. A silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer on a support, wherein at least one of the silver halide emulsion layers has a silver chloride content of 90 mol% or more. 3. The silver halide photographic light-sensitive material according to claim 2, which contains silver halide grains. 10. The silver halide photographic light-sensitive material according to claim 2, wherein at least one of the silver halide emulsion layers contains silver halide grains having a silver chloride content of 95 mol% or more. 11. A silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer on a support, wherein at least one silver halide emulsion layer has a silver chloride content of 90 mol% or more. The silver halide photographic light-sensitive material according to claim 3, which contains silver halide grains. 12. The silver halide photographic light-sensitive material according to claim 3, wherein at least one of the silver halide emulsion layers contains silver halide grains having a silver chloride content of 95 mol% or more.