JPH09114033A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a sensitive material having high sensitivity and less liable to a change in the sensitivity due to a humidity change in the exposure by incorporating specified compds. into a silver halide emulsion layer. SOLUTION: This sensitive material contains a compd. represented by formula I and a compd. represented by formula II in one of the silver halide emulsion layers. In the formula I, each of R1 -R5 is H, alkyl, -X-R6 or -X-R9 , X is -C(R7 )(R8 )-, -O- or -S-, at least one of R1 -R5 is -X-R9 , R6 is alkyl or aryl, each of R7 and R8 is H or alkyl and R9 is aryl. In the formula II, each of R21 and R22 is -OR25 or -N(R26 )R27 , R25 is H, alkyl, aryl or a heterocyclic group, each of R23 , R24 , R26 and R27 is H, alkyl, aryl, a heterocyclic group, sulfonyl, carbamoyl or a group accelerating adsorption on silver halide.

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 having a high sensitivity, a small sensitivity fluctuation due to a humidity change at the time of exposure, and a small sensitivity fluctuation even when the light-sensitive material is stored for a long period of time. .

[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, the fluctuation of the humidity at the time of exposure is one of the serious problems. It was also found that this problem is remarkable especially when a blue sensitized emulsion is used.

Japanese Patent Publication Nos. 55-12581 and 62-20
1440, JP-A-62-260241, JP-A-1-
Nos. 291250 and 4-253053 disclose a technique for improving latent image stability by incorporating a specific thiazolium compound. These techniques describe the stability of the resulting latent image for a relatively long time, and nothing 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. Also, JP-A-7-72598
Japanese Patent Laid-Open No. 7-72599 describes a technique for improving the aging property of photographic properties after exposure by incorporating a bisphenol compound in the emulsion layer, but it improves sensitivity fluctuation due to humidity change during exposure. No technology is mentioned. JP-A-7-20608 describes a technique for improving the storage stability by incorporating a bisphenol compound in a layer containing colloidal silver. However, regarding the technique for improving sensitivity fluctuation due to humidity change during exposure, Not listed at all.

[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 and has small sensitivity fluctuation due to humidity change during exposure.

[0009]

The above objects of the present invention have been attained by the following constitutions.

(1). In a silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer on a support, a compound represented by the following general formula (I) in at least one of the silver halide emulsion layers, and A silver halide photographic light-sensitive material containing a compound represented by the general formula (II).

[0011]

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[Wherein R ₁ , R ₂ , R ₃ , R ₄ and R
₅ are each a hydrogen atom, an alkyl group, a -X-R ₆ or -X-R _9, which may be identical or different, or may be bonded to each other to form a ring. Where X is -C
_{(R 7) (R 8)} -, - represents a O- or -S-. Provided that at least one of R ₁ , R ₂ , R ₃ , R ₄ and R ₅
One represents -X-R _9. R ₆ represents an alkyl group or an aryl group, R ₇ and R ₈ each represent a hydrogen atom or an alkyl group, R ₉ represents an aryl group, and when there are a plurality of groups, they may be the same or different, or They may combine with each other to form a ring. ]

[0013]

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[In the formula, R ₂₁ and R ₂₂ may be the same or different and each is —OR ₂₅ or —N (R ₂₆ ) R ₂₇
R ₂₅ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ₂₃ , R ₂₄ , R ₂₆ and R
_{27, which} may be the same or different, each represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a sulfonyl group, a carbonyl group, a carbamoyl group or a silver halide adsorption promoting group. Provided that at least one of R ₂₃ , R ₂₄ , R ₂₅ , R _26, and R ₂₇ is a group promoting adsorption to silver halide, or a group substituted with a group promoting adsorption to silver halide. is there. (2). The silver halide photographic light-sensitive material according to (1), which contains a compound represented by the following general formula (III).

[0015]

[Chemical 6]

[Wherein R ₃₁ represents a hydrogen atom, an alkyl group,
It represents an alkenyl group, an aralkyl group, an aryl group, an alkoxyl group, a carbonyl group or a heterocyclic group. R ₃₂ and R ₃₃ each represent a hydrogen atom, a halogen atom, an alkyl, an aryl, a heterocyclic group, a cyano group, an alkylthio group, an arylthio group, an alkylsulfooxide group, an alkylsulfonyl group or an alkylsulfinyl group. Further, R ₃₂ and R ₃₃ may combine with each other to form a benzene ring which may have a substituent. ] (3). A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support,
The silver halide photographic light-sensitive material according to (1) or (2), wherein at least one of the silver halide emulsion layers contains silver halide grains having a silver chloride content of 90 mol% or more.

(4). In a silver halide photographic light-sensitive material having at least one light-sensitive 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 95 mol% or more. The silver halide photographic light-sensitive material as described in (1) or (2), which further comprises:

(5). A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support and a non-light-sensitive layer containing colloidal silver, wherein the non-light-sensitive layer containing the colloidal silver has the above-mentioned general formula. A non-photosensitive layer containing the compound represented by the formula (I) and at least one layer adjacent to the non-photosensitive layer containing the colloidal silver, the compound represented by the general formula (II) being contained. A silver halide photographic light-sensitive material.

Hereinafter, the present invention will be described in detail.

The compound represented by formula (I) of the present invention will be described.

In the above general formula (I), R ₁ , R ₂ , R
Examples of the alkyl group represented by ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ include a methyl group, an ethyl group, a propyl group, i
-Propyl group, butyl group, t-butyl group, pentyl group,
Examples thereof include a cyclopentyl group, a hexyl group, a cyclohexyl group, an octyl group and a dodecyl group.

Examples of the aryl group represented by R ₆ and R ₉ include phenyl and naphthyl.

Each of the above-mentioned alkyl group and aryl group includes those further having a substituent, for example, a halogen atom (eg, chlorine atom, bromine atom, fluorine atom, etc.), an alkyl group (eg, methyl group, ethyl group, Propyl group, i
-Propyl group, butyl group, t-butyl group, pentyl group,
Cyclopentyl group, hexyl group, cyclohexyl group, octyl group, dodecyl group, etc., alkoxyl group (for example, methoxy group, ethoxy group, 1,1-dimethylethoxy group,
Hexyloxy group, dodecyloxy group etc.), aryloxy group (eg phenoxy group, naphthyloxy group etc.),
Aryl group (eg phenyl group, naphthyl group etc.), alkoxycarbonyl group (eg methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, 2-ethylhexylcarbonyl group etc.), aryloxycarbonyl group (eg phenoxycarbonyl group, naphthyloxycarbonyl group) Group, etc.), heterocyclic group (for example, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, morpholyl group,
Piperidyl group, piperazyl group, selenazolyl group, sulforanyl group, piperidinyl group, tetrazolyl group, thiazolyl group, oxazolyl group, imidazolyl group, thienyl group,
Pyrrolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, pyrimidyl group, pyrazolyl group, furyl group, etc.),
Amino group (eg, amino group, N, N-dimethylamino group, anilino group, etc.), hydroxyl group, cyano group, sulfo group, carboxyl group, sulfonamide group (eg, methylsulfonylamino group, ethylsulfonylamino group, butylsulfonylamino group) Group, octylsulfonylamino group, phenylsulfonylamino group, etc.) and the like.

The compound represented by formula (II) of the present invention will be described.

In the general formula (II), R ₂₃ , R ₂₄ ,
Examples of the alkyl group represented by R ₂₅ , R ₂₆ and R ₂₇ include
For example, methyl group, ethyl group, propyl group, i-propyl group, butyl group, t-butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, octyl group,
Dodecyl group and the like can be mentioned.

Examples of the aryl group represented by R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ and R ₂₇ include a phenyl group and a naphthyl group.

The heterocyclic group represented by R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ and R ₂₇ is, for example, 2-pyridyl group or 3-pyridyl group.
Pyridyl group, 4-pyridyl group, morpholyl group, piperidyl group, piperazyl group, selenazolyl group, sulforanyl group, piperidinyl group, tetrazolyl group, thiazolyl group,
Examples thereof include an oxazolyl group, an imidazolyl group, a thienyl group, a pyrrolyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, a pyrimidyl group, a pyrazolyl group and a furyl group.

Examples of the sulfonyl group represented by R ₂₃ , R ₂₄ , R ₂₆ and R ₂₇ include a methylsulfonyl group, an ethylsulfonyl group and a phenylsulfonyl group.

Examples of the carbonyl group represented by R ₂₃ , R ₂₄ , R ₂₆ and R ₂₇ include a methylcarbonyl group, an ethylcarbonyl group and a phenylcarbonyl group.

Examples of the carbamoyl group represented by R ₂₃ , R ₂₄ , R ₂₆ and R ₂₇ include a carbamoyl group, a methylcarbamoyl group and a phenylcarbamoyl group.

The above-mentioned alkyl group, aryl group, heterocyclic group, sulfonyl group and carbamoyl group include those having a substituent, for example, a halogen atom (eg, chlorine atom, bromine atom, fluorine atom, etc.), Alkyl group (for example, methyl group, ethyl group, propyl group, i-propyl group, butyl group, t-butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, octyl group,
Dodecyl group, etc., alkoxyl group (eg methoxy group,
Ethoxy group, 1,1-dimethylethoxy group, hexyloxy group, dodecyloxy group etc.), aryloxy group (eg phenoxy group, naphthyloxy group etc.), aryl group (eg phenyl group, naphthyl group etc.), alkoxycarbonyl group (Eg, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, 2-ethylhexylcarbonyl group, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, naphthyloxycarbonyl group, etc.), heterocyclic group (eg, 2-pyridyl group, 3 -Pyridyl group, 4-pyridyl group, morpholyl group, piperidyl group, piperazyl group, selenazolyl group, sulforanyl group,
Piperidinyl group, tetrazolyl group, thiazolyl group, oxazolyl group, imidazolyl group, thienyl group, pyrrolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group,
Pyrimidyl group, pyrazolyl group, furyl group, etc.), amino group (eg, amino group, N, N-dimethylamino group, anilino group, etc.), hydroxyl group, cyano group, sulfo group, carboxyl group, sulfonamide group (eg, methylsulfonyl group) Amino group, ethylsulfonylamino group, butylsulfonylamino group, octylsulfonylamino group, phenylsulfonylamino group, etc.) and the like.

A group containing a thioamide moiety (for example, thiourea, thiourethane, dithiocarbamic acid ester, 4-thiazoline-group) is used as an adsorption promoting group for silver halide.
2-thione, 4-imidazoline-2-thione, 2-thiohydantoin, rhodanine, thiobarbituric acid, tetrazoline-5-thione, 1,2,4-triazoline-3
-Thione, 1,3,4-thiadiazoline-2-thione,
1,3,4-oxadiazoline-2-thione, benzimidazoline-2-thione, benzoxazoline-2-thione, groups derived from benzthiazoline-2-thione, etc.), mercapto group, and sulfide moiety Group (eg, methylthio group, ethylthio group, phenylthio group, etc.), group containing disulfide moiety (eg, methyldithio group, ethyldithio group, phenyldithio group, etc.), 5- to 6-membered nitrogen-containing heterocyclic group (eg, benzotriazole, triazole) , Tetrazole, indazole, benzimidazole, imidazole, benzothiazole, thiazole, benzoxazole, oxazole, triazine and the like) and the like.

The compound represented by formula (III) of the present invention will be described.

Examples of the alkyl group represented by R ₃₁ , R ₃₂ and R ₃₃ in the general formula (III) include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, a t-butyl group, Examples thereof include a pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, an octyl group and a dodecyl group.

Examples of the alkenyl group represented by R ₃₁ include an ethenyl group, a propenyl group and a butenyl group.

Examples of the aralkyl group represented by R ₃₁ include a benzyl group, a phenethyl group and a naphthylmethyl group.

Examples of the aryl group represented by R ₃₁ , R ₃₂ and R ₃₃ include a phenyl group and a naphthyl group.

As the alkoxyl group represented by R ₃₁ ,
For example, a methoxy group, an ethoxy group, a propoxy group and the like can be mentioned.

Examples of the carbonyl group represented by R ₃₁ include a methylcarbonyl group, an ethylcarbonyl group and a phenylcarbonyl group.

The heterocyclic group represented by R ₃₁ , R ₃₂ and R ₃₃ is, for example, 2-pyridyl group, 3-pyridyl group,
4-pyridyl group, morpholyl group, piperidyl group, piperazyl group, selenazolyl group, sulforanyl group, piperidinyl group, tetrazolyl group, thiazolyl group, oxazolyl group, imidazolyl group, thienyl group, pyrrolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, Examples thereof include pyrimidyl group, pyrazolyl group and furyl group.

The alkylthio group represented by R ₃₂ and R _33, an arylthio group, an alkyl sulfoxide group, the alkyl group moiety of the alkylsulfonyl group or an alkylsulfinyl group, synonymous with the alkyl group represented by R ₃₂ and R ₃₃ Is.

Examples of the arylthio group represented by R ₃₂ and R ₃₃ include a phenylthio group and a naphthylthio group.

Each of these above groups also includes those having a substituent, such as a halogen atom (eg, chlorine atom, bromine atom, fluorine atom, etc.), an alkyl group (eg, methyl group, ethyl group, propyl group, i-propyl group). Group, butyl group, t-
Butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, octyl group, dodecyl group, etc.),
Alkoxyl groups (eg methoxy, ethoxy, 1,
1-dimethylethoxy group, hexyloxy group, dodecyloxy group etc.), aryloxy group (eg phenoxy group, naphthyloxy group etc.), aryl group (eg phenyl group, naphthyl group etc.), alkoxycarbonyl group (eg methoxycarbonyl group) , Ethoxycarbonyl group, butoxycarbonyl group, 2-ethylhexylcarbonyl group, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, naphthyloxycarbonyl group, etc.), heterocyclic group (eg, 2-pyridyl group, 3-pyridyl group, 4 −
Pyridyl group, morpholyl group, piperidyl group, piperazyl group, selenazolyl group, sulforanyl group, piperidinyl group, tetrazolyl group, thiazolyl group, oxazolyl group,
Imidazolyl group, thienyl group, pyrrolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, pyrimidyl group,
Pyrazolyl group, furyl group etc.), amino group (eg amino group, N, N-dimethylamino group, anilino group etc.), hydroxyl group, cyano group, sulfo group, carboxyl group, sulfonamide group (eg methylsulfonylamino group, Ethylsulfonylamino group, butylsulfonylamino group,
Octylsulfonylamino group, phenylsulfonylamino group, etc.) and the like.

In the following, general formulas (I), (II) and (III)
Specific examples of the compound represented by are shown below, but the present invention is not limited thereto.

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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The composition of the silver halide photographic emulsion according to the present invention has any halogen composition such as silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide and silver chloroiodide. However, silver chlorobromide containing 95 mol% or more of silver chloride and containing substantially no silver iodide is preferable. Quick processing,
From the viewpoint of processing stability, a silver halide emulsion containing preferably 97 mol% or more, and more preferably 98 to 99.9 mol% silver chloride is preferable.

In order 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 silver bromide in a high concentration may form a shell, or a so-called epitaxy junction in which a region having a different composition is partially present without forming a complete layer is formed. It may be Further, the composition may change continuously or discontinuously. The portion where silver bromide is present at a high concentration is particularly preferably present at the apex 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 salt or complex salt.

When the heavy metal ion forms a complex, its ligand or ion is cyanide ion, thiocyanate ion, isothiocyanate ion, cyanate ion, chloride ion, bromide ion, iodide ion, Carbonyl, 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 above-mentioned heavy metal ions 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.

The silver halide grains according to the present invention are preferably grains having a single shape, 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.

This grain size can be measured using the projected area of the grain or an 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 grain size distribution, and R is the average grain size.) Various devices known in the art can be used as the apparatus and method for preparing the silver halide emulsion. Any method 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 and 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 the one 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.

Further, 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 kind of silver halide emulsion to be applied and the magnitude of expected effect, but it is 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.

As the gold sensitizer according to the present invention, various gold complexes other than chloroauric acid, gold sulfide and the like can be added. Examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, and mercaptotriazole. The amount of the gold compound used is not uniform depending on the type of silver halide emulsion, the type of compound to be used, the ripening conditions, etc., but usually 1 × 10 ^-4 to 1 × 10 ^-8 mol per mol of silver halide. It is preferred that More preferably, 1 × 10 ^-5 to 1
× 10 ^-8 mol.

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

The compound represented by the general formula (I) is a silver halide emulsion layer or a layer containing colloidal silver in the case of a light-sensitive material having colloidal silver, and a silver halide emulsion in the case of other light-sensitive materials. It is contained in the layer, and the added amount is
It is preferably 5 × 10 ^{−5 to} 0.5 g / m ² , more preferably 2 × 10 ^{−4 to} 0.2 g / m ² , and particularly preferably 5 × 1.
It is 0 ^{−4 to} 0.1 g / m ² .

The compound represented by the general formula (I) may be added to the silver halide photographic emulsion in the usual manner. For example, it can be dissolved in methanol, ethanol, methyl cellosolve, acetone, water, a mixed solvent thereof or the like and added as a solution. Further, it may be added as a dispersion liquid prepared by solid dispersion, emulsion dispersion, ultrasonic dispersion, oil protect dispersion, or the like.

The compound represented by formula (I) 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 preparation step.

The amount of the compound represented by the general formula (I) added to the silver halide photographic emulsion is preferably 2 × 10 ^{−6 to} 0.2 mol, and more preferably 1 × per mol of silver halide.
It is 10 ^{−5 to} 0.02 mol.

The compound represented by the general formula (II) is preferably contained in a silver halide emulsion layer or a layer adjacent to the silver halide emulsion layer, and is added to a hydrophilic colloid layer having a water-permeable relationship with the silver halide emulsion layer. In that case, the addition amount is
It is preferably 2 × 10 ^{−5 to} 0.2 g / m ² , more preferably 1 × 10 ^{−4 to} 0.1 g / m ² , and particularly preferably 2 × 1.
It is 0 ^{−4 to} 0.05 g / m ² .

The compound represented by the general formula (II) may be added to the silver halide photographic emulsion in the usual manner. For example, it can be dissolved in methanol, ethanol, methyl cellosolve, acetone, water, a mixed solvent thereof or the like and added as a solution. Further, it may be added as a dispersion liquid prepared by solid dispersion, emulsion dispersion, ultrasonic dispersion, oil protect dispersion, or the like.

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

The compound represented by the general formula (III) is preferably contained in a silver halide emulsion layer or a layer adjacent to the silver halide emulsion layer, and is added to a hydrophilic colloid layer having a water-permeable relationship with the silver halide emulsion layer. In that case, the addition amount is preferably 2 × 10 ^{−5 to} 0.2 g / m ² , more preferably 1 × 10 ^{−4 to} 0.1 g / m ² , and particularly preferably 2
× 10 ^{-4 to} 0.05 g / m ² .

The compound represented by the general formula (III) may be added to the silver halide photographic emulsion in the usual manner. For example, it can be dissolved in methanol, ethanol, methyl cellosolve, acetone, water, a mixed solvent thereof or the like and added as a solution. Further, it may be added as a dispersion liquid prepared by solid dispersion, emulsion dispersion, ultrasonic dispersion, oil protect dispersion, or the like.

The compound represented by formula (III) 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 timing in the present invention is at the end of silver halide grain formation or at the coating solution adjusting step.

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

The compound represented by the general formula (I) of the present invention is added to a layer containing colloidal silver. Even if the colloidal silver is yellow colloidal silver for a yellow filter, it is black for antihalation. Although colloidal silver may be used, colloidal silver for antihalation is particularly preferable.

Next, the colloidal silver used in the present invention will be described. In the silver halide color photographic light-sensitive material, the colloidal silver is generally yellow colloidal silver for yellow filters and black colloidal silver for antihalation, but in the present invention, in addition to these, orange brown or brown gray It may be colloidal silver.

These colloidal silvers can be produced by a conventionally known method, for example, a method of reducing a soluble silver salt with a hydroquinone in a gelatin solution as shown in US Pat. No. 2,688,601, US Pat. , 096,
No. 193, a method of reducing a poorly soluble silver salt with hydrazine, a method of reducing silver with tannic acid as described in US Pat. No. 2,921,914, and JP-A-5-134358. As described above, it is possible to use a method of forming silver particles by electroless plating.

The method of adding these colloidal silver to the light-sensitive material is described in the above-mentioned patent and US Pat. No. 1,126,79.
7, U.S. Pat. Nos. 4,460,679 and 4,563.
No. 406, No. 3,333,960 and U.S. Defense Publication No. T900,010 can be used.

The silver halide emulsion according to the present invention is intended to prevent fog that occurs during the process of preparing a silver halide photographic light-sensitive material, reduce performance fluctuation during storage, and prevent fog that occurs during development. Antifoggant known in
Stabilizers can be used. As examples of preferred compounds that can be used for such purposes, JP-A-2-14
General formula (II) described in the lower column of page 7 of JP-A-6036
Examples of more preferable specific compounds include (IIa-1) to (IIa-8) and (IIb-1) to (IIb-) described on page 8 of the publication.
7) or 1- (3-methoxyphenyl) -5-
Examples thereof include compounds such as mercaptotetrazole and 1- (4-ethoxyphenyl) -5-mercaptotetrazole. These compounds, depending on their purpose,
It is added in the steps of preparing the silver halide emulsion grains, the chemical sensitization step, the completion of the chemical sensitization step, and the coating liquid preparation step. When chemical sensitization is performed in the presence of these compounds, 1 × 10 ⁻⁵ mol to 5 × 10 ⁵ mol per mol of silver halide is used.
It is preferably used in an amount of about ^-4 mol. When added at the end of chemical sensitization, 1 × 10 1 per mol of silver halide
^-6 mol to ^{1x10 -2} mol is preferable and ^1x10 is preferable.
^-5 mol to 5 x 10 ^-3 mol is more preferable. When added to the silver halide emulsion layer in the coating liquid preparation step,
The amount is preferably about 1 × 10 ^-6 mol to 1 × 10 ^-1 mol, and more preferably 1 × 10 ^-5 mol to 1 × 10 ^-2 mol, per 1 mol of silver halide. When it is added to a layer other than the silver halide emulsion layer, the amount in the coating film is 1 × per 1 m ^2.
An amount of about 10 ⁻⁹ mol to 1 × 10 ⁻³ mol is preferable.

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. For the purpose of improving sharpness, the amount of these dyes added is preferably such that the spectral reflection density at 680 nm of the untreated sample of the light-sensitive material is 0.7 or more, more preferably 0.8 or more. More preferable.

It is preferable to add a fluorescent whitening agent to the light-sensitive material according to the present invention since the whiteness can be improved. Preferred examples of the compound include a compound represented by the general formula II described in JP-A-2-232652.

When the silver halide photographic light-sensitive material according to the present invention is used as a color photographic light-sensitive material, it is spectrally sensitized in a specific region of a wavelength range of 400 to 900 nm by combining it with a yellow coupler, a magenta coupler and a cyan coupler. It has a layer containing a silver halide emulsion. The silver halide emulsion contains one kind or a combination of two or more kinds of sensitizing dyes.

As the spectral sensitizing dye for use in the silver halide emulsion according to the present invention, any of the known compounds 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. In the case of performing image exposure with infrared light using a semiconductor laser or the like, it is necessary to use an infrared-sensitive sensitizing dye. The dyes of IRS-1 to 11 described in JP-A No. 6-8 are preferably used. These infrared, red, green, and blue photosensitive sensitizing dyes may be added to supersensitizers SS-1 to SS-9 described in JP-A-4-285950, pp. 8-9, and JP-A-5-66515. Nos. S-1 to S-17 described on pages 15 to 17
Are preferably used 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, dimethylformamide or the like or water, or adding it as a solid dispersion. It may be added.

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 a wavelength range longer than 340 nm by 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:
The couplers represented by the general formulas (C-I) and (C-II) described in JP-A-4-114154, page 5, lower left column can be mentioned. Specific compounds include those described as CC-1 to CC-9 in page 5, lower right column to page 6, lower left column in the same publication.

As magenta couplers that can be preferably used in the silver halide photographic light-sensitive material according to the present invention, the general formulas (M-I) and (M-II) described in the upper right column of page 4 of JP-A-4-114154 can be used. ) And a coupler represented by Specific compounds include those described as MC-1 to MC-11 in the lower left column of page 4 to the upper right column of page 5 of the publication. More preferred among the above magenta couplers are couplers represented by the general formula (MI) described in the upper right column on page 4 of the publication, wherein the RM of the general formula (MI) is a tertiary alkyl. The coupler which is a group is excellent in light resistance and particularly preferable. MC-8 to M described in the upper column on page 5 of the publication
C-11 is preferable because it is excellent in reproducing colors ranging from blue to purple and red, and is also excellent in detail description power.

The yellow coupler which can be preferably used in the silver halide photographic light-sensitive material according to the present invention is a coupler represented by the general formula (YI) described in JP-A-4-114154, page 3, upper right column. Can be mentioned. Specific compounds include those described as YC-1 to YC-9 in the lower left column on page 3 of the publication. Among them, couplers in which RY1 of the general formula [Y-1] in the publication is an alkoxyl group or JP-A-6-206
The coupler represented by the general formula [I] described in JP-A-67388 is preferable because it can reproduce yellow of a preferable color tone. Of these, examples of particularly preferable compounds are JP-A-4-11415.
No. 4 publication, YC-8, Y described in the lower left column on page 4
C-9, and JP-A-6-67388, 13-14.
No. described on the page Compounds represented by (1) to (47) can be mentioned. The most preferred compounds are disclosed in JP-A-4-81847, page 1, and JP-A-4-81847.
A compound represented by the general formula [Y-1] described on pages 17 to 17.

When the oil-in-water type emulsion dispersion method is used to add the coupler and other organic compounds 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. As the high-boiling organic solvent that can be used to dissolve and disperse the coupler, dioctyl phthalate, diisodecyl phthalate, phthalates such as dibutyl phthalate, tricresyl phosphate, phosphates such as trioctyl phosphate, 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 include 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.

An anti-fading agent is preferably used 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 general formulas I and II described on page 3 of JP-A-2-66541, phenolic compounds represented by general formula IIIB described in JP-A-3-174150, and Amine compounds represented by the general formula A described in JP-A-64-90445;
General formulas XII, XIII, XIV, XV described in -182741
Are particularly preferred 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, compound (d-11) described in the lower left column of page 9 of JP-A-4-114154 and compound (A'-1) described in the lower left column of page 10 of JP-A-4-114154 are disclosed. And the like. 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 according to the present invention, a compound which reacts with an oxidized product of a developing agent is added to a layer between the light-sensitive layers to prevent color turbidity or to form a silver halide emulsion layer. It is preferable to add it 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.
A particularly preferred compound is the compound represented by the general formula II described in JP-A No. 4-133056, and JP-A Nos. 13 to 1
Compounds II-1 to II-14 described on page 4 and compound 1 described on page 17 can be mentioned.

It is preferable to add an ultraviolet absorber to the light-sensitive material of the present invention to prevent static fog or to improve the light fastness of a dye image. Preferable ultraviolet absorbers include benzotriazoles. Particularly preferred compounds are compounds represented by the formula III-3 described in JP-A-1-250944, and JP-A-64-6664.
6, a compound represented by the general formula III,
UV-1L to UV-27 described in 3-187240
L, compounds represented by the general formula I described in JP-A-4-1633, and compounds represented by the general formulas (I) and (II) described in JP-A-5-165144.

For the silver halide photographic light-sensitive material of the present invention, it is advantageous to use gelatin as a binder, but if necessary, other gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, gelatin. Other than the above, hydrophilic colloids such as proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as single or copolymers 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, a polyethylene terephthalate support, baryta paper or the like 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 degree of dispersion 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. Further, the value of the center surface average roughness (SRa) of the support is 0.15 μm or less, and further, it is 0.
It is more preferable that the thickness be 12 μm or less because the effect that the glossiness is good 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.

The silver halide photographic light-sensitive material according to the present invention may be directly or undercoated (adhesiveness of the surface of the support) after subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc. Applied through one or more undercoat layers for improving antistatic properties, dimensional stability, abrasion resistance, hardness, antihalation properties, friction properties and / or other properties) Good.

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.

In order 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 bonded onto the silver halide photographic light-sensitive material to be printed. It may be imaged and printed, or after the image is once converted into digital information, the image is formed on a CRT (cathode ray tube) and then formed on the silver halide photographic light-sensitive material to be printed. Printing may be performed, or the scanning may be performed 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 examples thereof include a color negative film and a color reversal film. These have colloidal silver as a filter layer and are suitable for applying the present invention. The present invention is particularly preferably applied to a light-sensitive material that forms 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. Particularly, it is preferable to provide a white pigment layer on the reflective support because the sharpness is improved, but further improvement can be achieved by further containing colloidal silver in the white pigment layer. A light-sensitive material containing such colloidal silver is a preferred embodiment of the present invention.

As the aromatic primary amine developing agent used in the present invention, known compounds can be used. The following compounds can 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 40 seconds or less, and more preferably 25 seconds or less.

To the color developing solution, a known developing solution component compound can be added in addition to the above 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. In the case of processing a large amount, it is usually a running process using an automatic processor, but at this time, the smaller the replenishing amount of the replenisher is, the more preferable the processing form from the viewpoint of environmental suitability is the tablet replenishing method. The addition of the treating agent in form, the method described in published technique 94-16935 being most preferred.

[0128]

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.

[0133]

[Table 1]

[0134]

Embedded image

SU-1: sodium tri-i-propylnaphthalene sulfonate SU-2: sulfosuccinate di (2-ethylhexyl) sodium salt SU-3: sulfosuccinate di (2,2,3,3,4) , 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 1 liter of 2% gelatin aqueous solution kept at 40 ° C, the following (A
(Solution) and (solution B) are simultaneously added over 30 minutes while controlling pAg = 7.3 and pH = 3.0, and further (C1 solution) below.
And (D solution) were simultaneously added over 180 minutes while controlling pAg = 8.0 and pH = 5.5. At this time, pAg was controlled by the method described in JP-A-59-45437.
The pH was controlled using sulfuric acid or an aqueous sodium hydroxide solution.

(Solution A) Sodium chloride 0.056 g Potassium bromide 0.0002 g Water was added to 200 ml (Solution B) Silver nitrate 10 g Water was added to 200 ml (Solution C1) Sodium chloride 1.757 g K ₂ IrCl ₆ 2 × 10 ^-5 g K ₄ Fe (CN) ₆ 7 × 10 ^-3 g Potassium bromide 0.008 g Water was added to 600 ml (solution D) Silver nitrate 300 g Water was added to 600 ml After the 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)) The same as in the preparation of high silver chloride monodisperse emulsion (EMP-1) except that (C1 solution) was changed to (C2 solution) below. Mean particle size 0.71 μm, coefficient of variation of particle size distribution 0.0
7. Monodisperse cubic emulsion EMP with silver chloride content of 90 mol%
-2 was obtained.

(Solution C2) Sodium chloride 1.59 g K ₂ IrCl ₆ 2 × 10 ⁻⁵ g K ₄ Fe (CN) ₆ 7 × 10 ⁻³ g Potassium bromide 0.176 g Water was added to give 600 ml (chlorobromide). Preparation of Silver Monodisperse Emulsion (EMP-3)) In the preparation of high silver chloride monodisperse emulsion (EMP-1) (C1 solution)
A monodispersed cubic emulsion EMP-3 having an average grain size of 0.71 μm, a variation coefficient of grain size distribution of 0.07, and a silver chloride content of 80 mol% was obtained in the same manner except that was changed to (C3 solution) below.

(C3 solution) Sodium chloride 1.413 g K ₂ IrCl ₆ 2 × 10 ⁻⁵ g K ₄ Fe (CN) ₆ 7 × 10 ⁻³ g Potassium bromide 0.3529 g Water was added to 600 ml (blue-sensitive halogen). Preparation of silver halide emulsion) EMP-1 to 3 above
In contrast, the following compounds were optimally chemically sensitized at 60 ° C. to obtain blue-sensitive silver halide emulsions (Em-B101) to
(Em-B103) 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: 1-phenyl-5-mercaptotetrazole Here, the sensitizing dyes BS-1 and BS-2 are Japanese Patent Application No. 5-09.
The sensitizing dye obtained by the method described on page 87 of the No. 8094 specification was added by an addition solution in which solid sensitizing dyes are present.

[0141]

Embedded image

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 117 were prepared in the same manner except that the compound shown in 1 was dissolved in ethanol and added. Samples 101 to 1
17 was kept in an atmosphere of 25 ° C. and 30% RH and 25 ° C. and 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.

Processing Step Processing Temperature Time Replenishment Amount Color Development 38.0 ± 0.3 ° C. 45 seconds 80 cc Bleach-fixing 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 developing 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-aminoaniline sulfate 6.0 g 10.0 g N, N-diethylhydroxylamine 6.8 g 6.0 g triethanolamine 10.0 g 10.0 g diethylenetriamine Pentaacetic acid sodium salt 2.0 g 2.0 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 2.0 g 2.5 g Potassium carbonate 30 g 30 g Water was added to make the total volume 1 liter, and the tank liquid had pH. = 10.10, the replenisher has 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 Add water to make the total volume 1 liter, and adjust to pH = 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,
For the sensitivity of ℃ · 30% RH, sample 101 is 100
Was expressed as a relative value. For the sensitivity of 25 ° C and 80% RH, the sensitivity of the same sample at 25 ° C and 30% RH is 1
It was expressed as a relative value as 00. Table 2 shows the results.

[0148]

[Table 2]

As is clear from Table 2, in Sample 101 using the silver halide emulsion not using the compound of the present invention,
There is a large decrease in sensitivity when exposed under high humidity, and the general formula (I
Sample 103 using only the compound of I) showed a large decrease in sensitivity. It can be seen that the sample of the present invention has high sensitivity, and the sensitivity decrease when exposed under high humidity is improved. Further, as can be seen from the samples 114 and 115, the general formula (II
The sample to which the compound of I) is added has higher sensitivity. Further, from the comparison between Samples 111 and 113 and Samples 107 and 112, when X of the compound of the general formula (I) is a carbon atom, the sensitivity decrease when exposed under high humidity is further improved. Also,
From the comparison of samples 108 and 110 and samples 107 and 109,
Higher sensitivity is obtained when R ₄ of the compound of the general formula (II) is a hydrogen atom. Further, from the comparison of Samples 107, 116, and 117, it was found that the silver halide content of silver halide of 90% or higher showed higher sensitivity, and the silver chloride content of 95% or higher showed higher sensitivity.

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 hardening agent (H-1), (H-2)
Was added. Surfactants (SU-
2) and (SU-3) were added to adjust the surface tension. The total amount of the compound III-1 of the general formula (III) is 0.0
It was added so as to be 4 g / m ² .

[0152]

[Table 3]

[0153]

[Table 4]

PVP: Polyvinylpyrrolidone DOP: Dioctylphthalate DIDP: Di-i-decylphthalate 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

[0155]

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[0156]

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[0157]

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[0158]

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[0159]

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(Preparation of blue-sensitive silver halide emulsion) (A
Solution) and (B solution) addition time and (C1 solution) and (D solution)
A monodisperse cubic emulsion having an average grain size of 0.64 μm, a variation coefficient of grain size distribution of 0.07, and a silver chloride content of 99.5 mol% in the same manner as in EMP-1 of Example 1 except that the addition time was changed. EMP-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 size is 0.40μ in the same manner as EMP-1 except that the addition time of (C1 liquid) and the addition time of (D liquid) are changed.
m, a coefficient of variation of 0.08 and a monodispersed cubic emulsion EMP-4 having a silver chloride content of 99.5%. Next, average particle size 0.5
A monodisperse cubic emulsion EMP-4B having a particle size of 0 μm, a coefficient of variation of 0.08 and a silver chloride content of 99.5% was obtained.

The above EMP-4 was optimally chemically sensitized at 55 ° C. using the following compounds. Also EMP-4B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-4 and EMP-4B were mixed in a silver amount of 1: 1 to obtain a green-sensitive silver halide emulsion (Em-G).

Sodium thiosulfate 1.5 mg / mol AgX Chlorauric 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 size is 0.40μ in the same manner as EMP-1 except that the addition time of (C1 liquid) and the addition time of (D liquid) are changed.
m, a coefficient of variation of 0.08, and a monodispersed cubic emulsion EMP-5 having a silver chloride content of 99.5%. The average particle size is 0.38
A monodisperse cubic emulsion EMP-5B having a thickness of 0.08 μm, a coefficient of variation of 0.08 and a silver chloride content of 99.5% was obtained.

The EMP-5 was optimally chemically sensitized at 60 ° C. using the following compounds. Also EMP-5B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-5 and EMP-5B were mixed in a silver ratio 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

[0167]

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[0168]

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To the red light-sensitive emulsion, the above 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 manufactured.

Samples 202 to 207 were prepared in the same manner as Sample 201 except that the compounds of the general formulas (I) and (II) were added as shown in Tables 5 and 6 (Table 5). , Table 6).

[0173]

[Table 5]

[0174]

[Table 6]

Samples 201 to 207 were exposed and developed in the same manner as in Example 1, and the obtained samples were measured for blue, green and red densities using a PDA-65 densitometer (manufactured by Konica Corporation). Evaluation was performed in the same manner as in Example 1. Table 7 shows the results.

[0176]

[Table 7]

As is clear from Table 7, in the sample 204 in which the compound of the general formula (I) and the compound of the general formula (II) are added to different layers, no improvement effect is shown, but the compound of the general formula (I) is It can be seen that the sample 205 in which the compound of Formula (II) and the compound of the general formula (II) were added to the same layer showed the same improvement effect in the multi-layer.

Example 3 In the preparation of Sample 202 of Example 2, Sample 301 was prepared by providing S-1 layer and S-2 layer shown in Table 8 below between the support and the first layer. Sample 3 was prepared except that the compounds shown in Table 9 and Table 10 were added in the preparation of Sample 301.
Samples 302 to 304 were prepared in the same manner as 01.

[0179]

[Table 8]

The above sample was evaluated in the same manner as in Example 2. The results are shown in Tables 9 and 10 below.

[0181]

[Table 9]

[0182]

[Table 10]

As can be seen from Tables 9 and 10, the sample in which the compound of the general formula (I) was added to the colloidal silver layer exhibited the same improvement effect as the sample added to the emulsion layer.

Example 4 Samples 201, 205, 206 and 20 prepared in Example 2
7 was exposed and developed through an already developed Konica Color LV-400 using an automatic processor (NPS-868J manufactured by Konica Corp .; ECOJET-P is used 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 Comparative Sample 201, a shift in the blue direction was observed when the humidity of the exposed portion increased. Sample 20 of the present invention
Nos. 5, 206, and 207 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.

[0185]

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

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshihiko Suda Konica Stock Company, 1 Sakura-cho, Hino-shi, Tokyo In-house

Claims (5)

[Claims] 1. 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 is represented by the following general formula (I). And a compound represented by the following general formula (II), a silver halide photographic light-sensitive material. Embedded image [In the formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ each represent a hydrogen atom, an alkyl group, -X-R ₆ or -X-R _{9, and} may be the same or different, or They may combine to form a ring. Here, X is _{-C (R 7) (R 8} ) -, -
Represents O- or -S-. However, at least one of R ₁ , R ₂ , R ₃ , R ₄ and R ₅ represents —X—R ₉ .
R ₆ represents an alkyl group or an aryl group, R ₇ and R ₈ each represent a hydrogen atom or an alkyl group, and R ₉
Represents an aryl group, and when there are plural aryl groups, they may be the same or different, and may be bonded to each other to form a ring. [Chemical formula 2] [In the formula, R ₂₁ and R ₂₂ may be the same or different,
Each represent -OR ₂₅ or _{-N (R 26) R 27,} R 25
Represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ₂₃ , R ₂₄ , R ₂₆ and R ₂₇ may be the same or different and each is a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. , A sulfonyl group, a carbonyl group, a carbamoyl group, or an adsorption promoting group to silver halide.
Provided that at least one of R ₂₃ , R ₂₄ , R ₂₅ , R _26, and R ₂₇ is a group promoting adsorption to silver halide, or a group substituted with a group promoting adsorption to silver halide. is there. ] 2. A silver halide photographic light-sensitive material according to claim 1, containing a compound represented by the following general formula (III). Embedded image [In the formula, R ₃₁ represents a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, an aryl group, an alkoxyl group, a carbonyl group or a heterocyclic group. R ₃₂ and R ₃₃ are
Each represents a hydrogen atom, a halogen atom, an alkyl, an aryl, a heterocyclic group, a cyano group, an alkylthio group, an arylthio group, an alkylsulfooxide group, an alkylsulfonyl group or an alkylsulfinyl group. Also, R ₃₂
And R ₃₃ may combine with each other to form a benzene ring which may have a substituent. ] 3. 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 1 or 2, which contains silver halide grains. 4. 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 95 mol% or more. The silver halide photographic light-sensitive material according to claim 1 or 2, which contains silver halide grains. 5. A silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer and a non-photosensitive layer containing colloidal silver on a support, the non-photosensitive material containing the colloidal silver. The layer contains the compound represented by the general formula (I), and the non-photosensitive layer containing the colloidal silver or at least one layer adjacent thereto contains the compound represented by the general formula (II). A silver halide photographic light-sensitive material characterized by being