JPH09138474A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material having high sensitivity, low fogging and excellent preserving performance. SOLUTION: The emulsion layers of the photographing sensitive material having at least one layer of the photosensitive silver halide emulsion layers on a base contain the photosensitive silver halide emulsions which are subjected to reduction sensitization. And are added with the compd. expressed by the formula R1 -X1 -X2 -R2 and an oxidizing agent for silver exclusive thereof during the production process. In the formula, R1 and R2 may be the same or different and respectively denote alkyl groups, aryl groups, heterocyclic groups, amino groups or acyl groups, etc.; X1 and X2 may be the same or different and respectively denote S, Se or Te; R1 , R2 , X1 and X2 may cooperatively form a ring.

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 material. In particular, the present invention relates to a silver halide photographic light-sensitive material which contains grains subjected to reduction sensitization and has high sensitivity, low fog, and excellent storage performance.

[0002]

2. Description of the Related Art In recent years, the image quality of color photosensitive materials, that is,
Color reproducibility, sharpness, and graininess have made remarkable progress.
However, the demand for the image quality of the light-sensitive material is not limited, and further progress is required. For this reason, various emulsion techniques, coupler techniques, and the like have been studied, and each has achieved great results.

[0003] It is well known in the art that, in order to improve the graininess of a light-sensitive material and to increase the sensitivity, it is important in the art to increase the sensitivity of silver halide grains by reducing the size thereof. is there. In recent years, in order to increase the sensitivity of fine particles of silver halide grains, for example, devising a reduction sensitization method described later has been studied, and great results have been achieved.

Attempts for reduction sensitization have been studied for a long time in order to increase the sensitivity. Carroll is a tin compound in US Pat. No. 2,487,850, Lowe et al. Is a polyamine compound in US Pat. No. 2,512,925, and Fallens et al. Is British Patent 789, No. 823 disclosed that thiourea dioxide compounds are useful as reduction sensitizers. Further Co
llier is Photographic Science and Engin
Eering, Vol. 23, page 113 (1979), compares the properties of silver nuclei produced by various reduction sensitization methods. She employed the methods of dimethylamine borane, stannous chloride, hydrazine, high pH aging, and low pAg aging. The method of reduction sensitization is further described in US Pat. No. 2,518,6.
No. 98, No. 3,201,254, No. 3,411,
No. 917, No. 3,779, 777, No. 3,93
No. 0,867. Regarding the improvement of the reduction sensitization method as well as the selection of the reduction sensitizer, JP-B-57-33
No. 572, No. 58-1410, JP-A-2-10513.
No. 9 is mentioned.

However, it has been found that an increase in sensitivity due to reduction sensitization is accompanied by an increase in the storage performance of the light-sensitive material, particularly an increase in fog and a deterioration in latent image assisting power. The photosensitive material for photographing may be developed immediately after photographing, or may be developed several months or one year after photographing, and it is desirable that the performance does not change during such a lapse of time. The stability of the latent image after exposure has been known for a long time as regression that moves as if sensitivity decreased at first glance and intensification that moves as if it rose, and recently, for example, The Jou by EF Thurston.
nal of Photographic Science Volume 38 (34-40 pages, 1990) and other research examples.

Regarding the technique for improving the storability of reduction-sensitized emulsions, JP-A-57-82831 and 60-178 are known.
No. 445. However, these techniques are not sufficient as general-purpose techniques for reduction-sensitized emulsions, and are particularly effective for storage stability of reduction-sensitized emulsions using green-sensitizing and red-sensitizing sensitizing dyes. The current situation is that it is not functioning.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic light-sensitive material having high sensitivity, low fog and excellent storage performance.

[0008]

The object of the present invention can be achieved by the following means. That is, in a photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, the emulsion layer is reduction-sensitized, and a compound represented by the following general formula (S1) A silver halide photographic light-sensitive material containing a light-sensitive halogenated emulsion to which an oxidizing agent for silver other than the above is added. General formula (S1)

[0009]

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In the formula, R ₁ and R ₂ may be the same or different and each represents an alkyl group, an aryl group, a heterocyclic group, an amino group or a group shown below.

[0011]

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In the formula, R ₃ and R ₅ may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. X ₁ and X ₂ may be the same or different and each represents S, Se or Te.
R ₁ , R ₂ , X ₁ and X ₂ may together form a ring.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. First, reduction sensitization in the present invention will be described. The production process of a silver halide emulsion includes grain formation, desalting,
It is roughly divided into processes such as chemical sensitization. Particle formation is nucleation
Divided into aging and growth. These steps are not performed uniformly, but the order of the steps is reversed or the steps are repeatedly performed. The fact that reduction sensitization is performed during the production process of a silver halide emulsion basically means that it may be performed at any process. Reduction sensitization may be performed during nucleation, which is the initial stage of grain formation, during physical ripening, or during growth, and may be performed prior to chemical sensitization other than reduction sensitization or after this chemical sensitization. . When performing chemical sensitization in combination with gold sensitization, reduction sensitization is preferably performed prior to chemical sensitization so as not to cause undesirable fog. Most preferred is a method of reduction sensitization during growth of silver halide grains. The term "during growth" here also refers to a method in which the silver halide grains are physically ripened or subjected to reduction sensitization while they are growing by the addition of a water-soluble silver salt and a water-soluble alkali halide, and the growth is temporarily stopped during the growth. It means that the method also includes a method of performing reduction sensitization in the above state and then further growing.

The reduction sensitization of the present invention means a method of adding a known reducing agent to a silver halide emulsion, pAg called silver ripening.
Either a method of growing or aging in a low pAg atmosphere of 1 to 7 or a method of growing or aging in a high pH atmosphere of pH 8 to 11 called high pH aging can be selected. Also, two or more methods can be used in combination.

The method of adding a reduction sensitizer is a preferable method because the level of reduction sensitization can be finely adjusted.

Known reduction sensitizers are stannous salts, amines and polyamic acids, hydrazine derivatives, formamidinesulfinic acid, silane compounds and borane compounds. In the present invention, these known compounds can be selected for use, and two or more compounds can be used in combination. Stannous chloride, thiourea dioxide, and dimethylamine borane are preferred compounds as reduction sensitizers. The addition amount of the reduction sensitizer depends on the emulsion production conditions, so it is necessary to select the addition amount, but 10 ^-7 to 10 ^-3 per mol of silver halide
A molar range is appropriate.

Ascorbic acid and its derivatives can also be used as the reduction sensitizer of the present invention.

Ascorbic acid and its derivatives (hereinafter
It is called "ascorbic acid compound". The following can be mentioned as specific examples of ()). (A-1) L-ascorbic acid (A-2) L-sodium ascorbate (A-3) L-ascorbate potassium (A-4) DL-ascorbic acid (A-5) D-ascorbate (A -6) L-ascorbic acid-6-acetate (A-7) L-ascorbic acid-6-palmitate (A-8) L-ascorbic acid-6-benzoate (A-9) L-ascorbic acid-5,6 -Diacetate (A-10) L-ascorbic acid-5,6-O-isopropylidene The ascorbic acid compound used in the present invention is used in a large amount as compared with the addition amount in which a reduction sensitizer is conventionally used preferably. Is desirable. For example, JP-B-57-33572
No. "The amount of reducing agent is usually 0.75 × g per silver ion.
Does not exceed 10 ^-2 meq (8 × 10 ^-4 mol / AgX mol). An amount of 0.1 to 10 mg per kg of silver nitrate (10 ^-7 to 10 ^-5 mol / AgX mol as ascorbic acid) is often effective. (The converted value is based on the inventors). U.S. Pat. No. 2,487,850 states that "the amount of tin compound which can be used as a reduction sensitizer is 1
× 10 ^{-7 to} 44 × 10 ^-6 mol ". JP-A-57-179835 states that it is appropriate to use about 0.01 mg to about 2 mg of thiourea dioxide per mole of silver halide and about 0.01 mg to about 3 mg of stannous chloride. It has been described. Ascorbic acid compound used in the present invention the particle size of the emulsion, the halogen composition, the humidity of the emulsion preparation, pH, depends preferably amount by factors such as pAg, per mole of silver halide 5 × 10 ^-5 to 1
It is desirable to select from the range of × 10 ^-1 mol. More preferably, it is preferably selected from the range of 5 × 10 ⁻⁴ mol to 1 × 10 ⁻² mol. Particularly preferred is 1 × 10 ⁻³ mol or more.
It is to select from a range of 1 × 10 ^-2 mol.

The reduction sensitizer is water or alcohols,
It can be dissolved in a solvent such as glycols, ketones, esters and amides and added during grain formation, before or after chemical sensitization. The compound may be added during any step of the emulsion production process, but a particularly preferable method is to add the compound during grain growth. It is good to add to the reaction vessel in advance,
It is preferable to add it at an appropriate time for grain formation. Alternatively, a reduction sensitizer may be added to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide in advance, and particles may be formed using these aqueous solutions. It is also a preferred method to add the solution of the reduction sensitizer in several portions as the grains are formed, or to add the solution continuously for a long time.

In the present invention, the oxidizing agent for silver means a compound that acts on metallic silver to convert it into silver ions. In particular, a compound capable of converting extremely fine silver atoms by-produced in the process of forming silver halide grains into silver ions is effective. The silver ions generated here are
A water-insoluble silver salt such as silver halide, silver sulfide, or silver selenide may be formed, or a water-soluble silver salt such as silver nitrate may be formed.

The oxidizing agent for silver, even if it is an inorganic substance,
It may be an organic substance. As the inorganic oxidizing agent, ozone, hydrogen peroxide and its adducts (for example, NaBO ₂
・ H ₂ O ₃ .3H ₂ O, 2NaCO ₃ .3H ₂ O ₂ , N
_{a 4 P 2 O 7 · 2H} 2 O 2, 2Na 2 SO 4 · H 2 O 2
2H ₂ O), peroxy acid salts (eg, K ₂ S)
₂ O ₈ , K ₂ C ₂ O ₆ , K ₂ P ₂ O ₈ ) and peroxy complex compounds (for example, K ₂ [Ti (O ₂ ) C ₂ O ₄ ] .3
_{H 2 O, K 2 SO 4} · Ti (O 2) OH · SO 4 · 2H
₂ O, Na _{3 [VO (O 2) (C 2} H 4) 2 · 6H
₂ O], permanganate (for example, KMnO ₄ ) and chromate (for example, K ₂ Cr ₂ O ₇ ) and other oxyacid salts, halogen elements such as iodine and bromine, and permanganate (for example, Potassium periodate) a salt of a high valence metal (eg,
Potassium hexacyanoferrate) and thiosulfonate.

As organic oxidants, quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogen (for example, N-bromosuccinimide and chloramine T). , Chloramine B). Preferred oxidizing agents of the present invention are ozone,
Hydrogen peroxide and its adducts, halogen elements, thiosulfonate inorganic oxidants and quinones organic oxidants.

The more preferred oxidizing agent is thiosulfonate, which can be selected from the compounds represented by the formulas (I) to (III). Most preferred among these are compounds of formula (I).

In the presence of silver, thiosulfonic acid oxidizes silver to form silver sulfide according to the following reaction formula, S. Gahle
r by Veroff wiss. Photolab Wolfen X, 63 (1
965).

RSO ₂ SM + 2Ag → RSO ₂ M + Ag ₂ S It has been experimentally confirmed that such oxidation occurs. (II) in _{R-SO 2 S-M (} III) R-SO 2 S-R 6 (IV) R-SO 2 S-Lm-SSO 2 -R 7 Formula, R, R _6, also R ₇ are the same They may be different and represent an aliphatic group, an aromatic group, or a heterocyclic group, and M represents a cation. L represents a divalent linking group, and m is 0 or 1.

The compounds of the general formulas (II) to (IV) have the formula (I
It may be a polymer containing a divalent group derived from the structure represented by I) to (IV) or a divalent group derived from the structure represented by (IV) as a repeating unit. When possible, R, R ₆ , R ₇ and L may combine with each other to form a ring.

The thiosulfonic acid compounds represented by the general formulas (II), (III) and (IV) will be described in more detail.
_{When 6} and R ₇ are aliphatic groups, it is a saturated or unsaturated, linear, branched or cyclic, aliphatic hydrocarbon group, preferably an alkyl group having 1 to 22 carbon atoms and 2 carbon atoms. To 22 alkenyl groups and alkynyl groups, which may have a substituent. As the alkyl group,
For example, methyl, ethyl, propyl, butyl, pentyl,
Hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, isopropyl, t-butyl.

Examples of the alkenyl group include allyl and butenyl.

Examples of the alkynyl group include propargyl and butynyl.

The aromatic group of R, R ₆ and R ₇ includes a monocyclic or condensed ring aromatic group, preferably having 6 to 20 carbon atoms, and examples thereof include phenyl and naphthyl. These may be substituted.

The heterocyclic group for R, R ₆ and R ₇ includes
A 3- to 15-membered ring having at least one element selected from nitrogen, oxygen, sulfur, selenium, and tellurium and having at least one carbon atom, preferably 3 to 6
Member rings are preferred, for example pyrrolidine, piperidine, pyridine, tetrahydrofuran, thiophene, oxazole, thiazole, imidazole, benzothiazole, benzoxazole, benzimidazole, selenazole, benzoselenazole, tellurazole, triazole, benzotriazole, tetrazole, oxadiazole, An example is the thiadiazole ring.

Substituents for R, R ₆ and R ₇ include, for example, alkyl groups (eg, methyl, ethyl, hexyl),
Alkoxy groups (eg methoxy, ethoxy, octyloxy), aryl groups (eg phenyl, naphthyl,
Tolyl), hydroxy group, halogen atom (eg fluorine, chlorine, bromine, iodine), aryloxy group (eg phenoxy), alkylthio group (eg methylthio, butylthio), arylthio group (eg phenylthio), acyl group (eg, Acetyl, propionyl, butyryl, valeryl), sulfonyl group (eg, methylsulfonyl, phenylsulfonyl), acylamino group (eg, acetylamino, benzoylamino), sulfonylamino group (eg, methanesulfonylamino, benzenesulfonylamino), acyloxy group (Eg, acetoxy, benzoxy), carboxyl group, cyano group, sulfo group, amino group, —SO ₂ SM group, and (M represents a monovalent cation) —SO ₂ R ¹ group.

As the divalent linking group represented by L,
An atom or an atomic group containing at least one selected from C, N, S and O. Specifically, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -O-,
-S -, - NH -, - CO -, - SO 2 - is made of a single or combination of such.

L is preferably a divalent aliphatic group or a divalent aromatic group. L is a divalent aliphatic group such as

[0035]

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An example is a xylene group. Examples of the divalent aromatic group include a phenylene group and a naphthylene group.

These substituents may be further substituted with the above-mentioned substituents.

M is preferably a metal ion or an organic cation. Examples of the metal ion include a lithium ion, a sodium ion, and a potassium ion. Examples of the organic cation include ammonium ion (for example, ammonium, tetramethylammonium, tetrabutylammonium), phosphonium ion (tetraphenylphosphonium), and guanidyl group.

When the general formulas (II) to (IV) are polymers, examples of the repeating units are as follows.

[0040]

[Chemical 6]

These polymers may be homopolymers or copolymers with other copolymerizable monomers.

Specific examples of the compounds represented by the general formula (II), (III) or (IV) are shown in the following chemical formulas 7 to 13, but not limited thereto.

The compounds of the general formulas (II), (III) and (IV) are described in JP-A-54-1019; British Patent No. 972,21.
1; Journal of Organic Chemistry, 53, 396 pages (1
988).

[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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The compound represented by formula (II), (III) or (IV) is 10 ^-7 to 10 ^-1 per mol of silver halide.
It is preferable to add them in moles. From 10 ^-6 to 10 ^-2
Particularly, the addition amount of 10 ⁻⁵ to 10 ⁻³ mol / mol Ag is preferable.

In order to add the compounds represented by the general formulas (II) to (IV) during the production process, a method which is usually used for adding an additive to a photographic emulsion can be applied. For example, the water-soluble compound is an aqueous solution having an appropriate concentration, and the water-insoluble or sparingly-soluble compound is a suitable organic solvent miscible with water, such as alcohols, glycols, ketones,
Of the esters and amides, it can be added as a solution obtained by dissolving in a solvent that does not adversely affect the photographic characteristics.

The compound represented by formula (II), (III) or (IV) may be added at any stage during grain formation of a silver halide emulsion, before chemical sensitization or after production.
Preferred is a method in which a compound is added before or during reduction sensitization. Particularly preferred is a method of adding during the grain growth.

It may be added to the reaction vessel in advance, but it is preferable to add it at an appropriate time for grain formation. Further, the compounds represented by the general formulas (II) to (IV) may be added in advance to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide, and particles may be formed using these aqueous solutions. It is also a preferable method to add the solutions of the compounds represented by the general formulas (II) to (IV) along with the formation of particles in several times or continuously for a long time.

The most preferable compound for the present invention is a compound represented by the general formula (II).

The general formula (S1) in the present invention will be described. General formula (S1)

[0057]

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In the formula, R ₁ and R ₂ may be the same or different and each represents an alkyl group, an aryl group, a heterocyclic group, an amino group or a group shown below.

[0059]

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In the formula, R ₃ and R ₅ may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. X ₁ and X ₂ may be the same or different and each represents S, Se or Te.
R ₁ , R ₂ , X ₁ and X ₂ may together form a ring. In the present invention, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , X ₁ and X _{2 in the} general formula (S1) will be described in detail below.

R ₁ and R ₂ may be the same or different and each represents an alkyl group, an aryl group, a heterocyclic group, an amino group or a group shown below.

[0062]

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In the formula, R ₃ and R ₅ may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. R ₄ represents an alkyl group, an aryl group or a heterocyclic group. When R ₁ and R ₂ are each an alkyl group, an aryl group or a heterocyclic group, these groups may further have a substituent. When R ₁ and R ₂ are each an alkyl group, examples of the substituent include a halogen atom, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a nitro group, a hydroxyl group, a carboxy group, a sulfo group, An alkoxy group, an aryloxy group,
Acylamino group, amino group, alkylamino group, anilino group, ureido group, thioureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxy Carbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyl group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphonyl group, aryloxycarbonyl group, acyl It is a base. These may be substituted with an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group, a halogen atom or other substituents formed by an oxygen atom, a nitrogen atom, a sulfur atom or a carbon atom. Good.

When R ₁ and R ₂ are each an aryl group or a heterocyclic group, examples of the substituent include a halogen atom,
Alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, nitro group, hydroxyl group, carboxy group, sulfo group, alkoxy group, aryloxy group, acylamino group, amino group, alkylamino group, anilino group , A ureido group, a thioureido group, a sulfamoylamino group, an alkylthio group, an arylthio group,
Alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyl group, silyloxy group, aryloxycarbonylamino group, imide Group, heterocyclic thio group, sulfinyl group, phosphonyl group,
An aryloxycarbonyl group and an acyl group. These may be substituted with an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group, a halogen atom or other substituents formed by an oxygen atom, a nitrogen atom, a sulfur atom or a carbon atom. Good. When R ₁ and R ₂ are each an amino group, the amino group is a —NH ₂ group or represents an amino group substituted with at least one alkyl group, aryl group or heterocyclic group. At this time, the details of the alkyl group, aryl group and heterocyclic group are the same as those described for R ₁ and R ₂ .

More specifically, examples in which R ₁ and R ₂ are each an alkyl group, an aryl group, a heterocyclic group or an amino group are shown. The alkyl group is a linear, branched or cyclic alkyl group having 1 to 24 carbon atoms, preferably 1 to 16 carbon atoms, and examples thereof include methyl, ethyl, propyl, isopropyl, t-butyl, 3-hydroxypropyl and benzyl. , 2-methanesulfonamidoethyl, 2-methanesulfonylethyl, 3-methoxypropyl, cyclopentyl, 4-acetamidobutyl, 2-carboxyethyl,
3-carbamoylpropyl, 3,4-dihydroxybutyl, n-hexyl, 2-hydroxypropyl, hexadecyl, 3-carbamoylaminopropyl, 4-carbamoylbutyl, 2-carbamoyl, 1-methylethyl, 4
-Nitrobutyl.

The aryl group is an aryl group having 6 to 24 carbon atoms, preferably 6 to 16 carbon atoms, for example, phenyl, naphthyl, 4-methoxyphenyl, 4-acetamidophenyl, 3-hydroxyphenyl, 3-methylphenyl, 4-carboxyphenyl, 3-diethylaminophenyl, 3-acetamidophenyl, 4-carbamoylphenyl, 4-sulfophenyl, 2-carboxyphenyl, 2-acetamidophenyl, 3-formamidophenyl, 2,3-dichlorophenyl, 5-hydroxynaphthyl , 2-methanesulfonamidophenyl, 2-trifluoroacetamidophenyl, 3-benzoylamidophenyl, 4-ethoxycarbonylaminophenyl. The heterocyclic group is a 5-membered or 6-membered saturated or unsaturated heterocyclic ring containing 1 or more oxygen atom, nitrogen atom, or sulfur atom having 1 to 5 carbon atoms, and the number of heteroatoms constituting the ring. And the number of kinds of elements may be one or more, for example, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-pyridyl, 5-benzotriazolyl, 2
-Imidazolyl, 4-pyrazolyl, 5-quinolyl. When R ₁ and R ₂ are each a heterocyclic group, X ₁ and X ₂ are linked to the carbon atom forming the heterocyclic group.

Examples of the amino group include amino, methylamino, hydroxyethylamino, diethylamino, pyrrolidino, piperazino, morpholino, anilino, 4-methoxyanilino, 2,5-dichloroanilino, 3-pyridylamino, 2-imidazolylamino. , 5-quinolylamino, 3-methylpyrazolyl-5-amino, 3-tetrahydrofurylamino and the like. R ₃ and R ₅ may be the same or different and each is a hydrogen atom,
It represents an alkyl group, an aryl group or a heterocyclic group, the details of which are the same as those described for R ₁ and R ₂ .
However, when each of R ₃ and R ₅ is a heterocyclic group, it is bonded to a carbon atom constituting the heterocycle of the heterocyclic group. R ₄ represents an alkyl group, an aryl group or a heterocyclic group, and the details are as defined for R ₁ and R ₂ . However, when R ₄ is a heterocyclic group, it is bonded to a carbon atom forming the heterocycle of the heterocyclic group.
X ₁ and X ₂ may be the same or different and each is S,
Represents Se or Te.

R ₁ , R ₂ , X ₁ and X ₂ may together form a ring. More specifically, the following general formula (S2)
Is represented by General formula (S2)

[0069]

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In the formula, X ₁ and X ₂ may be the same or different and each represents S, Se or Te. Z represents a nonmetallic atomic group necessary for forming a ring. X ₁ , X ₂ and Z
The number of ring members is 4 to 16. However, each element that binds to X ₁ and X ₂ is a carbon atom. The element constituting Z may have a substituent as much as possible, and the details thereof are the same as those described as the substituent that may be possessed when R ₁ is an aryl group.

Among the compounds represented by the general formula (S1), the compound represented by the general formula (S2) or the compound represented by the following general formula (SS1) is preferable. General formula (SS1)

[0072]

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In the formula, R ₆ represents an aryl group or a pyridyl group. When R ₆ is a pyridyl group, it also includes those having a substituent on the pyridine ring. X ₃ represents a sulfur atom or a selenium atom. As a more preferable compound, a compound represented by the general formula (SS
The compound represented by 2) can be mentioned. General formula (SS2)

[0074]

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In the formula, R ₇ represents a substituent. Here, the substituent has the same meaning as described when R ₁ is an aryl group. p represents an integer of 0 to 2. General formula (SS2)
With respect to R ₇ and p therein, preferable combinations thereof will be described below. R ₇ is a halogen atom, an alkyl group,
Aryl group, cyano group, nitro group, hydroxyl group, carboxy group, sulfo group, alkoxy group, acylamino group, amino group, alkylamino group, urend group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl It is preferably a group, a sulfonyl group, an alkoxycarbonyl group, an acyloxy group, a carbamoyloxy group, an acyl group, and p is 1 or 2. Here, these substituents include those substituted by other substituents. Next, specific examples of the compound represented by formula (S1) in the present invention are shown, but the invention is not limited thereto.

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The compound represented by the general formula (S1) can be prepared according to the method described in, for example, “Synthesis and Reaction III of Organic Compound III” 1735 (1978, Maruzen), edited by The Chemical Society of Japan, Vol. And can be easily synthesized.

The compound represented by formula (S1) may be added at any stage during the production of the silver halide emulsion after grain formation. Preferred is a method in which the compound is added after grain formation but before or during chemical sensitization. Particularly preferred is a method of adding the grains between after washing and dispersing and immediately before chemical sensitization. The compound represented by the general formula (S1) is 1 per mol of silver halide.
It is preferable to add from ^{x10 -7} to 1 x 10 ^-1 mol. Further, the addition amount of 1 × 10 ⁻⁶ to 1 × 10 ⁻³ , particularly 1 × 10 ⁻⁶ to 1 × 10 ⁻⁵ mol / mol Ag is preferable.

The light-sensitive material of the present invention may have at least one light-sensitive layer provided on a support. A typical example is a silver halide photographic light-sensitive material having at least one light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. It is. The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic material, the arrangement of the unit photosensitive layers is generally A red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are provided in this order from the support side. However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity. A non-light-sensitive layer may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer. These may contain a coupler, a DIR compound, a color mixing inhibitor, etc. described later. A plurality of silver halide emulsion layers constituting each unit light-sensitive layer are formed by sequentially exposing two layers, a high-speed emulsion layer and a low-speed emulsion layer, to a support as described in DE 1,121,470 or GB 923,045. It is preferable to arrange them so that the degree is low. In addition, JP-A-57-112751, 62-200350, 62-2
As described in 06541 and 62-206543, a low-sensitivity emulsion layer may be provided on the side farther from the support and a high-sensitivity emulsion layer may be provided on the side closer to the support. As specific examples, from the farthest side from the support, a low-sensitivity blue-sensitive layer (BL) / a high-sensitivity blue-sensitive layer (BH) / a high-sensitivity green-sensitive layer (GH) / a low-sensitivity green-sensitive layer (GL) / High-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL), or BH / BL / GL / GH / RH / RL, or BH / BL / GH / GL / RL / RH And so on. Also, as described in JP-B-55-34932, the blue-sensitive layer / GH / RH / GL starts from the side farthest from the support.
/ RL can be arranged in this order. JP-A-56-2573
8, as described in JP-A-62-63936, the layers may be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support. Further, as described in JP-B-49-15495, the upper layer is the silver halide emulsion layer having the highest sensitivity, the middle layer is the silver halide emulsion layer having a lower sensitivity, and the lower layer is a silver halide emulsion layer having a higher sensitivity than the middle layer. An example is an arrangement in which low silver halide emulsion layers are arranged and three layers having different sensitivities are sequentially lowered toward the support. Even when it is composed of such three layers having different sensitivities, as described in JP-A-59-202464, in the same color-sensitive layer, the medium-sensitivity emulsion layer / high-sensitivity layer is separated from the side distant from the support. You may arrange in order of a speed emulsion layer / a low speed emulsion layer. In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. The arrangement may be changed as described above even in the case of four or more layers. In order to improve color reproducibility, BL, GL, described in US 4,663,271, 4,705,744, 4,707,436, JP-A-62-160448 and 63-89850, are described.
It is preferable that a donor layer (CL) having a multilayer effect having a spectral sensitivity distribution different from that of the main photosensitive layer such as RL is disposed adjacent to or close to the main photosensitive layer.

The preferred silver halide used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing less than about 30 mol% of silver iodide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide. Silver halide grains in photographic emulsions include those having regular crystals such as cubic, octahedral and tetradecahedral, those having irregular crystal forms such as spheres and plates, twin planes, etc. Or a composite form thereof. The grain size of silver halide is about 0.2 μm or less
It may be large-sized grains up to 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (hereinafter abbreviated as RD) No. 17643 (December 1978), 22-23.
Page, "I. Emulsion preparation and type
s) ”and ibid. No. 18716 (November 1979), p. 648, ibid N.
o.307105 (November 1989), pp.863-865, and Grafkid, "Physics and Chemistry of Photography", published by Paul Montell (P.Gl.
afkides, Chemie et Phisique Photographique, Paul M
ontel, 1967), Duffin, Photographic Emulsion Chemistry, Focal Press (GF Duffin, Photographic Emulsion C)
hemistry, Focal Press, 1966), "Manufacturing and coating of photographic emulsions" by Zelikmann et al., published by Focal Press (VL Ze
likman, et al., Making and Coating Photographic Em
ulsion, Focal Press, 1964).

US 3,574,628, US 3,655,394 and GB 1,4
Monodisperse emulsions described in 13,748 are also preferred. Tabular grains having an aspect ratio of about 3 or more can also be used in the present invention. Tabular grains are described in Gutof, Photographic Science and Engineering (Gutof
f, Photographic Science and Engineering), Volume 14
248-257 (1970); US 4,434,226, US 4,414,310,
It can be easily prepared by the methods described in 4,433,048, 4,439,520 and GB 2,112,157. The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, or may have a layered structure. Silver halides having different compositions may be joined by epitaxial joining, or may be joined to a compound other than silver halide, such as, for example, silver rhodanate or lead oxide. Also, a mixture of particles of various crystal forms may be used. The above emulsion is a surface latent image type that forms a latent image mainly on the surface,
Either an internal latent image type formed inside the grain or a type having a latent image both on the surface and inside may be used, but it is necessary that the emulsion is a negative type. Of the internal latent image types, JP-A-6
The core / shell type internal latent image type emulsion described in 3-264740 may be used, and its preparation method is described in JP-A-59-133542. The thickness of the shell of this emulsion varies depending on the development process, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion usually used is one subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such a process are RD No. 17643 and RD No. 187.
16 and No. 307105, and the relevant portions are summarized in the table below. In the light-sensitive material of the present invention, two or more types of emulsions having at least one characteristic different from each other in the grain size, grain size distribution, halogen composition, grain shape and sensitivity of the photosensitive silver halide emulsion are mixed in the same layer. Can be used. US Pat. No. 4,082,553, the surface of which is covered with silver halide grains, US Pat. No. 4,626,498, and JP-A-59-21.
4852, a silver halide grain in which the inside of the grain is fogged,
It is preferred to apply colloidal silver to the light-sensitive silver halide emulsion layer and / or the substantially light-insensitive hydrophilic colloid layer. The fogged silver halide grain inside or on the surface means a silver halide grain which enables uniform (non-imagewise) development regardless of the unexposed area and exposed area of the light-sensitive material. , Its preparation method is described in US 4,626,498 and JP-A-59-214852. The silver halide forming the internal nucleus of the core / shell type silver halide grain having the inside of the grain fogged may have a different halogen composition.
As the silver halide having the inside or surface of the grain fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The average grain size of these fogged silver halide grains is 0.01 to 0.75 μm,
Particularly, the thickness is preferably 0.05 to 0.6 μm. The grains may be regular grains or polydispersed emulsions, but may be monodisperse (at least 95% of the weight or the number of silver halide grains).
% Having a particle diameter within ± 40% of the average particle diameter).

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is silver halide fine grains that are not exposed during imagewise exposure to obtain a dye image and are not substantially developed in the developing process, and are preferably not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and / or silver iodide, if necessary. Preferably, it contains 0.5 to 10 mol% of silver iodide. Fine grain silver halide has an average grain size (average value of circle equivalent diameter of projected area)
Is preferably 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. Fine grain silver halide can be prepared by the same method as that for ordinary photosensitive silver halide. The surface of the silver halide grains does not need to be optically sensitized, and no spectral sensitization is required. However, prior to adding this to the coating solution, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound in advance. Colloidal silver can be contained in the layer containing fine silver halide grains. Coated silver amount of the light-sensitive material of the present invention is preferably 6.0 g / m ² or less, 4.5 g / m ² or less is most preferred.

The photographic additives that can be used in the present invention are also described in RD, and the relevant portions are shown in the following table. Type of additive RD17643 RD18716 RD307105 Chemical sensitizer page 23, page 648, right column, page 866 2. Sensitivity enhancer page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column 866 to 868 Super sensitizer, page 649, right column 4. Brightener 24 page 647, right column page 868 5 Light absorbers, pages 25 to 26, page 649, right column, page 873 Filters, page 650, left column Dyes, ultraviolet absorbers 6. Binders, page 26, page 651, left column 873 to 874 7. Plasticizers, page 27, page 650, right Column 876 Lubricant 8. Coating aid, pages 26 to 27 Page 650 Right column 875 to 876 Surfactant 9. Static 27 page 650 650 Right column 876 to 877 Inhibitor 10. Mast agent 878 to 879

Various dye-forming couplers can be used in the light-sensitive material of the present invention, and the following couplers are particularly preferable. Yellow couplers: Couplers represented by formulas (I) and (II) of EP 502,424A; couplers represented by formulas (1) and (2) of EP 513,496A (particularly Y-28 on page 18); EP 568,037A5 Claim 1
A coupler represented by the formula (I) in US Pat. No. 5,066,576, column 1, lines 45 to 55; a coupler represented by the formula (I) in paragraph 0008 of JP-A-4-274425; A coupler according to claim 1 of EP 498,38A1 on page 40 (particularly D-35 on page 18); a coupler of formula (Y) on page 4 of EP 447,969A1 (especially Y-1 (page 17), Y -54 (p. 41)); US
Couplers represented by formulas (II) to (IV) at 4,476,219, column 7, lines 36 to 58 (especially II-17,19 (column 17), II-24 (column 19)). Magenta coupler; JP-A-3-39737 (L-57 (page 11, lower right), L-
68 (lower right of page 12), L-77 (lower right of page 13); EP 456,257 (A-4
-63 (p. 134), (A-4) -73, -75 (p. 139); EP 486,965
M-4, -6 (page 26), M-7 (page 27); EP 571,959A M-45 (19
(M-1) of JP-A-5-204106 (page 6); M-22 of paragraph 0237 of JP-A-4-32631. Cyan coupler: CX-1,3,4,5,11,12,1 of JP-A-4-204843
4,15 (pages 14 to 16); C-7,10 (page 35) of JP-A-4-43345, 3
4,35 (page 37), (I-1), (I-17) (pages 42 to 43); JP-A-6-67385
A coupler represented by the general formula (Ia) or (Ib) according to claim 1. Polymer coupler: P-1, P-5 (p. 11) of JP-A-2-44345.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US 4,366,237, GB 2,125,570, EP 96,570,
Those described in DE 3,234,533 are preferred. Couplers for correcting unnecessary absorption of color-forming dyes are yellow colored cyan couplers represented by the formulas (CI), (CII), (CIII), and (CIV) described on page 5 of EP 456,257A1 (especially on page 84). YC-86), the EP
Yellow colored magenta coupler ExM-7 (202
), EX-1 (page 249), EX-7 (page 251), US 4,833,069
Magenta colored cyan coupler CC-9 (column
8), CC-13 (column 10), (2) of US 4,837,136 (column 8),
Colorless masking couplers of formula (A) in claim 1 of WO 92/11575 (especially the exemplified compounds on pages 36 to 45) are preferred. Examples of the compound (including a coupler) which releases a photographically useful compound residue by reacting with an oxidized developing agent include the following. Development inhibitor releasing compound: EP 37
Compounds represented by the formulas (I), (II), (III) and (IV) described on page 11 of 8,236A1 (especially T-101 (page 30), T-104 (page 31), T-113 ( 36
T-131 (p. 45), T-144 (p. 51), T-158 (p. 58)), EP436, 93
Compounds of formula (I) described on page 7 of 8A2 (particularly D-4
9 (page 51)), compounds represented by formula (1) of EP 5,68,037A (particularly (23) (page 117)), formulas (I) and (II of EP 440,195A2 on pages 5 to 6 ), (III) (especially page 29, I-
(1)); Bleaching accelerator releasing compounds: compounds represented by formulas (I) and (I ′) on page 5 of EP 310,125A2 (especially (60) and (6) on page 61)
1)) and the compound represented by formula (I) of claim 1 of JP-A-6-59411 (particularly (7) (page 7)); Ligand releasing compound: US
Compound represented by LIG-X described in claim 1 of 4,555,478 (especially compound on lines 21 to 41 of column 12); Leuco dye-releasing compound: compound 1 of columns 3 to 8 of US 4,749,641
~ 6; Fluorescent dye-releasing compound: C in claim 1 of US 4,774,181
Compounds represented by OUP-DYE (particularly compounds 1 to 11 in columns 7 to 10); development accelerator or fogging agent releasing compound: US
4,656,123, the compounds of formulas (1), (2) and (3) in column 3 (especially (I-22) in column 25) and EP 450,637A2
ExZK-2, p. 75, lines 36-38; Compound which releases a group which becomes a dye only when it is cleaved: Formula (I) of claim 1 of US 4,857,447
(Especially Y-1 to Y-19 in columns 25 to 36)
.

As the additives other than the coupler, the following are preferable. Dispersion medium of oil-soluble organic compound: P-3,5, JP-A-62-215272
16,19,25,30,42,49,54,55,66,81,85,86,93 (140-144
Page); Latex for impregnation of oil-soluble organic compounds: US 4,199,
Latex described in 363; Oxidized developer scavenger: a compound represented by the formula (I) in column 2, lines 54 to 62 of US Pat. ) (Column 4-
5), US Pat. No. 4,923,787, columns 5 to 10 of formula (particularly compound 1 (column 3); stain inhibitor: EP 298321A 4
Formulas (I) to (III) on page 30-33, especially I-47, 72, III-1, 27 (24
-48 pages); Anti-fading agent: A-6, 7, 20, 21, 23, 2 of EP 298321A
4,25,26,30,37,40,42,48,63,90,92,94,164 (69-118
P.), US 5,122,444, columns 25-38 II-1 to III-23, especially
III-10, EP 471347A I-1 to III-4 on pages 8 to 12, especially II-
2, US 5,139,931 columns 32-40 A-1 to 48, especially A-39,
42; Material that reduces the amount of color enhancer or color mixture inhibitor used: I-1 to II-15 on pages 5 to 24 of EP 411324A, especially I-4
6; Formalin scavenger: EP 477932A, pages 24 to 29 SCV-1 to 28, especially SCV-8; Hardener: JP-A 1-214845
Formulas in columns 13-23 of H-1,4,6,8,14, US 4,618,573 on page 17
Compounds (H-1 to 54) represented by (VII) to (XII),
214852, page 8, lower right, compound represented by formula (6) (H-1 to 7
6), especially the compound described in claim 1 of H-14, US 3,325,287; Development inhibitor precursor: P-2 of JP-A-62-168139
4,37,39 (pages 6-7); compounds as claimed in claim 1 of US 5,019,492, in particular column 7, 28,29; preservatives, fungicides: US
4,923,790 columns 3 to 15 I-1 to III-43, especially II-1,
9,10,18, III-25; Stabilizer, antifoggant: US 4,923,79
I-1 to (14) in columns 6 to 16 of 3, especially I-1,60, (2), (13), U
S 4,952,483 columns 25-32 compounds 1-65, especially 36:
Chemical sensitizer: triphenylphosphine selenide, compound 50 of JP-A-5-40324; dye: 15-18 of JP-A-3-156450
A-1 to b-20, especially a-1,12,18,27,35,36, b-5,27 to 29
Pages V-1 to 23, especially V-1, EP 445627A pages 33 to 55 FI-
1 to F-II-43, especially FI-11, F-II-8, EP 457153A 17 to 28
Pages III-1 to 36, especially III-1,3, WO 88/04794 8-26
Microcrystalline dispersion of Dye-1 to 124, compounds 1 to 22 of EP 319999A, pages 6 to 11, especially compound 1, compounds D-1 to 87 (3) represented by formulas (1) to (3) of EP 519306A. ~ Page 28), US 4,26
8,622 compounds represented by the formula (I) (columns 3 to 1)
0), compounds (1) to (4) of US Pat.
(31) (Columns 2 to 9); UV absorber: Formula of JP-A-46-3335
Compounds (18b) to (18r), 101 to 427 (6 to
9), and the compounds (3) to (6) represented by the formula (I) in EP 520938A.
6) (Pages 10 to 44) and compound HBT-1 represented by formula (III)
~ 10 (page 14), a compound represented by formula (1) in EP 521823A
(1) to (31) (columns 2 to 9).

The present invention can be applied to various color light-sensitive materials such as color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. In addition, Japanese Patent Publication No.
Suitable for the lens-fitted film unit described in 3-39784. Suitable supports that can be used in the present invention are
For example, the RD. Page 28 of No.17643, 6 of No.18716
From page 47, right column to page 648, left column, and No. 307105, page 879. In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, and 18 μm or less.
m or less, more preferably 16 μm or less. Further, the film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. T _1/2 is the time required for the film thickness to reach 1/2 when the saturated film thickness is 90% of the maximum swollen film thickness reached when the color developing solution is processed at 30 ° C. for 3 minutes and 15 seconds. Is defined. The film thickness means the film thickness measured at 25 ° C. and 55% relative humidity (2 days), and T _1/2 is A Green (A.Gr
een) et al., Photographic Science and Engineering (Photogr.Sci.Eng.), 19 volumes, 2,124 ~
It can be measured by using a swellometer (swelling meter) of the type described on page 129. T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swelling film thickness under the conditions described above by the following formula: (maximum swelling film thickness-film thickness) / film thickness. In the light-sensitive material of the present invention, a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm is preferably provided on the side opposite to the side having the emulsion layer. The back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, and surfactant. The swelling ratio of the back layer is preferably from 150 to 500%.

The light-sensitive material of the present invention has the RD. No.176
No. 18716, No. 18716, left column to right column, and No. 18716
No. 307105, pages 880 to 881 can be used for development. The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution mainly containing an aromatic primary amine color developing agent. Aminophenol compounds are also useful as the color developing agent, but p-phenylenediamine compounds are preferably used.Typical examples and preferred examples thereof are compounds described in EP 556700A, page 28, lines 43 to 52. Is mentioned. These compounds can be used in combination of two or more depending on the purpose. The color developing solution is an alkali metal carbonate,
PH buffers such as borates or phosphates, and development inhibitors or antifoggants such as chlorides, bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds. General. Also, as required, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazide, triethanolamine, various preservatives such as catecholsulfonic acid, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol,
Development accelerators such as polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competing couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids, aminopolyphosphones. Acid, alkylphosphonic acid, various chelating agents represented by phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene- 1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid,
Ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and their salts are added.

When the reversal processing is carried out, black and white development is usually carried out before color development. In this black-and-white developer, known black-and-white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol are used alone. Alternatively, they can be used in combination. The pH of these color developing solutions and black-and-white developing solutions is generally 9 to 12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per square meter of the photographic material, and is reduced to 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also. When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. The processing effect due to the contact between the photographic processing solution and the air in the processing tank is determined by the aperture ratio (= [the contact area between the processing solution and the air c
m ² ] ÷ [volume of treatment liquid cm ³ ]). This aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0.05. As a method for reducing the aperture ratio, in addition to providing a cover such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033 and JP-A-63-216050 are disclosed. The slit development processing method described can be mentioned. The aperture ratio is preferably reduced not only in both the color development and black-and-white development steps but also in the following various steps, for example, in all the steps such as bleaching, bleach-fixing, fixing, washing and stabilization. The amount of replenishment can also be reduced by using means for suppressing the accumulation of bromide ions in the developer. The time for color development processing is usually set between 2 and 5 minutes, but by using high temperature, high pH, and using a high concentration of color developing agent,
Further, the processing time can be reduced.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Further, processing in two successive bleach-fixing baths, fixing before bleach-fixing, or bleaching after bleach-fixing can be arbitrarily performed according to the purpose. As the bleaching agent, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. Typical bleaching agents include organic complex salts of iron (III) such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid and glycol etherdiaminetetraacetic acid. Polycarboxylic acids or complex salts of citric acid, tartaric acid, malic acid and the like can be used. Of these, aminopolycarboxylic acid iron (III) complex salts including ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminopropanetetraacetic acid iron (III) complex salts are preferable from the viewpoint of rapid treatment and prevention of environmental pollution. . Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in a bleaching solution and a bleach-fixing solution. The pH of a bleaching solution or a bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8, but a lower pH can be used for speeding up the processing.

In the bleaching solution, the bleach-fixing solution and the prebath thereof, a bleaching accelerator can be used if necessary.
Specific examples of useful bleach accelerators are described in the following specifications: US 3,893,858, DE 1,290,812, 2,059,988, JP-A-53-32736, 53-57831, 53-37418, 53-72623. ,
53-95630, 53-95631, 53-104232, 53-12442
4, Compounds 53-141623, 53-28426 and RD No. 17129 (July 1978), compounds having a mercapto group or a disulfide group; thiazolidine derivatives described in JP-A-50-140129; , JP-A-52-20832, JP-A-53-32735,
Thiourea derivatives described in US 3,706,561; DE 1,127,715,
Iodide salts described in JP-A-58-16,235; DE 966,410,
2,748,430, polyoxyethylene compounds; JP-B-45-8836, polyamine compounds; and others, JP-A-49-4
0,943, 49-59,644, 53-94,927, 54-35,727,
Compounds described in JP-A-55-26,506 and JP-A-58-163,940; bromide ions can be used. Among them, compounds having a mercapto group or a disulfide group are preferred in view of a large accelerating effect, and particularly, US 3,893,858, DE 1,290,812, and JP-A-53-95,63.
The compounds described in 0 are preferred. Further, compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography. The bleaching solution and the bleach-fixing solution preferably contain an organic acid in order to prevent bleaching stain in addition to the above compounds. Particularly preferred organic acids are compounds having an acid dissociation constant (pKa) of 2 to 5, specifically acetic acid, propionic acid, hydroxyacetic acid and the like. Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts, but thiosulfates are generally used. Yes, especially ammonium thiosulfate can be used most widely. Also,
Thiosulfates and thiocyanates, thioether compounds,
A combined use of thiourea is also preferable. As a preservative of the fixing solution or the bleach-fixing solution, a sulfite, a bisulfite, a carbonyl bisulfite adduct or a sulfinic acid compound described in EP 294769A is preferable. Furthermore, aminopolycarboxylic acids or organic phosphonic acids are preferably added to the fixing solution or the bleach-fixing solution for the purpose of stabilizing the solution. In the present invention, the fixer or the bleach-fixer contains a compound having a pKa of 6.0 to 9.0 for pH adjustment, preferably an imidazole such as imidazole, 1-methylimidazole, 1-ethylimidazole or 2-methylimidazole. It is preferable to add 0.1 to 10 mol per liter.

The total time of the desilvering process is preferably as short as possible so long as no desilvering failure occurs. Preferred time is 1 minute to 3
Minutes, more preferably 1 to 2 minutes. The processing temperature is from 25 ° C to 50 ° C, preferably from 35 ° C to 45 ° C. In a preferable temperature range, the desilvering speed is improved, and generation of stain after processing is effectively prevented. In the desilvering step, it is preferable that the stirring is strengthened as much as possible.
As a specific method of strengthening the stirring, a method of impinging a jet of a processing solution on the emulsion surface of the photosensitive material described in JP-A-62-183460, or a stirring effect using the rotating means of JP-A-62-183461 can be used. A method of raising the stirring effect by moving the photosensitive material while bringing the wiper blade provided in the liquid into contact with the emulsion surface, and making the emulsion surface turbulent. There is a method of increasing. Such a stirring improving means is effective for any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently increases the desilvering speed. Further, the above-mentioned means for improving the stirring is more effective when a bleaching accelerator is used, and can significantly increase the accelerating effect or eliminate the fixing inhibiting effect of the bleaching accelerator. The automatic developing machine used for the light-sensitive material of the present invention is disclosed in JP-A-60-191257,
It is preferable to have the photosensitive material conveying means described in 60-191258 and 60-191259. As described in the above-mentioned JP-A-60-191257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath, has a high effect of preventing the performance deterioration of the treatment liquid, and It is particularly effective in shortening the processing time and reducing the replenishment amount of the processing liquid.

The light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering process. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, the material used such as a coupler), the intended use, the rinsing water temperature, the number of rinsing tanks (number of stages), the replenishment method such as countercurrent, forward flow, and other various conditions. Can be set widely. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent system is described in the Journal of t
he Society of MotionPicture and Television Enginee
rs, Vol. 64, pages 248-253 (May 1955). According to the multi-stage countercurrent method described in this document, the amount of washing water can be significantly reduced, but bacteria increase due to the increase in the residence time of water in the tank, and the generated suspended matter adheres to the photosensitive material. Problem arises. As a solution to this problem, the method of reducing calcium and magnesium ions described in JP-A-62-288,838 is extremely effective. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8,542, chlorine-based germicides such as chlorinated sodium isocyanurate, and other benzotriazoles, Hiroshi Horiguchi, "Chemistry of antifungal agents"
(1986) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan Society of Antimicrobial and Antifungal Activities, "Encyclopedia of Antimicrobial and Antifungal Agents" (1986) The bactericides described can also be used. The pH of the washing water in the processing of the light-sensitive material of the present invention is from 4 to 9, preferably from 5 to 8.
The washing temperature and washing time can also be set according to the characteristics and application of the photosensitive material, but in general, the range is 20 seconds to 10 minutes at 15 to 45 ° C, preferably 30 seconds to 5 minutes at 25 to 40 ° C. . Furthermore,
The light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned water washing. In such stabilization treatment, known methods described in JP-A-57-8543, JP-A-58-14834, and JP-A-58-220345 can be applied. Further, there is a case where further stabilization treatment is carried out after the water washing treatment, and an example thereof is a stabilizing bath containing a dye stabilizer and a surfactant used as a final bath of a color light-sensitive material for photographing. You can Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine and aldehyde sulfite adducts. Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic developing machine or the like, when each of the above processing solutions is concentrated by evaporation,
It is preferable to correct the concentration by adding water. The light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing. In order to incorporate the color developing agent, it is preferable to use a precursor of a color developing agent. For example US 3,34
Indaniline compounds described in 2,597, 3,342,599,
Research Disclosure No.14,850 and No.15,
159, an aldol compound described in 13,924, a metal salt complex described in US 3,719,492,
The urethane compounds described in 53-135628 can be mentioned. The light-sensitive material of the present invention may optionally contain various 1-phenyl-3-pyrazolidones for the purpose of accelerating color development. Typical compounds are described in JP-A-56-64339,
57-144547 and 58-115438. The processing solution used for processing the photosensitive material of the present invention is 10 ° C to 50 ° C.
Used in Usually, a temperature of 33 ° C to 38 ° C is standard, but higher temperatures can accelerate the processing and shorten the processing time, and lower temperatures can improve the image quality and improve the stability of the processing solution. it can.

Next, the transparent magnetic recording layer used in the present invention will be described. The transparent magnetic recording layer used in the present invention is one in which an aqueous or organic solvent-based coating liquid in which magnetic particles are dispersed in a binder is coated on a support.
Magnetic particles used in the present invention include ferromagnetic iron oxide such as γFe ₂ O _3, Co deposited γFe ₂ O _3, Co-coated magnetite ,, Co
Containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metal,
Ferromagnetic alloy, hexagonal Ba ferrite, Sr ferrite,
Pb ferrite, Ca ferrite, etc. can be used. Co-deposited ferromagnetic iron oxides such as Co-deposited γFe ₂ O ₃ are preferred. The shape may be needle-like, rice grain-like, spherical, cubic, plate-like or the like. In terms of specific surface area, S _BET is preferably 20 m ² / g or more,
30 m ² / g or more is particularly preferable. Saturation magnetization (σs) of ferromagnet
Is preferably 3.0 × 10 ⁴ to 3.0 × 10 ⁵ A / m, particularly preferably 4.0 × 10 ^{4 to} 2.5 × 10 ⁵ A / m. The ferromagnetic particles may be subjected to a surface treatment with silica and / or alumina or an organic material. Further, the surface of the magnetic particles may be treated with a silane coupling agent or a titanium coupling agent as described in JP-A-6-161032.
In addition, the surface of the inorganic particles described in JP-A-4-259911 and 5-81652 is
Magnetic particles coated with an organic substance can also be used.

Next, the binder used for the magnetic particles is
Thermoplastic resin described in JP-A-4-219569, thermosetting resin,
Radiation-curable resins, reactive resins, acids, alkalis or biodegradable polymers, natural polymers (cellulose derivatives, sugar derivatives, etc.) and mixtures thereof can be used. The above resin has a Tg of -40 ° C to 300 ° C and a weight average molecular weight of 2,000 to 1,000,000. Examples thereof include vinyl copolymers, cellulose diacetate, cellulose triacetate, cellulose derivatives such as cellulose acetate propionate, cellulose acetate butyrate, and cellulose tripropionate, acrylic resins and polyvinyl acetal resins, and gelatin is also preferable. Particularly, cellulose di (tri) acetate is preferable. The binder can be cured by adding an epoxy-based, aziridine-based, or isocyanate-based crosslinking agent. Examples of the isocyanate-based crosslinking agent include isocyanates such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, and xylylene diisocyanate, and reaction products of these isocyanates with polyalcohol (for example, 3mol of isocyanate and 1m of trimethylolpropane
ol reaction product), and polyisocyanates formed by condensation of these isocyanates.
For example, it is described in JP-A-6-59357.

As a method for dispersing the above-mentioned magnetic material in the binder, a kneader, a pin type mill, an annular type mill or the like is preferable and a combination thereof is also preferable, as in the method described in JP-A-6-35092. Dispersants described in JP-A-5-088283 and other known dispersants can be used. The thickness of the magnetic recording layer is 0.1 μm to 10 μm, preferably 0.2 μm to 5 μm.
m, more preferably 0.3 μm to 3 μm. The weight ratio between the magnetic particles and the binder is preferably 0.5: 100 to 60: 100.
And more preferably from 1: 100 to 30: 100. The coating amount of the magnetic particles 0.005~ 3g / m ^2, preferably from 0.01 to 2
g / m ² , more preferably 0.02 to 0.5 g / m ² . The magnetic recording layer used in the present invention can be provided on the back surface of the photographic support by coating or printing and provided in the entire surface or in a stripe shape. As a method of applying the magnetic recording layer, an air doctor, a blade, an air knife, a squeeze, an impregnation, a reverse roll, a transfer roll, a gravure, a kiss,
Cast, spray, dip, bar, extrusion and the like can be used, and the coating liquid described in JP-A-5-341436 is preferable.

In the magnetic recording layer, improvement of lubricity, curl adjustment,
It may have functions such as antistatic, anti-adhesion and head polishing, or may be provided with another functional layer to impart these functions, and at least one kind of particles has a Mohs hardness of 5 or more. The above-mentioned non-spherical inorganic particle abrasives are preferable. As the composition of the non-spherical inorganic particles, oxides such as aluminum oxide, chromium oxide, silicon dioxide, titanium dioxide and silicon carbide, carbides such as silicon carbide and titanium carbide, and fine powders such as diamond are preferable. These abrasives may have their surfaces treated with a silane coupling agent or a titanium coupling agent. These particles may be added to the magnetic recording layer, or may be overcoated (for example, a protective layer, a lubricant layer, etc.) on the magnetic recording layer. As the binder used at this time, the above-mentioned binders can be used, and the same binder as the binder for the magnetic recording layer is preferable. For photosensitive materials having a magnetic recording layer, see US Pat.
5,229,259, 5,215,874 and EP 466,130.

Next, the polyester support used in the present invention will be described. For details including the light-sensitive material, processing, cartridges and examples described later, open technical report, official technique number 94-6023 (Invention Society; 1994.3). .15.).
The polyester used in the present invention is formed by using a diol and an aromatic dicarboxylic acid as essential components, and 2,6-, 1,5-, 1,4-, and 2,7 as aromatic dicarboxylic acids.
-Naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, diethylene glycol as diol,
Examples include triethylene glycol, cyclohexanedimethanol, bisphenol A, and bisphenol.
Examples of the polymerized polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Particularly preferred is a polyester containing 50 to 100 mol% of 2,6-naphthalenedicarboxylic acid. Among them, polyethylene 2,6-naphthalate is particularly preferred. Average molecular weight ranges from about 5,000 to
It is 200,000. The Tg of the polyester of the present invention is 50 ° C. or higher, preferably 90 ° C. or higher.

Next, the polyester support is subjected to a heat treatment at a heat treatment temperature of 40 ° C. or higher and lower than Tg, more preferably Tg−20 ° C. or higher and lower than Tg in order to prevent the curling tendency. The heat treatment may be performed at a constant temperature within this temperature range, or may be performed while cooling. The heat treatment time is 0.1 to 1500 hours, more preferably 0.5 to 200 hours. The heat treatment of the support may be performed in the form of a roll, or may be performed while transporting the support in the form of a web.
Surface irregularities may be imparted (for example, conductive inorganic fine particles such as SnO ₂ or Sb ₂ O ₅ may be applied) to improve the surface state. It is also desirable to take measures such as applying knurls to the ends and raising the ends only slightly to prevent cut-out of the core. These heat treatments are performed after forming the support, after surface treatment,
It may be carried out at any stage after application of the back layer (antistatic agent, slip agent, etc.) and after application of the undercoat. Preferably after application of the antistatic agent. An ultraviolet absorber may be incorporated into this polyester. Also, to prevent light piping,
The purpose can be achieved by kneading dyes or pigments commercially available for polyesters such as Diaresin manufactured by Mitsubishi Kasei and Kayaset manufactured by Nippon Kayaku.

Next, in the present invention, a surface treatment is preferably carried out in order to bond the support and the light-sensitive material constituting layer. Chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment,
Surface activation treatments such as laser treatment, mixed acid treatment, ozone oxidation treatment and the like can be mentioned. Among the surface treatments, ultraviolet irradiation treatment, flame treatment, corona treatment, and glow treatment are preferable. Next, the undercoating method will be described. It may be a single layer or two or more layers. As the binder for the undercoat layer, vinyl chloride, vinylidene chloride, butadiene, methacrylic acid,
Examples include a copolymer using a monomer selected from acrylic acid, itaconic acid, maleic anhydride and the like as a starting material, polyethylene imine, epoxy resin, grafted gelatin, nitrocellulose, and gelatin. Compounds that swell the support include resorcin and p-chlorophenol. As a gelatin hardening agent for the undercoat layer, chromium salts (chrome alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6-) are used.
Hydroxy-S-triazine, etc.), epichlorohydrin resin, active vinyl sulfone compound and the like. SiO ₂ , TiO ₂ , inorganic fine particles or polymethylmethacrylate copolymer fine particles (0.01 to 10 μm) may be contained as a matting agent.

In the present invention, an antistatic agent is preferably used. Examples of these antistatic agents include carboxylic acids and carboxylates, polymers containing sulfonates, cationic polymers, and ionic surfactant compounds. The most preferred antistatic agent is Z
_{nO, TiO 2, SnO 2,} Al 2 O 3, In 2 O 3, SiO 2, MgO, BaO,
MoO ₃ , at least one selected from V ₂ O ₅ has a volume resistivity of 10 ⁷ Ω · cm or less, more preferably 10 ⁵ Ω · cm or less. Fine particles of oxides or composite oxides thereof (Sb, P, B, In, S, Si, C, etc.), and sol-like metal oxides or fine particles of these composite oxides. The content in the photosensitive material should be between 5 and
500 mg / m ² are preferred and particularly preferably 10 to 350 mg / m ^2. The ratio of the amount of the conductive crystalline oxide or its composite oxide to the binder is preferably from 1/300 to 100/1, more preferably from 1/100 to 100/5.

The light-sensitive material of the present invention preferably has a slip property. The slip agent-containing layer is preferably used on both the photosensitive layer surface and the back surface. A preferable slip property is a dynamic friction coefficient of 0.
It is 25 or less and 0.01 or more. The measurement at this time represents the value when the stainless steel ball with a diameter of 5 mm is transported at 60 cm / min (25
℃, 60% RH). In this evaluation, even if the surface of the photosensitive layer is replaced as the partner material, the values are almost the same level. Examples of the slip agent usable in the present invention include polyorganosiloxanes, higher fatty acid amides, higher fatty acid metal salts, esters of higher fatty acids and higher alcohols, and polyorganosiloxanes such as polydimethyl siloxane, polydiethyl siloxane, poly Styrylmethylsiloxane, polymethylphenylsiloxane, or the like can be used. The additional layer is preferably the outermost layer of the emulsion layer or the back layer. Particularly, polydimethylsiloxane or an ester having a long-chain alkyl group is preferable.

The photosensitive material of the present invention preferably contains a matting agent. The matting agent may be on either the emulsion side or the back side, but is particularly preferably added to the outermost layer on the emulsion side.
The matting agent may be soluble in the processing solution or insoluble in the processing solution, and preferably both are used in combination. For example, polymethylmethacrylate, poly (methylmethacrylate / methacrylic acid = 9/1 or 5/5 (molar ratio)), polystyrene particles and the like are preferable. The particle size is preferably 0.8 to 10 μm, and the particle size distribution is preferably narrow, and the average particle size is 0.9 to 1.
It is preferable that 90% or more of the total number of particles be contained in one time. It is also preferable to simultaneously add fine particles having a size of 0.8 μm or less in order to enhance the matting property. For example, polymethyl methacrylate (0.2 μm), poly (methyl methacrylate /
Methacrylic acid = 9/1 (molar ratio, 0.3 µm)), polystyrene particles (0.25 µm), colloidal silica (0.03 µm).

Next, the film cartridge used in the present invention will be described. The main material of the patrone used in the present invention may be metal or synthetic plastic. Preferred plastic materials are polystyrene, polyethylene, polypropylene, polyphenyl ether and the like. Further, the patrone of the present invention may contain various antistatic agents, and carbon black, metal oxide particles, nonionic, anionic, cationic and betaine surfactants or polymers can be preferably used. These antistatic patrones are described in JP-A 1-312537 and JP-A 1-312538. Particularly, the resistance at 25 ° C. and 25% RH is preferably 10 ¹² Ω or less. Usually, a plastic patrone is manufactured using a plastic into which carbon black, a pigment, or the like is kneaded in order to impart light shielding properties. The size of the patrone may be 135 size at present, and for miniaturization of the camera,
It is also effective to reduce the diameter of the current 135 size 25 mm cartridge to 22 mm or less. The volume of the patrone case is preferably 30 cm ³ or less, more preferably 25 cm ³ or less. The weight of the plastic used for the patrone and the patrone case is preferably 5 g to 15 g.

Further, a patrone used in the present invention may be one that rotates the spool to feed the film. Further, a structure may be employed in which the leading end of the film is housed in the cartridge body, and the leading end of the film is sent out from the port of the cartridge by rotating the spool shaft in the film sending direction. These are disclosed in US Pat. Nos. 4,834,306 and 5,226,613. The photographic film used in the present invention may be a so-called raw film before development, or may be a photographic film subjected to development processing. Also, raw film and developed photographic film may be stored in the same new patrone,
Different patrones may be used.

[0116]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Example 1 (1) Preparation of emulsion (Preparation of seed emulsion) Aqueous solution containing 0.75 g of gelatin 15
00 ml was kept at 35 ° C. and stirred. The silver electrode was adjusted to -10 mV with respect to the saturated calomel electrode, and the pH was adjusted to 1.90. AgNO ₃ (0.85g) aqueous solution and KBr (0.59)
g) The aqueous solution was added by the double jet method over 15 seconds. After the temperature was raised to 60 ° C., 8.3 g of gelatin was added. After adjusting the pH to 5.5, the silver potential was adjusted to -20 mV with respect to the saturated calomel electrode. AgNO ₃ (227.
1 g) Aqueous solution and KBr aqueous solution were added over 45 minutes while accelerating the flow rate by the double jet method. At this time, the silver potential was kept at -20 mV against the saturated calomel electrode. After desalting, 50 g of gelatin was added and the pH was adjusted to 5.
8, pAg was adjusted to 8.8 to prepare a seed emulsion. This seed emulsion contains 1 mol of Ag and 8 mol of gelatin per kg of emulsion.
The tabular grains contained 0 g, had an average equivalent circle diameter of 0.71 μm, a variation coefficient of equivalent circle diameter of 17%, an average thickness of 0.081 μm, and an average aspect ratio of 8.8.

(Formation of core) 134 g of the above seed emulsion, KB
1,200 ml of an aqueous solution containing 1.9 g of r and 38 g of gelatin was kept at 65 ° C. and stirred. After adding 1.4 × 10 ^-5 mol of thiourea dioxide per mol of silver, AgNO ₃ (4
The 3.9 g) aqueous solution and the KBr aqueous solution were added over 23 minutes while accelerating the flow rate by the double jet method. At this time, the silver potential was kept at -20 mV against the saturated calomel electrode.

(Formation of First Shell) After the formation of the core particles, an AgNO ₃ (43.9 g) aqueous solution and a KBr aqueous solution containing KI were added over 19 minutes while accelerating the flow rate by the double jet method. At this time, the silver potential was kept at -20 mV against the saturated calomel electrode.

(Formation of Second Shell) After the formation of the first shell, an AgNO ₃ (42.6 g) aqueous solution and a KBr aqueous solution containing KI were added over 8 minutes while accelerating the flow rate by the double jet method. At this time, the silver potential was kept at +20 mV with respect to the saturated calomel electrode.

(Formation of Third Shell) After the formation of the second shell, benzenethiosulfonic acid is added in an amount of 2.2 × 10 ⁻⁴ mol per unit mol of silver, and an aqueous KBr solution is added to adjust the silver potential. Adjusted to -80 mV. Average circle equivalent diameter 0.025μ
m, a silver iodide fine grain emulsion having a coefficient of variation of equivalent circle diameter of 18% is 5
Within a second, 8.5 g of AgNO ₃ was added rapidly.

(Formation of Fourth Shell) Thirty seconds after the above silver iodide fine grain emulsion was added, an aqueous AgNO ₃ (66.4 g) solution was added over 4 minutes while reducing the flow rate. Iridium potassium hexachloride was added on the way. The silver potential after the addition was -10 mV. Normal washing was performed, gelatin was added, and the pH was adjusted to 5.9 and pAg 8.7 at 40 ° C. This emulsion was designated as Emulsion A. Emulsion A-1 had an average equivalent circle diameter of 1.40 μm, a variation coefficient of equivalent circle diameter of 20%, an average thickness of 0.16 μm, an average aspect ratio of 8.8, an average equivalent spherical diameter of 0.78 μm, and a variation coefficient of equivalent spherical diameter of 18. % Tabular grains. Further, particles having an aspect ratio of 8 or more occupied 88% of the total projected area. For emulsion A, after the formation of the second shell, the third shell was formed without adding benzenethiosulfonic acid.
Emulsion B by forming shell and fourth shell
Was prepared.

(Emulsion A-1 to A-9 and Emulsion B-1 to
Preparation of B-9) Emulsion A and Emulsion B were desalted by a usual flocculation method and then heated to 56 ° C. to obtain sensitizing dyes I, II and III and compound I, potassium thiocyanate and chloroauric acid. , Sodium thiosulfate and N, N-dimethylselenourea were added for optimum chemical sensitization. This emulsion was designated as Emulsion A-1 and Emulsion B-1.

[0123]

Embedded image

After the emulsion A-1 was chemically sensitized, the compounds shown in Table 1 below were added to the emulsion A-1 at a concentration of 6 × per mol mol of silver.
Emulsions A-2 to A-5 were obtained by adding 10 ^-6 mol. Further, to the emulsion A-1, after desalting by a usual flocculation method and before chemical sensitization, 6 × 10 ^-6 mol per mol of silver is added to the compounds shown in Table 1 below. Thus, emulsions A-6 to A-9 were obtained. Emulsions B-2 to B-5 were obtained by chemically sensitizing Emulsion B-1 and then adding the compounds shown in Table 1 below at 6 × 10 ⁻⁶ mol per mol mol of silver. For emulsion B-1,
After desalting by an ordinary flocculation method and before chemical sensitization, the compounds shown in Table 1 below are added in an amount of 6 × 10 ^-6 mol per mol of silver to prepare emulsions B-6 to B-.
9 was obtained. The compounds added and the timing of addition for each emulsion are shown in Table 2 below.

(2) Coating of photosensitive layer

On the cellulose triacetate film support provided with an undercoat layer, the above emulsions A-1 to A-9 and emulsions B-1 to B-9 were provided with protective layers under the coating conditions shown in Table 1 below. And applied to prepare samples 101 to 118.

[0127]

[Table 1]

These samples were exposed for sensitometry (1/100 seconds) and subjected to the following color development processing.

Treatment method Treatment time Treatment temperature Complementary amount Tank capacity Color development 2 minutes 45 seconds 38 ℃ 33ml 20 liters Bleach 6 minutes 30 seconds 38 ℃ 25ml 40 liters Water wash 2 minutes 10 seconds 24 ℃ 1200ml 20 liters Fixed amount 4 minutes 20 seconds 38 ℃ 25ml 30 liters Washing with water (1) 1 minute 05 seconds 24 ℃ From (2) to (1) 10 liters countercurrent piping system Washing with water (2) 1 minute 00 seconds 24 ℃ 1200ml 10 liters Safety 1 Minutes 05 seconds 38 ℃ 25ml 10 liters Dry 4 minutes 20 seconds 55 ℃ Replenishment amount is 35mm width 1m length. The composition of the treatment liquid is described below. (Color developer) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 3.2 Sodium sulfite 4.0 4.4 Potassium carbonate 30.0 37.0 Potassium bromide 1.4 0.7 Potassium iodide 1.5 mg-hydroxylamine sulfate 2.4 2.8 4- [N-ethyl-N-β-hydroxyethylamino] -2 -Methylaniline sulfate 4.5 5.5 Add water 1.0 liter 1.0 liter pH 10.05 10.05 (bleaching solution) Mother liquor (g) Replenishing solution (g) Ethylenediaminetetraacetic acid sodium ferric acid Trihydrate 100.0 120.0 Ethylenediaminetetraacetic acid disodium salt 10.0 11.0 Ammonium bromide 140.0 160.0 Ammonium nitrate 30.0 35.0 Ammonia water 27%) 6.5 ml 4.0 ml Add water 1.0 liter 1.0 liter pH 6.0 5.7 (fixer) Mother liquor (g) Replenisher (g) Ethylenediaminetetraacetic acid sodium salt 0.5 0 .7 Sodium sulfite 7.0 8.0 Sodium bisulfite 5.0 5.5 Ammonium thiosulfate aqueous solution (70%) 170.0 ml 200.0 ml Water was added to 1.0 liter 1.0 liter pH 6.7 6. 6 (Stabilizer) Mother liquor (g) Replenisher (g) Formalin (37%) 2.7 ml 3.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 0.45 Ethylenediamine-4 Acetic acid disodium salt 0.05 0.08 Add water 1.0 liter 1.0 liter pH 5.8-8.0 5.8-8.0

The density of the treated sample was measured with a green filter. The sensitivity was defined as the reciprocal of the exposure dose that gave a density 0.2 higher than the fog density, and the sensitivity of each sample was expressed as a relative value with the value of Sample 101 as 100. Next, the following processing was performed in order to evaluate the fogging with time of each sample. Each sample was aged in an atmosphere of a temperature of 50 ° C. and a relative humidity of 30% for 14 days, and then subjected to sensitometric exposure and color development processing in the same manner as above, and compared with the data exposed without aging, the fog density was compared. The difference was defined as the width of fog over time. The results thus obtained are shown in Table 2.

[0131]

[Table 2]

From Table 2, it can be seen that the samples of the present invention have low fog and high sensitivity. Furthermore, it can be seen that the samples of the present invention show a very small increase in fog concentration over time. Example 2 1) Preparation of support The support used in this example was prepared by the following method. Polyethylene-2,6-naphthalate polymer 1
After drying 00 parts by weight and 2 parts by weight of Tinuvin P.326 (manufactured by Ciba-Geigy Co., Ltd.) as an ultraviolet absorber, they were melted at 300 ° C. and extruded from a T-shaped die,
The film was stretched 3.3 times at 0 ° C, and then stretched at 130 ° C.
The film was stretched three times in the horizontal direction, and heat-set at 250 ° C. for 6 seconds to obtain a PEN film having a thickness of 90 μm. This PE
Blue dye, magenta dye and yellow dye are used for the N film (I-1, I-4, I-6, I-24, I-26, I-2 described in Kokai Giho No. 94-6023).
7, II-5) was added in an appropriate amount. Further, the support was wound around a stainless steel core having a diameter of 20 cm to give a heat history of 110 ° C. and 48 hours, thereby providing a support with which a winding habit was not easily formed.

2) Coating of Undercoat Layer The above-mentioned support was subjected to corona discharge treatment, UV discharge treatment and glow discharge treatment on both sides thereof, and then gelatin 0.1 g / m ² and sodium α-on each side. Sulfodi-2-ethylhexyl succinate 0.01 g / m ² , salicylic acid 0.04 g / m ² , p-chlorophenol 0.2 g / m ² ,
(CH ₂ = CHSO ₂ CH ₂ CH ₂ NHCO) ₂ CH ₂ 0.012 g / m ² , polyamide-epichlorohydrin polycondensate 0.02 g / m ² undercoat liquid was applied (10 cc / m ² , using a bar coder) ), An undercoat layer was provided on the high-temperature side during stretching. Drying was carried out at 115 ° C. for 6 minutes (all rollers and transport devices in the drying zone were 1
15 ° C).

3) Coating of Back Layer After the undercoating, an antistatic layer having the following composition, a magnetic recording layer, and a sliding layer were coated as back layers on one surface of the support.

3-1) Coating of Antistatic Layer A dispersion of fine particle powder having a specific resistance of 5 Ω · cm of a tin oxide-antimony oxide composite having an average particle size of 0.005 μm (secondary agglomerated particle size of about 0.08 μm). ) and 0.2 g / m ^2, gelatin _{^{0.05g / m 2, (CH 2}} = CHSO 2 CH 2 CH 2 NHCO) 2 CH 2 0.02
It was coated with g / m ² , poly (degree of polymerization 10) oxyethylene-p-nonylphenol 0.005 g / m ² and resorcin.

3-2) Coating of magnetic recording layer Cobalt-γ-iron oxide coated with 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by weight) (specific surface area: 43 m ² / G, long axis 0.
14 μm, uniaxial 0.03 μm, saturation magnetization 89 emu /
g, Fe ²⁺ / Fe ³⁺ = 6/94, the surface is treated with aluminum oxide silicon oxide at 2% by weight of iron oxide) 0.06 g
/ M ² of diacetyl cellulose 1.2 g / m ² (iron oxide was dispersed by an open kneader and a sand mill), C ₂ H ₅ C (CH ₂ OCONH-C ₆ H ₃ (CH ₃ ) NCO) as a curing agent ₃ 0.3 g / m ²
Was applied with a bar coater using acetone, methyl ethyl ketone, and cyclohexanone as a solvent to obtain a film thickness of 1.2.
A μm magnetic recording layer was obtained. Silica particles (0.3 μm) and 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by weight) as a matting agent
Aluminum oxide (0.15 μm) as an abrasive coated with
Were added so that the respective amounts would be 10 mg / m ² . Drying is 1
It was carried out at 15 ° C for 6 minutes (115 ° C for all rollers and conveying devices in the drying zone). X- light (blue filter) The increase of the color density of about 0.1 D ^B of the magnetic recording layer in,
The saturation magnetization moment of the magnetic recording layer is 4.2 emu /
g, the coercive force was 7.3 × 10 ⁴ A / m, and the squareness ratio was 65%.

3-3) Preparation of sliding layer Diacetyl cellulose (25 mg / m ² ), C ₆ H ₁₃ CH (OH) C ₁₀
H ₂₀ COOC ₄₀ H ₈₁ (compound a, 6 mg / m ² ) / C ₅₀ H ₁₀₁ O (CH ₂ CH
₂ O) ₁₆ H (compound b, 9 mg / m ² ) mixture was applied. This mixture was prepared by pouring and dispersing it in xylene / propylene monomethyl ether (10-fold amount), and then added to a dispersion (average particle size: 0.01 μm) in acetone. 15 mg each of silica particles (0.3 μm) as a matting agent and aluminum oxide (0.15 μm) coated with an abrasive 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by weight) / M ²
Was added so that Drying was performed at 115 ° C. for 6 minutes (all rollers and conveying devices in the drying zone were 115 ° C.).
° C). The sliding layer has a dynamic friction coefficient of 0.06 (stainless steel hard ball of 5 mmφ, load of 100 g, speed of 6 cm / min), a static friction coefficient of 0.07 (grip method), and a kinetic friction coefficient of an emulsion surface and a sliding layer described later of 0.12. Excellent characteristics.

4) Coating of Photosensitive Layer Next, on the opposite side of the back layer obtained above, each layer having the following composition was multilayer coated to prepare a color negative film.
This is designated as Sample 201.

(Photosensitive layer composition) The main materials used for each layer are classified as follows: ExC: Cyan coupler ExV: UV absorber ExM: Magenta coupler HBS: High boiling organic solvent ExY: Yellow coupler H: Gelatin hardening agent ExS: Sensitizing dye The number corresponding to each component indicates the coating amount expressed in g / m ² , and for silver halide, the coating amount in terms of silver is mol.
Expressed in units. Regarding the sensitizing dye, the coating amount per mol of silver halide in the same layer is shown in mol.

First Layer (Antihalation Layer) Black Colloidal Silver Silver 0.09 Gelatin 1.60 ExM-1 0.12 ExF-1 2.0 × 10 ^-3 Solid Disperse Dye ExF-2 0.030 Solid Disperse Dye ExF-3 0.040 HBS-1 0.15 HBS- 2 0.02

Second layer (intermediate layer) Silver iodobromide emulsion N silver 0.065 ExC-2 0.04 polyethyl acrylate latex 0.20 gelatin 1.04

Third Layer (Low-Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide emulsion C Silver 0.25 Silver iodobromide emulsion D Silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-6 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87

Fourth Layer (Medium-Sensitivity Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion 0.25 0.25 ExS-1 3.5 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.1 × 10 ^-4 ExC-1 0.13 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.015 ExC-6 0.0070 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.75

Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion F Silver 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.10 ExC-3 0.045 ExC-6 0.020 ExC-7 0.010 Cpd-2 0.050 HBS-1 0.22 Gelatin 1.10

Sixth layer (intermediate layer) Cpd-1 0.090 Solid disperse dye ExF-4 0.030 HBS-1 0.050 Polyethyl acrylate latex 0.15 Gelatin 1.10

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide emulsion G Silver 0.15 Silver iodobromide emulsion H Silver 0.10 Silver iodobromide emulsion I Silver 0.10 ExS-4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73

Eighth Layer (Medium-Sensitivity Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion J Silver 0.80 ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-6 8.4 × 10 ^-4 ExC-8 0.010 ExM-2 0.10 ExM-3 0.025 ExY-1 0.018 ExY-4 0.010 HBS-1 0.13 HBS-3 4.0 × 10 ^-3 Gelatin 0.80

Ninth layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion A-1 Silver 1.25 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC- 1 0.010 ExM-1 0.020 ExM-4 0.025 ExM-5 0.040 Cpd-3 0.040 HBS-1 0.25 Polyethyl acrylate latex 0.15 Gelatin 1.33

10th layer (yellow filter layer) Yellow colloidal silver Silver 0.015 Cpd-1 0.16 Solid disperse dye ExF-5 0.060 Solid disperse dye ExF-6 0.060 Oil-soluble dye ExF-7 0.010 HBS-1 0.60 Gelatin 0.60

Eleventh layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion K Silver 0.09 Silver iodobromide emulsion L Silver 0.09 ExS-7 8.6 × 10 ^-4 ExC-8 7.0 × 10 ^-3 ExY-1 0.050 ExY-2 0.22 ExY-3 0.50 ExY-4 0.020 Cpd-2 0.10 Cpd-3 4.0 × 10 ^-3 HBS-1 0.28 Gelatin 1.20

12th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion M Silver 1.40 ExS-7 5.4 × 10 ^-4 ExY-2 0.10 ExY-3 0.10 ExY-4 0.010 Cpd-2 0.10 Cpd-3 1.0 × 10 ^-3 HBS-1 0.070 Gelatin 0.70

13th layer (first protective layer) UV-1 0.19 UV-2 0.075 UV-3 0.065 HBS-1 5.0 × 10 ^-2 HBS-4 5.0 × 10 ^-2 gelatin 1.8

14th layer (second protective layer) Silver iodobromide emulsion N silver 0.10 H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.15 B-3 0.05 S-1 0.20 Gelatin 0.70

Further, in order to improve the storability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property of each layer, W-1 to W-3, B-4 to B- may be used.
6, F-1 to F-17, and iron salt, lead salt, gold salt, platinum salt, palladium salt, iridium salt, and rhodium salt. Table 3 for emulsions A-1 and emulsions C-N
It was shown to.

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[Table 3]

In Table 3, (1) Emulsion A-1 has the same meaning as Emulsion A-1 of Example 1. (2) Emulsions K to M were reduction-sensitized at the time of grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938. (3) Emulsions C to J were subjected to gold sensitization and sulfur sensitization selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. There is. (4) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. (5) Dislocation lines as described in JP-A-3-237450 are observed in the tabular grains by using a high voltage electron microscope. (6) Emulsion M is a double-structured grain containing an internal high iodine core described in JP-A-60-143331.

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(Preparation of Samples 202 to 214) Sample 201
Samples 202 to 218 were prepared by changing the emulsions for the ninth layer from the emulsions A-2 to A-9 and emulsions B-1 to B-9 in Example 1.

These samples were exposed for sensitometry (1/100 second) and subjected to the following color development processing.

(Processing step) Step Processing time Processing temperature Replenishment amount ^* Tank capacity Color development 3 minutes 5 seconds 37.8 ℃ 20ml 11.5 liter Bleach 50 seconds 38 ℃ 5ml 5 liter Bleach fixing (1) 50 seconds 38 ℃ -5 liter Bleach Fixing (2) 50 seconds 38 ℃ 8ml 5 liters Water wash 30 seconds 38 ℃ 17ml 3 liters Stability (1) 20 seconds 38 ℃ − 3 liters Stability (2) 20 seconds 38 ℃ 15ml 3 liters Dry 1 minute 30 seconds 60 ℃ * Replenishment amount is 35mm width 1.1m per length (equivalent to 24Ex. 1) Stabilizer and fixer are countercurrent method from (2) to (1), and all overflow liquid of washing solution is fixed Introduced into bath (2). The amount of developing solution brought into the bleaching process, the amount of bleaching solution brought into the fixing process, and the amount of fixing solution brought into the washing process were 2.5 ml per 35 mm width of the light-sensitive material and 1.1 m, respectively.
It was 2.0 ml and 2.0 ml. The crossover time is 6 seconds in all cases, and this time is included in the processing time of the previous step. Open area 100 cm ² in the color developing solution in the processing machine, 120 cm ² in the bleaching solution, the other processing solutions 1
It was 00 cm ² .

The composition of the processing liquid is shown below. (Color developer) Tank liquid (g) Replenisher (g) Diethylenetriamine pentaacetic acid 3.0 3.0 Disodium catechol-3,5-disulfonate 0.3 0.3 Sodium sulfite 3.9 5.3 Potassium carbonate 39.0 39.0 Disodium-N, N-bis (2-sulfonate ethyl) hydroxylamine 1.5 2.0 Potassium bromide 1.3 0.3 Potassium iodide 1.3 mg-4-hydroxy-6- Methyl-1,3,3a, 7-tetrazaindene 0.05-hydroxylamine sulfate 2.4 3.3 2-methyl-4- [N-ethyl-N- (β-hydroxyethylamino] -aniline sulfate Salt 4.5 3.3 Add water 1.0 liter 1.0 liter pH 10.05 10.18

(Bleaching Solution) Tank Solution (g) Replenishing Solution (g) 1,3-Diaminopropanetetraacetic Acid Ferric Ammonium Monohydrate 113.0 170.0 Ammonium Bromide 70.0 105.0 Ammonium Nitrate 14. 0 21.0 Succinic acid 34.0 51.0 Maleic acid 28.0 42.0 Add water 1.0 liter 1.0 liter pH (prepared with aqueous ammonia) 4.6 4.0

(Fixing Solution (1) Tank Solution) A mixed solution of the above bleaching tank solution and the following fixing tank solution in a ratio of 5:95 (volume ratio).
(PH 6.8) (Fixer solution (2)) Tank solution (g) Replenisher solution (g) Ammonium thiosulfate aqueous solution 240.0 ml 720.0 ml (750 g / liter) Imidazole 7.0 ml 21.0 ml Ammonium methanethiosulfonate 5. 0 ml 15.0 ml Ammonium methanesulfinate 10.0 ml 30.0 ml Methylenediamine tetraacetic acid 13.0 ml 39.0 ml Water was added to 1.0 liter 1.0 liter pH [prepared with aqueous ammonia and acetic acid] 7.4 7. 45

(Rinsing water) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite I manufactured by Rohm and Haas).
R-120B) and an OH-type strongly basic anion exchange resin (Amberlite IR-400) are passed through a mixed bed column to treat calcium and magnesium ions at a concentration of 3 mg / liter or less. 20 mg / liter of sodium isocyanurate dichloride and 150 mg / liter of sodium sulfate were added. The pH of this solution is 6.5
〜7.5. (Stabilizer) mother liquor, replenisher common (unit g) sodium p-toluenesulfinate 0.03 polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.2 1,2-benzisothiazoline-3- On, sodium 0.10 ethylenediaminetetraacetic acid disodium salt 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added 1.0 liter pH 8.5

The density of the treated sample was measured with a green filter. For each sample, the fog density was defined as the increment with respect to the density when the sample was directly fixed. The sensitivity was defined as the reciprocal of the exposure amount giving a density 0.2 higher than the fog density, and the sensitivity of each sample was represented by a relative value with the value of sample 201 being 100. The aging fog was compared by the same definition as in Example 1. Table 4 shows the obtained results.

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[Table 4]

From Table 4, it can be seen that the sample of the present invention has low fog and high sensitivity even in multilayer coating, and further, the increase in fog density with time is very small.

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INDUSTRIAL APPLICABILITY As described above, the present invention can provide a silver halide photographic light-sensitive material having high sensitivity, low fog, and excellent storage stability.

Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical display location G03C 1/34 G03C 1/34 7/00 510 7/00 510 530 530 530

Claims (4)

[Claims] 1. A photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, the emulsion layer being subjected to reduction sensitization.
A silver halide photographic light-sensitive material comprising a compound represented by 1) and a light-sensitive halogenated emulsion to which an oxidizing agent for silver other than the above is added. General formula (S1) In the formula, R ₁ and R ₂ may be the same or different,
Each represents an alkyl group, an aryl group, a heterocyclic group, an amino group or a group shown below. Embedded image In the formula, R ₃ and R ₅ may be the same or different,
Each represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. X ₁ and X ₂ may be the same or different and each represents S, Se or Te. R ₁ , R ₂ , X ₁
And X ₂ may together form a ring. 2. An oxidizing agent for silver is represented by the following general formula (II):
The silver halide light-sensitive material according to claim 1, which is represented by (III) or (IV). In the general formula _{(II) R-SO 2 S} -M Formula _{(III) R-SO 2 S} -R 6 Formula _{(IV) R-SO 2 S} -L m -SSO 2 -R 7 Formula, R, R ₆ , R ₇ may be the same or different and each represents an aliphatic group, an aromatic group, or a heterocyclic group, M represents a cation, L represents a divalent linking group, m represents 0 or 1. is there. The compounds of the general formulas (II) to (IV) are (I
It may be a polymer containing a divalent group derived from the structures represented by I) to (IV) as a repeating unit. 3. The method according to claim 1, wherein the compound represented by formula (S1) is added after the formation of silver halide grains and before the chemical sensitization. Silver halide light-sensitive material. 4. The silver halide photographic material according to claim 1, wherein the support has a transparent magnetic recording layer.