JPH1069040A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain high sensitivity and low fog and superior storage stability by containing 2 kinds of specified compounds. SOLUTION: The silver halide photographic sensitive material contains the compound represented by formula I and the compound represented by formula II, and in formulae I and II, R<11> is an H atom or a group to be released by reaction with the oxidation product of an aromatic primary amine color developing agent; R<12> is an aryl group; R<13> is a substituent; n1 is an integer of 1-5, and when n1 is >=2, plural R<13> may be the same or different; Het is a 5- or 6- membered N-containing hetero ring not substituted by a mercapto or blocked mercapto group; J is a (m2 +1) valent bonding group; Q is a water-soluble group; n2 is an integer of 0-5; and m2 is an integer of >=1, thus permitting fog to be lowered and sensitivity to be enhanced and storage stability to be improved.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material having low fog, high sensitivity, and improved storage stability.

[0002]

2. Description of the Related Art A conventional silver halide color photographic light-sensitive material undergoes color development processing after exposure to cause a reaction between a coupler and an oxidized color developing agent to form an image with the generated dye. Generally, in this photographic method, color reproduction is performed by a subtractive color method, and yellow, magenta, and cyan color images are formed.

As magenta dye-forming couplers (magenta couplers), pyrazolone-based, pyrazolinobenzimidazole-based, indanone-based, pyrazolotriazole-based couplers and the like are known. Among them, various 5-pyrazolone derivatives have been widely used. It has been.

As the 3-position substituent of the 5-pyrazolone derivative, for example, an alkyl group, an aryl group, US Pat.
No. 439,098, 2,369,
Nos. 489 and 2,600,788 and the like, and an ureido group described in 3,558,319 and the like are known. However, the above couplers have a drawback that the coupling activity with an oxidized developing agent is low and it is difficult to obtain a high-density magenta image.

In addition, US Pat. Nos. 2,311,081, 3,677,764, 3,684,514, British Patents 956,261, and 1,173,513 described in US Pat. Anilino-5-pyrazolone couplers have high coupling activity and high color development, but have drawbacks such as a large rise in fog and poor storage stability.

[0006]

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

[0007]

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

(1) A silver halide photographic material comprising at least one compound represented by the following general formula [I] and at least one compound represented by the following general formula [II]: .

[0009]

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[In the formula, R ¹¹ represents a hydrogen atom or a group capable of leaving by reaction with an oxidized form of an aromatic primary amine color developing agent. R ¹² represents an aryl group. R ¹³ represents a substituent, and n ₁ represents an integer of ₁ to 5. When n ₁ is 2 or more, R ¹³ may be the same or different. ]

[0011]

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Wherein Het is a 5- to 6-membered compound having no mercapto group or a blocked mercapto group as a substituent.
Represents a membered nitrogen-containing heterocyclic ring, J represents a (m ₂ +1) -valent linking group, and Q represents a water-soluble group. n ₂ represents an integer of 0 to 5, m ₂ represents an integer of 1 or more. (2) A silver halide photographic light-sensitive material comprising at least one compound represented by the above general formula [I] and at least one compound represented by the following general formula [III].

[0013]

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Wherein R ³¹ and R ³² represent an aliphatic group, an aromatic group, or a heterocyclic group. R ³¹ and R ³² may be the same or different, and when R ³¹ and R ³² are an aliphatic group, they may combine with each other to form a ring. n ₃ represents an integer of 2 or more. (3) The silver halide photographic material as described in (1), wherein the general formula [II] is represented by the general formula [IV] or the general formula [V].

[0015]

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[In the general formula [IV], W represents an oxygen atom, a sulfur atom, a nitrogen atom or C (R ₄₁ ), and X represents a nitrogen atom or C (R ₄₁ ). Z represents an atomic group necessary for forming a 5- to 6-membered nitrogen-containing aromatic heterocyclic ring having no mercapto group or a blocked mercapto group as a substituent. R ₄₁ represents a substituent other than a mercapto group or a blocked mercapto group, or a hydrogen atom. J, Q, n
₂ and m ₂ have the same meanings as in the case of the general formula [II].

In the general formula [V], P, Q ', R and T represent a nitrogen atom or C (R ₄₁ ), and J, Q, n ₂ and m ₂ have the same meanings as in the general formula [II]. is there. Hereinafter, the present invention will be described in detail.

The compound represented by the general formula [I] will be described.

In the above general formula [I], R ¹¹ represents a hydrogen atom or a group which can be eliminated by reaction with an oxidized aromatic primary amine color developing agent. R ¹¹ is preferably a group capable of leaving by reaction with an oxidized form of an aromatic primary amine color developing agent, and more preferably an arylthio group, from the viewpoint of saving silver and improving resistance to harmful gases.

R ¹² represents an aryl group such as phenyl, pentachlorophenyl, 2,4,6-trichlorophenyl, 2,5-dichlorophenyl, 2,4-
Dichlorophenyl group, 2,6-dichloro-4-methylphenyl group, 2,6-dichloro-4-methanesulfonylphenyl group, 2,6-dichloro-4-cyanophenyl group,
2,6-dichloro-4-morpholinosulfonylphenyl group, 2,4-dichloro-6-methoxyphenyl group, 2,
4-dichloro-6-methylphenyl group and the like.

When the compound of the present invention is used in a color negative film, R ¹² is a pentachlorophenyl group and 2,6- is preferred in that the spectral absorption wavelength of a color dye obtained by reacting with an oxidized form of a color developing agent is preferable. Preferred are a dichloro-4-methanesulfonylphenyl group, a 2,6-dichloro-4-cyanophenyl group, and a 2,6-dichloro-4-morpholinosulfonylphenyl group.

R ¹³ represents a substituent, for example, chlorine, bromine,
Halogen atoms such as fluorine, alkoxy groups such as methoxy and ethoxy, aryloxy groups such as phenoxy groups, 2,6
-Dichlorobenzoylamino group, benzoylamino group such as 2,6-dimethoxybenzoylamino group, alkylsulfonyl group such as hexadecylsulfonyl, acylamino group such as acetylamino group, cyano group, nitro group, carboxyl group, amino group, Examples thereof include an alkoxycarbonyl group such as an ethoxycarbonyl group, and an alkyl group such as a methyl group, an ethyl group, and an isopropyl group. Of course, other monovalent substituents may be used.

It is preferable that at least one atom or group of R ¹³ is a halogen atom or an alkoxy group in terms of color development and spectral absorption wavelength.

Specific examples of the compound represented by the general formula [I] of the present invention are shown below, but the present invention is not limited to these.

[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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The compound represented by the general formula [I] (hereinafter, also referred to as a magenta coupler represented by the general formula [I]) according to the present invention may be added to a photosensitive layer. May be added. In order to introduce the magenta coupler represented by the general formula [I] according to the present invention into a silver halide color photographic light-sensitive material, the magenta coupler may be dispersed and added by various known dispersion methods described below. A mixture of a high-boiling solvent such as dibutyl phthalate or tricresyl phosphate and a low-boiling solvent such as butyl acetate or ethyl acetate, or a low-boiling solvent alone, may be used alone or in combination with the compound represented by the general formula [I]. After dissolution, the mixture is mixed with a gelatin aqueous solution containing a surfactant, and then emulsified and dispersed using a high-speed rotary mixer, a colloid mill or an ultrasonic disperser, and directly added to the silver halide emulsion. be able to. Alternatively, the above emulsified dispersion may be set, shredded, washed with water, and then added to the silver halide emulsion.

In the present invention, the following general formula [VI]
By containing at least one compound represented by the formula, the object of the present invention can be achieved more efficiently.

[0035]

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In the formula, R ⁶¹ and R ⁶² represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and R ⁶³ , R ⁶⁴ and R ⁶⁵ represent substituents.

R ⁶¹ and R ⁶² , R ⁶³ and R ⁶⁴ , and R ⁶⁴ and R ⁶⁵ may each form a ring.

In the general formula [VI], the substituents represented by R ⁶¹ and R ⁶² are respectively a hydrogen atom and an alkyl group (for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group and a tert-butyl group). , N-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group,
n-octyl group, n-dodecyl group, etc.), alkenyl group (eg, vinyl group, allyl group, etc.), alkynyl group (eg, propargyl group, etc.), aryl group (eg, phenyl group, naphthyl group, etc.), heterocyclic ring Groups (e.g., pyridyl, thiazolyl, oxazolyl, imidazolyl,
Furyl group, prolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, selenazolyl group, sulfolanyl group, piperidinyl group, pyrazolyl group, tetrazolyl group, etc.). These substituents may themselves have further substituents.

In the general formula [VI], examples of the substituent represented by R ⁶³ , R ⁶⁴ and R ⁶⁵ include an alkyl group (for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group,
tert-butyl group, n-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-octyl group, n-dodecyl group, etc., alkenyl group (eg, vinyl group, allyl group, etc.), alkynyl group (eg, , Propargyl group, etc.), aryl group (eg, phenyl group, naphthyl group, etc.), heterocyclic group (eg, pyridyl group, thiazolyl group, oxazolyl group, imidazolyl group, furyl group, prolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl) Group, selenazolyl group, sulfolanyl group, piperidinyl group, pyrazolyl group, tetrazolyl group, etc.), halogen atom (eg, chlorine atom, bromine atom, iodine atom, fluorine atom, etc.), alkoxy group (eg, methoxy group, ethoxy group, propyl group) Oxy group, n-pentyloxy group, cyclopentyloxy group, n Hexyloxy group, cyclohexyloxy group, n-octyloxy group, n-dodecyloxy group, etc., aryloxy group (eg, phenoxy group, naphthyloxy group, etc.), alkoxycarbonyl group (eg, methyloxycarbonyl group, ethyloxy Carbonyl group, n-butyloxycarbonyl group, n-octyloxycarbonyl group, n-dodecyloxycarbonyl group, etc., aryloxycarbonyl group (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfonamide group (eg, , Methylsulfonylamino group, ethylsulfonylamino group, n-butylsulfonylamino group, n-hexylsulfonylamino group, cyclohexylsulfonylamino group, n-octylsulfonylamino group, n-dodecylsulfonylamino , Etc. phenylsulfonylamino group), a sulfamoyl group (e.g., aminosulfonyl group, methylaminosulfonyl group,
Dimethylaminosulfonyl group, n-butylaminosulfonyl group, n-hexylaminosulfonyl group, cyclohexylaminosulfonyl group, n-octylaminosulfonyl group, n-dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2- Pyridylaminosulfonyl group), ureido group (for example,
Methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, n-octylureido group, n-dodecylureido group, phenylureido group,
A naphthylureido group, a 2-pyridylaminoureido group, etc., an acyl group (for example, an acetyl group, an ethylcarbonyl group, a propylcarbonyl group, an n-pentylcarbonyl group, a cyclohexylcarbonyl group, an n-octylcarbonyl group, a 2-ethylhexylcarbonyl group, n-dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc., carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, n-pentylaminocarbonyl group) , A cyclohexylaminocarbonyl group, an n-dodecylaminocarbonyl group, a phenylaminocarbonyl group, a naphthylaminocarbonyl group, a 2-pyridylaminocarbonyl group, etc., an amide group (for example, Acetamide group, an ethylcarbonyl group, a propyl carbonyl amino group, n- pentyl carbonylamino group, a cyclohexylcarbonyl group, a 2-ethylhexyl carbonylamino radical, n
-Octylcarbonylamino group, dodecylcarbonylamino group, benzoylamino group, naphthylcarbonylamino group, etc., sulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, n-butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group) , Dodecylsulfonyl group, phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (for example, amino group, ethylamino group,
Dimethylamino group, n-butylamino group, cyclopentylamino group, 2-ethylhexylamino group, n-dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, etc.), cyano group, nitro group, carboxyl group, hydroxyl Group, sulfo group, hydrogen atom and the like.
These groups can be substituted by the alkyl groups represented by R ⁶¹ and R ⁶² , and the same groups as the substituents of the alkyl groups.

[0040] As the ring which can be formed by R ⁶¹ and R ⁶² are, for example piperidine ring, pyrrolidine ring, morpholine ring, pyrrole ring, piperazine ring, and thiomorpholine rings and the like. The ring formed by R ⁶³ and R ⁶⁴ , R ⁶⁴ and R ⁶⁵ includes
For example, a benzene ring, a thiophene ring, a furan ring, a pyrrole ring and the like can be mentioned.

Specific examples of the compound represented by formula (VI) preferably used in the present invention are shown below, but it should not be construed that the invention is limited thereto.

[0042]

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The general formula [VI] preferably used in the present invention
The compound represented by the formula (1) is preferably added in the range of 1% by weight to 300% by weight based on the magenta coupler represented by the general formula [I]. More preferably 5% by weight or more 15
0% by weight or less is added. The layer to be added may be the same as or different from the layer to which the magenta coupler represented by the general formula [I] is added, but is preferably added to the same layer.

The compound represented by the general formula [VI] can be introduced into the light-sensitive material by various known dispersion methods described later, similarly to the magenta coupler represented by the general formula [I]. The compound represented by the general formula (VI) may be mixed and dispersed at the same time as the magenta coupler represented by the general formula (I) and added to the light-sensitive material, or may be separately dispersed and added to the magenta coupler. Good, but it is desirable to mix and disperse them at the same time.

Hereinafter, the compound represented by formula (II), (IV) or (V) will be described in detail.

The blocked mercapto group in the compound represented by the general formula [II], [IV] or [V] is
A group in which a blocking group can be cleaved into a mercapto group during development processing, and specific examples of the blocking group include an acyl group,
Examples include a sulfonyl group and a cyanoethyl group. Specific examples of the nitrogen-containing heterocycle represented by Het in the general formula (II) include pyrrolidine, piperidine, morpholine, thiomorpholine, pyrrole, pyridine, pyrimidine, pyrazine, triazine, imidazole, pyrazole, oxazole, thiazole, isoxazole, and iso Thiazole,
Heterocycles such as triazole, tetrazole, thiadiazole and oxadiazole, and condensed rings thereof with a benzene ring can be mentioned.

The linking group represented by J in the general formulas [II], [IV] or [V] is specifically an alkylene, an arylene, a heteroarylene, -SO _2- , -SO-, -O
—, —S—, and —N (R ₂₃ ) — alone or in combination. Here, R ₂₃ represents an alkyl group, an aryl group, or a hydrogen atom. J is preferably arylene, most preferably phenylene. n
₂ is preferably 0 or 1.

The water-soluble group represented by Q in the general formulas [II], [IV] or [V] represents a group capable of being anionized in a developer, and specifically includes a sulfonamide group and a sulfamoyl group. Phenolic hydroxyl group, carboxyl group, sulfo group, and salts thereof. Preferred are a carboxyl group and a sulfo group. m ₂ is preferably 1 or 2.

In the general formula [IV], 5 to Z
Examples of the 6-membered nitrogen-containing aromatic hetero ring include pyridine, pyrimidine, pyrazine, triazine, imidazole, pyrazole, oxazole, thiazole, isoxazole, isothiazole, triazole, tetrazole, thiadiazole, oxadiazole rings and benzene rings thereof. Condensed rings. Preferably triazole,
It is tetrazole.

Specific examples of the substituent represented by R ₄₁ in the general formula [IV] include a halogen atom (a chlorine atom, a bromine atom, etc.) and an alkyl group (for example, a methyl group, an ethyl group, an isopropyl group, a hydroxyethyl group). , Methoxymethyl group, trifluoromethyl group, t-butyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), aralkyl group (eg, benzyl group, 2-phenethyl group, etc.), aryl group (eg, phenyl group, Naphthyl group, p-tolyl group, p-chlorophenyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, isopropoxy group, n-butoxy group, etc.), aryloxy group (eg, phenoxy group, etc.), cyano group, acylamino Groups (eg, acetylamino, propionylamino, alkylthio groups (eg, methylthio , Ethylthio group, n-butylthio group, etc.), arylthio group (eg, phenylthio group, etc.), sulfonylamino group (eg, methanesulfonylamino group, benzenesulfonylamino group, etc.), ureido group (eg, 3-methylureido, 3,3- Dimethylureido group, 1,3-dimethylureido group, etc.), sulfamoylamide group (dimethylsulfamoylamino group, etc.), carbamoyl group (eg, methylcarbamoyl group, ethylcarbamoyl group, dimethylcarbamoyl group, etc.), sulfamoyl group ( For example, ethylsulfamoyl group, dimethylsulfamoyl group, etc., alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, etc.), sulfonyl group (eg, methanesulfonyl group) Honyl group, butanesulfonyl group, phenylsulfonyl group, etc.),
Acyl group (for example, acetyl group, propanoyl group, butyroyl group, etc.), amino group (methylamino group, ethylamino group, dimethylamino group, etc.), hydroxy group, nitro group,
A nitroso group, an amine oxide group (eg, a pyridine-oxide group), an imide group (eg, a phthalimide group), a disulfide group (eg, a benzene disulfide group, a benzothiazolyl-2-disulfide group, etc.), a carboxyl group,
Examples include a sulfo group and a heterocyclic group (for example, a pyridyl group, a benzimidazolyl group, a benzothiazolyl group, a benzoxazolyl group, and the like).

In the general formula [V], three of P, Q ', R and T are preferably N atoms, and particularly preferably, P, Q' and R are nitrogen atoms.

[0052] Formula [II], [IV] or the compound represented by [V] - have a (Q) m ₂ substituent other than the substitution position of the heterocyclic ring - (J) n ₂ Specific examples thereof include the above-mentioned substituents.

Hereinafter, specific examples of the compound represented by the general formula [II], [IV] or [V] of the present invention will be shown, but the present invention is not limited thereto.

[0054]

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[0055]

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The compound represented by the general formula [II], [IV] or [V] of the present invention can be prepared by a method described in known literature such as Journal of Plastic Chemistry [2], 124, 286. And can be easily synthesized. The synthesis example of the exemplary compound II-1 is shown below.

<Synthesis Example> Synthesis of Exemplified Compound II-1 1- (4-carboxyphenyl) -tetrazole 4.5
g to 20 ml of methanol and 5 ml of concentrated aqueous ammonia.
To complete dissolution. Next, 2 ml of 35% aqueous hydrogen peroxide was added and the mixture was stirred at room temperature for 12 hours. Crystals precipitated after acidification by adding 1N hydrochloric acid were filtered and recrystallized from methanol to obtain 3.7 g of Exemplified Compound 1 (96% yield).

The compound represented by formula (III) will be described below.

In the general formula [III], R ₃₁ and R
_Examples of the aliphatic group represented by ₃₂ include a linear or branched alkyl, alkenyl, alkynyl, or cycloalkyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
Specifically, methyl, ethyl, propyl, butyl, hexyl, decyl, dodecyl, isopropyl, t-butyl,
2-ethylhexyl, allyl, 2-butenyl, 7-octenyl, propargyl, 2-butynyl, cyclopropyl, cyclopentyl, cyclohexyl, cyclododecyl. Examples of the aromatic group represented by R ₃₁ and R ₃₂ include those having 6 to 20 carbon atoms, and specifically include phenyl, naphthyl and anthranyl groups. The heterocyclic group represented by R ₃₁ and R ₃₂ may be a single ring or a condensed ring, and includes a 5- to 6-membered hetero ring having at least one of O, S, and N atoms in the ring. Specifically, pyrrolidine, piperidine, tetrahydrofuran, tetrahydropyran, oxirane, morpholine, thiomorpholine,
Examples include thiopyran, tetrahydrothiophene, pyrrole, pyridine, furan, thiophene, imidazole, pyrazole, oxazole, thiazole, isoxazole, isothiazole, triazole, tetrazole, thiadiazole, oxadiazole, and benzerogues thereof. The ring forming a ring with R ₃₁ and R ₃₂ includes a 4- to 7-membered ring. It is preferably a 5- to 7-membered ring. Preferred groups for R ₃₁ and R ₃₂ are heterocyclic groups, and more preferred are heteroaromatic ring groups. The aliphatic group, aromatic group, or heterocyclic group represented by R ₃₁ and R ₃₂ may be further substituted, and the substituent may be a halogen atom (eg, a chlorine atom or a bromine atom), an alkyl group (eg, Methyl group, ethyl group, isopropyl group, hydroxyethyl group, methoxymethyl group, trifluoromethyl group, t-butyl group, etc., cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), aralkyl group (eg, benzyl group, Phenethyl group, etc.), aryl group (for example, phenyl group, naphthyl group, p-tolyl group, p
-Chlorophenyl group, etc.), alkoxy group (for example, methoxy group, ethoxy group, isopropoxy group, n-butoxy group, etc.), aryloxy group (for example, phenoxy group, etc.), cyano group, acylamino group (for example, acetylamino group, propionylamino Group), alkylthio group (eg, methylthio group, ethylthio group, n-butylthio group, etc.), arylthio group (eg, phenylthio group, etc.), sulfonylamino group (eg, methanesulfonylamino group, benzenesulfonylamino group, etc.), ureido group ( For example, 3-methylureido group, 3,3-dimethylureido group, 1,3-dimethylureido group, etc., sulfamoylamino group (dimethylsulfamoylamino group, etc.), carbamoyl group (eg, methylcarbamoyl group, ethylcarbamoyl group) Group, dimethylcarbamoy Group), sulfamoyl group (eg, ethylsulfamoyl group, dimethylsulfamoyl group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, etc.), sulfonyl Group (eg, methanesulfonyl group, butanesulfonyl group, phenylsulfonyl group, etc.), acyl group (eg, acetyl group, propanoyl group, butyroyl group, etc.), amino group (methylamino group, ethylamino group, dimethylamino group, etc.), hydroxy Group, nitro group, nitroso group, amine oxide group (for example, pyridine-oxide group), imide group (for example, phthalimido group, etc.), disulfide group (for example, benzene disulfide group, benzothiazolyl 2-disulfide group, etc.), heterocyclic group (for example, Lysyl group, benzimidazolyl group, benzothiazolyl group, benzoxazolyl group). R ₃₁ and R ₃₂ may have one or more of these substituents. Further, each substituent may be further substituted with the above substituent. n ₃ is an integer of 2 or more, preferably 2 to 6, and more preferably n ₃ = 2.

The following formula (III) used in the present invention
Specific examples of the compound represented by are listed, but the present invention is not limited thereto.

[0061]

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[0062]

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[0063]

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The method for adding the compounds represented by the general formulas [II] to [V] of the present invention to a silver halide emulsion includes:
Methods well known in the art can be used. For example, the compound can be directly dispersed in the emulsion or dissolved in a water-soluble solvent such as pyridine, methanol, ethanol, methyl cellosolve, acetone, fluorinated alcohol, dimethylformamide, or a mixture thereof,
Alternatively, it can be diluted with water or dissolved in water and added to the emulsion in the form of a solution. Ultrasonic vibration can be used during the dissolution process.

Further, the compounds represented by the general formulas [II] to [V] of the present invention are dissolved in a volatile organic solvent as described in US Pat. No. 3,469,987, etc. A method of adding a dispersion dispersed in an aqueous colloid to an emulsion, dispersing in a water-soluble solvent without dissolving a water-insoluble dye as described in JP-B-46-24185,
A method of adding this dispersion to an emulsion is also used.

The compounds represented by the general formulas [II] to [V] of the present invention can be added to the emulsion in the form of a dispersion by an acid dispersing method.

The compounds represented by the general formulas [II] to [V] of the present invention may be added anywhere during the period from the formation of silver halide grains to the time of coating. It is preferable to add the compound until the completion of chemical sensitization.

In the present invention, the silver halide emulsion is a Research Disclosure No. 308119 (hereinafter R
D308119). The places to be described are shown below.

[0069]

[Table 1]

In the present invention, it is preferable to use a silver halide emulsion which has been subjected to physical ripening, chemical ripening and spectral sensitization.

In the present invention, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer, or the like can be used as a chemical sensitizer.

Examples of the sulfur sensitizer applicable in the present invention include thiourea derivatives such as 1,3-diphenylthiourea, triethylthiourea, 1-ethyl-3- (2-thiazolyl) thiourea, rhodanine derivatives, dithicarbamine Preferred examples include acids, polysulfide organic compounds, sodium thiosulfate, and sulfur alone. still,
As the simple substance of sulfur, α-sulfur belonging to the orthorhombic system is preferable.

Other sulfur sensitizers include those described in US Pat. Nos. 1,574,944, 2,410,689, 2,278,947, 2,728,668, and 3,501, Nos. 313, 3,656,955, etc., West German Application Publication (OLS) 1,422,869.
Sensitizers described in JP-A-56-24937 and JP-A-55-45016 can also be used.

In the present invention, selenium sensitizers that can be used include a wide variety of selenium compounds. For example, US Pat. Nos. 1,574,944 and 1,602,
592, 1,623,499, JP-A-60-15
0046, JP-A-4-25832, JP-A-4-1092
No. 40 and No. 4-147250. Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate, etc.), selenoureas (eg, N, N-dimethylselenourea, N, N, N′-triethylseleno). Urea, N,
N, N'-trimethyl-N'-heptafluoroselenourea, N, N, N'-trimethyl-N'-heptafluoropropylcarbonylselenourea, N, N, N'-trimethyl-N'-4-nitrophenyl Carbonyl selenoureas), seleno ketones (eg, selenoacetone, selenoacetophenone, etc.), selenoamides (eg, selenoacetamide, N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids, and selenoesters (eg, 2-selenopropionic acid) , Methyl-3-selenobutyrate, etc.), selenophosphates (eg, tri-p-
Triselenophosphate, etc.) and selenides (dimethyl selenide, diethyl diselenide, etc.). Particularly preferred selenium sensitizers are selenoureas, selenamides, and selenoketones.

Specific examples of the techniques for using these selenium sensitizers are disclosed in the following patent specifications. US Patent No. 1,
No. 574,944, No. 1,602,592, No. 1,
623,499, 3,297,466, 3,2
Nos. 97,447, 3,320,069, 3,40
8,196, 3,408,197, 3,44
2,653, 3,420,670 and 3,59
1,385, French Patent 2,693,038,
2,093,209, JP-B-52-34491,
Nos. 52-34492, 53-295, 57-2
No. 2090, JP-A-59-180536 and JP-A-59-1
Nos. 85330, 59-181337, 59-18
Nos. 7338, 59-192241, 60-150
No. 046, No. 60-151637, No. 61-2467
No. 38, JP-A-3-4221 and JP-A-3-24537,
3-1-111838, 3-116132, 3-
148648, 3-237450, 4-168
No. 38, No. 4-25832, No. 4-32831, No. 4-96059, No. 4-109240, No. 4-14
No. 0738, No. 4-140739, No. 4-14725
No. 0, No. 4-149337, No. 4-184331,
4-190225, 4-191729, 4-
195035, British Patent 255,846, 86
No. 1,984; E. FIG. Jou by Spencer et al.
nal of PhotographicScience
e, 31, 158-169 (1983).

Regarding tellurium sensitizers and sensitization methods usable in the present invention, see US Pat. No. 1,623,499.
Nos. 3,320,069 and 3,772,031
Nos. 3,531,289 and 3,655,394
No., British Patent Nos. 235,211 and 1,121,46.
9, No. 1,295,462, No. 1,396,696
No., Canadian Patent No. 800,958, JP-A-4-204
No. 64, etc. Examples of useful tellurium sensitizers include telluroreas, telluramides, and the like.

The addition amounts of the sulfur sensitizer, selenium sensitizer, and tellurium sensitizer are not uniform depending on the type of silver halide emulsion, the type of compound used, the ripening conditions, and the like. It is preferably from 1 × 10 ⁻⁴ mol to 1 × 10 ⁻⁹ mol per mol. More preferably, it is 1 × 10 ⁻⁵ mol to 1 × 10 ⁻⁸ mol.

In the chemical sensitization of the present invention, the sensitivity can be further increased by using gold sensitization in combination. Useful gold sensitizers include chloroauric acid, gold thiosulfate, gold thiocyanate, and the like, as well as U.S. Patent Nos. 2,597,856 and 5,044.
9,484, 5,049,485, Tokubyo Sho 44-
No. 15748, JP-A-1-147537, 4-70
No. 650 and the like.

The above-mentioned various sensitizers can be added by a method of adding them by dissolving them in water or an organic solvent such as methanol or ethanol, alone or in a mixed solvent, or by adding A method in which the mixture is added in advance with a solution or a method disclosed in JP-A-4-140739, that is, a method in which the mixture is added in the form of an emulsified dispersion of a mixed solution with an organic solvent-soluble polymer may be used.

In the present invention, when the chemical sensitization is performed in the presence of a silver halide-adsorbing compound, the effect of the present invention is further enhanced. As the silver halide-adsorbing compound, sensitizing dyes, antifoggants, stabilizers and the like containing the compounds represented by formulas [II] to [V] of the present invention can be used.

Examples of sensitizing dyes include polymethine dyes containing cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, hemioxonol dyes, oxonol, merostyryl and streptocyanin. Can be mentioned.

Examples of antifoggants and stabilizers include tetrazaindenes and azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, promobenzimidazoles and mercaptothiazoles , Mercaptobenzimidazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole), etc., and mercaptopyrimidines, mercaptotriazines, for example, thioketo such as oxazolythion. Compounds, furthermore benzenethiosulfinic acid,
Benzenesulfinic acid, benzenesulfonamide,
Hydroquinone derivatives, aminophenol derivatives, gallic acid derivatives and ascorbic acid derivatives can be mentioned.

In the present invention, good results are often obtained when sensitization is carried out in the presence of a silver halide solvent.

Examples of the silver halide solvent used in the present invention include US Pat. Nos. 3,271,157 and 3,53.
(A) Organic thioethyls described in JP-A Nos. 1,2891, 3,574,628, JP-A-54-1019, JP-A-54-158917, etc .;
-82408, 55-77737, 55-29
No. 82, each of (b) thiourea derivatives, and JP-A-53-144319, (c) a halogenated compound having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom. Silver solvent, JP-A-54-10071
No. 7, (d) imidazoles, (e) sulfites, (f) thiocyanates and the like.

The specific compounds are shown below.

[0086]

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[0087]

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Particularly preferred solvents include thiocyanate and tetramethylthiourea. Although the amount of the solvent used varies depending on the kind, for example, in the case of thiocyanate, the preferable amount is 5 mg per mol of silver halide.
１1 g.

Known photographic additives that can be used in the present invention are also described in Research Disclosure below. The places to be described are shown below.

[0090]

[Table 2]

Various couplers can be used in the present invention, and specific examples are described in the following Research Disclosure. The relevant sections are described below.

[0092]

[Table 3]

The additive used in the present invention is RD3081
It can be added by the dispersion method described in 19 XIV.

In the present invention, the aforementioned RD17643
28 pages, RD18716 pages 647-8 and RD308
The support described in XIX 119 can be used.

The light-sensitive material of the present invention includes the aforementioned RD3081
An auxiliary layer such as a filter layer or an intermediate layer described in the section 19VII-K can be provided.

The light-sensitive material of the present invention can be obtained by using the RD30811 described above.
Various layer configurations such as a normal layer, a reverse layer, and a unit configuration described in section 9VII-K can be employed.

The present invention can be applied to various color light-sensitive materials represented by color negative films for general use or movies, color reversal films for slides or televisions, and color positive films.

In these color light-sensitive materials, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 24 μm or less, more preferably 20 μm or less.
It is more preferably 18 μm or less. Also, the membrane swelling speed T _1/2
Is preferably 30 seconds or less, more preferably 20 seconds or less.
The film thickness means a film thickness measured at 25 ° C. and a relative humidity of 55% under humidity control (2 hr), and the film expansion _/ swelling rate T _1/2 can be measured according to a method known in the art.

The swelling _/ swelling rate T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging conditions after coating. or,
The swelling ratio is preferably from 150 to 400%. The swelling ratio can be calculated from the maximum swelling film thickness under the conditions described above according to the formula: (maximum swelling film thickness-film thickness) / film thickness.

The color photographic material is RD17643 as described above.
Pages 28 and 29 and RD18716 at page 615, left column to right column.

When the color light-sensitive material is used in the form of a roll, it is preferable to take the form stored in a cartridge. The most common cartridge is a 135 format cartridge currently available. Others
The cartridge proposed in the following patent can also be used.

JP-A-58-67329, JP-A-58-67329
181035, U.S. Pat. No. 4,221,479, JP-A Nos. 1-231045 and 2-199451, U.S. Pat. Nos. 4,846,418, 4,848,693, and 4,832,275.

The present invention can be applied to a "small photographic roll film cartridge and film camera" filed on Jan. 31, 1992 (Toshihiko Yagi et al.).

The light-sensitive material of the present invention is the same as that of RD17643 described above.
Pages 28 to 29, RD18716 page 615 and RD30
The development can be carried out by the usual method described in XIX of No. 8119.

[0105]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Example 1 On a triacetyl cellulose film support provided with an undercoat layer, layers having the following compositions were sequentially formed from the support side to prepare a multilayer color photographic light-sensitive material, Sample 1.

The amount of addition is expressed in grams per m ² .
However, silver halide and colloidal silver were converted to the amount of silver, and sensitizing dyes (indicated by SD) were shown in moles per mole of silver.

First Layer (Antihalation Layer) Black Colloidal Silver 0.16 UV-1 0.3 CM-1 0.044 OIL-1 0.044 Gelatin 1.33 Second Layer (Intermediate Layer) AS-10 .160 OIL-1 0.20 Gelatin 1.40 Third layer (low-sensitivity red-sensitive layer) Silver iodobromide a 0.12 Silver iodobromide b 0.50 SD-1 3.0 × 10 ^-5 SD-2 1.5 × 10 ^-4 SD-3 3.0 × 10 ^-4 SD-4 3.0 × 10 ^-6 C-1 0.51 CC-1 0.047 OIL-2 0.45 AS- 2 0.005 Gelatin 1.40 4th layer (medium-speed red-sensitive layer) Silver iodobromide c 0.64 SD-1 3.0 × 10 ^-5 SD-2 1.5 × 10 ^-4 SD- ^{3 3.0 × 10 -4 C-2} 0.22 CC-1 0.028 DI-1 0.002 OIL-2 0.21 AS-3 0.006 peptidase Chin 0.87 Fifth Layer (high sensitivity red-sensitive layer) Silver iodobromide c 0.13 Silver iodobromide d 1.14 SD-1 3.0 × 10 -5 SD-2 1.5 × 10 ^-4 SD-3 3.0 × 10 ^-4 C-2 0.17 CC-1 0.029 DI-1 0.027 OIL-2 0.23 AS-3 0.013 Gelatin 1.23 6th layer ( Intermediate layer) OIL-1 0.29 AS-1 0.23 Gelatin 1.00 Seventh layer (low-sensitivity green color-sensitive layer) Silver iodobromide a 0.245 Silver iodobromide b 0.105 SD-4 5.0 × 10 ^-4 SD-5 5.0 × 10 ^-4 M-1 0.21 CM-2 0.039 OIL-1 0.25 AS-2 0.003 AS-4 0.063 Gelatin 98 8th layer (middle layer) M-1 0.03 CM-2 0.005 OIL-1 0.16 AS-1 0.11 Gelatin 0.80 Layer (medium sensitivity green-sensitive layer) Silver iodobromide e 0.87 SD-6 3.0 × 10 -4 SD-7 6.0 × 10 -5 SD-8 4.0 × 10 -5 M- 1 0.17 CM-2 0.048 CM-3 0.059 DI-2 0.012 OIL-1 0.29 AS-4 0.05 AS-2 0.005 Gelatin 1.43 10th layer (high sensitivity Green color-sensitive layer) Silver iodobromide f 1.19 Comparative compound-4 (described after Table 4) as a comparison of compounds of general formulas [II] and [III] 2 × 10 ^-5 SD-6 0 × 10 ^-4 SD-7 8.0 × 10 ^-5 SD-8 5.0 × 10 ^-5 M-1 0.09 CM-3 0.020 DI-3 0.005 OIL-1 0.11 AS -4 0.026 AS-5 0.014 AS-6 0.006 Gelatin 0.78 11th layer (yellow filter layer) Yellow colloidal silver 0.05 OI L-1 0.18 AS-7 0.16 Gelatin 1.00 12th layer (low-sensitivity blue-sensitive layer) Silver iodobromide g 0.29 Silver iodobromide h 0.19 SD-9 8.0 × 10 ^-4 SD-10 3.1 × 10 ^-4 Y-1 0.91 DI-4 0.022 OIL-1 0.37 AS-2 0.002 Gelatin 1.29 13th layer (high sensitivity blue Color layer) Silver iodobromide h 0.13 Silver iodobromide i 1.00 SD-9 4.4 × 10 ^-4 SD-10 1.5 × 10 ^-4 Y-1 0.48 DI-40 0.019 OIL-1 0.21 AS-2 0.004 Gelatin 1.55 14th layer (first protective layer) Silver iodobromide j 0.30 UV-1 0.055 UV-2 0.110 OIL-2 0.63 gelatin 1.32 15th layer (second protective layer) PM-1 0.15 PM-2 0.04 WAX-1 0.02 D-1 0.0 01 Gelatin 0.55 The characteristics of the above silver iodobromide are shown below (average particle size is one side length of a cube of the same volume).

Emulsion No. Average particle size (μm) Average AgI amount (mol%) Diameter / thickness ratio Silver iodobromide a 0.30 2.0 1.0 b 0.40 8.0 1.4 c 0.60 7.0 3.0. 1 d 0.74 7.0 5.0 e 0.60 7.0 4.1 f 0.65 8.7 6.5 g 0.40 2.0 4.0 h 0.65 8.0 1. 4 i 1.00 8.0 2.0 j 0.05 2.0 1.0 As a typical example of forming silver halide grains of the present invention, a production example of silver iodobromide d and f is described below. Shown in

For the silver halide emulsion according to the present invention, seed crystal emulsion-1 was first prepared as follows.

Preparation of Seed Emulsion-1 A seed emulsion was prepared as follows.

JP-B-58-58288, 58-58
No. 289, a silver nitrate aqueous solution (1.161 mol) was added to the following solution A1 adjusted to 35 ° C.
And a mixed aqueous solution of potassium bromide and potassium iodide (potassium iodide 2 mol%) while maintaining the silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) at 0 mV. For 2 minutes to form nuclei. Subsequently, the temperature of the solution was raised to 60 ° C. over a period of 60 minutes, the pH was adjusted to 5.0 with an aqueous solution of sodium carbonate, and then an aqueous solution of silver nitrate (5.902 mol), potassium bromide and iodide were added. A mixed aqueous solution of potassium (2 mol% of potassium iodide) was added over 42 minutes by a double jet method while keeping the silver potential at 9 mV. After the addition was completed, the temperature was lowered to 40 ° C., and desalting and washing were immediately performed using a normal flocculation method.

The resulting seed crystal emulsion had an average sphere-equivalent diameter of 0.24 μm, an average aspect ratio of 4.8, and a maximum side length ratio (maximum side ratio of each grain) of 90% or more of the total projected area of silver halide grains. The emulsion was composed of hexagonal tabular grains having a ratio of a side length to a minimum side length of 1.0 to 2.0. This emulsion is referred to as seed emulsion-1.

[Solution A1] Ossein gelatin 24.2 g Potassium bromide 10.8 g HO (CH ₂ CH ₂ O) _m (CH (CH ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) (10% ethanol solution) 6.78 ml 10% nitric acid 114 ml H ₂ O 9657 ml Preparation of silver iodide fine grain emulsion SMC-1 6.0% by weight gelatin aqueous solution containing 0.06 mol of potassium iodide 7.06 with vigorous stirring of 5 liters
An aqueous silver nitrate solution and an aqueous 7.06 mol potassium iodide solution, 2 liters each, were added over 10 minutes. During this time, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the particles are prepared, the pH is adjusted using an aqueous sodium carbonate solution.
Was adjusted to 5.0. The average particle size of the obtained silver iodide fine particles was 0.05 μm. This emulsion is designated as SMC-1.

Preparation of silver iodobromide d 0.178 mol of seed crystal emulsion-1 and HO (CH ₂ CH ₂
O) _m (CH (CH ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n
H (m + n = 9.77) in 10% ethanol solution 0.5
4.5% by weight of an aqueous inert gelatin solution 70
0 ml at 75 ° C., pAg 8.4, pH 5.0.
Then, particles were formed by the simultaneous mixing method with vigorous stirring by the following procedure.

1) An aqueous solution of 3.093 mol of silver nitrate, 0.287 mol of SMC-1 and an aqueous solution of potassium bromide were added while maintaining pAg at 8.4 and pH at 5.0.

2) Subsequently, the solution was cooled to 60 ° C.
g was adjusted to 9.8. Thereafter, 0.071 mol of SM
C-1 was added and aging was performed for 2 minutes (introduction of dislocation lines).

3) An aqueous solution of 0.959 mol of silver nitrate, 0.03 mol of SMC-1 and an aqueous solution of potassium bromide were added while maintaining the pAg at 9.8 and the pH at 5.0.

Each solution was added at an optimum rate throughout the particle formation so as to prevent formation of new nuclei and Ostwald ripening between particles. After completion of the addition, the resultant was subjected to a water washing treatment at 40 ° C. using a normal flocculation method, and then gelatin was added and redispersed to adjust the pAg to 8.1 and the pH to 5.8.

The obtained emulsion had a particle size (cubic 1 of the same volume).
Tabular grains having a halogen composition having a side length of 0.74 μm, an average aspect ratio of 5.0, and a silver iodide content of 2 / 8.5 / X / 3 mol% (X is a dislocation line introduction position) from the inside of the grains. Emulsion. When this emulsion was observed with an electron microscope, five or more dislocation lines were observed both in the fringe portion and in the inside of the grain in 60% or more of the total projected area of the grain in the emulsion. The surface silver iodide content was 6.7 mol%.

Preparation of silver iodobromide f In the preparation of silver iodobromide d, pAg was adjusted to 8. in step 1).
8 and the amount of silver nitrate to be added was 2.077 mol SMC-1.
And the amount of silver nitrate added in step 3) was 0.91 mol and the amount of SMC-1 was 0.079 mol in the same manner as for silver iodobromide d. Silver fide f was prepared.

The obtained emulsion had a particle size (cubic 1 of the same volume).
Edge length) 0.65 μm, average aspect ratio 6.5, silver iodide content 2 / 9.5 / X / 8.0 mol% from the inside of the grain
The emulsion was composed of tabular grains having a halogen composition of (X is a dislocation line introduction position). When this emulsion was observed with an electron microscope, five or more dislocation lines were observed both in the fringe portion and in the inside of the grain in 60% or more of the total projected area of the grain in the emulsion. The surface silver iodide content was 11.9 mol%.

After the above-described sensitizing dyes were added to each of the above emulsions and ripened, triphenylphosphine selenide, sodium thiosulfate, chloroauric acid, potassium thiocyanate,
Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (ST-1) and 2-mercaptotetrazole (AF-3) are added, and fog and sensitivity are optimized according to a conventional method. Chemical sensitization was applied.

Further, silver iodobromide a, b, c, e, g, h,
i and j were also prepared according to the above silver iodobromide d and f and subjected to spectral sensitization and chemical sensitization.

Next, the coupler M-1 in the tenth layer of the sample 1
And a compound of the general formulas [II] and [III] (Comparative Compound-4 for comparison (the structure is described after Table 4)).
Layer, ninth layer, tenth layer), coupler, general formula [II],
Multilayer samples, Samples 2 to 28, were prepared in the same manner as in Sample 1, except that the compound [III], emulsion, amount added, etc. were replaced as shown in Table 4.

Incidentally, in addition to the above composition, a coating aid SU-
1, SU-2, SU-3, dispersing aid SU-4, viscosity modifier V-1, stabilizer ST-2, antifoggant AF-1, weight average molecular weight: 10,000 and weight average molecular weight: 1 ,
100,000 two types of polyvinylpyrrolidone (AF-
2) Hardeners H-1, H-2 and preservative Dse-1 were added.

The structure of the compound used in the above sample is shown below.

[0128]

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[0129]

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[0130]

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[0131]

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[0132]

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[0133]

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[0134]

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[0135]

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[0136]

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The obtained sample was processed into a usual 135 size, packed in a patrone, and sealed in a plastic container under an atmosphere of 20 ° C. and a relative humidity of 55%. The following evaluation was performed about the sample produced as mentioned above.

[Evaluation of Sensitivity and Fog Immediately After Coating] The prepared sample was exposed to a white neutral wedge and subjected to a color development process described later. After drying, the green light transmission density was measured with a densitometer manufactured by X-rite to obtain sensitometry.
The minimum density of the obtained sensitometry was regarded as fog, and the sensitivity was determined from the reciprocal of the exposure amount giving a density of minimum density + 0.3. As a result, the fog and sensitivity of sample 1 were 9
8, 102, and shown as relative values.

[Evaluation of Sensitivity Fog Over Time] The deterioration over time was evaluated in the same manner as the sample immediately after application after leaving the prepared sample packed in a patrone at 40 ° C. for 5 days.
As a result, the fog and the sensitivity of the sample 1 immediately after coating were 9
8, 102, and shown as relative values.

<< Color development processing >> (Processing step) Process Processing time Processing temperature Replenishment amount * Color development 3 minutes 15 seconds 38 ± 0.3 ° C. 780 ml Bleaching 45 seconds 38 ± 2.0 ° C. 150 ml Fixing 1 minute 30 38 ± 2.0 ° C. 830 ml Stability 60 seconds 38 ± 5.0 ° C. 830 ml Drying 60 seconds 55 ± 5.0 ° C.-* The replenishing amount is a value per 1 m ² of the photosensitive material.

<Preparation of processing agent> (Composition of color developing solution) Water 800 ml Potassium carbonate 30 g Sodium hydrogen carbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxyamine sulfate 2.5 g Sodium chloride 0.6 g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 4.5 g Diethylenetetraaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g Finish to 2.0 liters and adjust to pH 10.06 with potassium hydroxide or 20% sulfuric acid.

(Composition of color developing replenisher) Water 800 ml Potassium carbonate 35 g Sodium hydrogen carbonate 3.0 g Potassium sulfite 5.0 g Sodium bromide 0.4 g Hydroxyamine sulfate 3.1 g 4-Amino-3-methyl-N-ethyl -N- (β-hydroxyethyl) aniline sulfate 6.3 g Diethylenetetraamine pentaacetic acid 3.0 g Potassium hydroxide 2.0 g Water was added to make up to 1.0 liter, and potassium hydroxide or 20% sulfuric acid was used. Adjust to pH 10.18.

(Bleach liquid composition) Water 700 ml 1,3-Diaminopropanetetraacetate ammonium (III) ammonium 125 g ethylenediaminetetraacetic acid 2 g sodium nitrate 40 g ammonium bromide 150 g glacial acetic acid 40 g Adjust to pH 4.4 with water or glacial acetic acid.

(Composition of bleaching replenisher) Water 700 ml 1,3-diaminopropanetetraacetic acid iron (III) ammonium 175 g ethylenediaminetetraacetic acid 2 g sodium nitrate 50 g ammonium bromide 200 g glacial acetic acid 56 g Adjust to pH 4.4 using aqueous ammonia or glacial acetic acid.

(Formulation of Fixing Solution) Water 800 ml Ammonium thiocyanate 120 g Ammonium thiosulfate 150 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid 2 g Add water to make up to 1.0 liter, and adjust to pH 6.2 using aqueous ammonia or glacial acetic acid.

(Formulation of Fixing Replenisher) Water 800 ml Ammonium thiocyanate 150 g Ammonium thiosulfate 180 g Sodium sulfite 20 g Ethylenediaminetetraacetic acid 2 g Add water to make up to 1.0 liter, and adjust to pH 6.5 using aqueous ammonia or glacial acetic acid. .

(Preparation of Stabilizing Solution and Stable Replenishing Solution) Water 900 ml p-octylphenol / ethylene oxide / 10 mol adduct 2.0 g dimethylolurea 0.5 g hexamethylenetetramine 0.2 g 1,2-benzoisothiazolin-3-one 1 g Siloxane (UCC L-77) 0.1 g Ammonia water 0.5 ml Add water to make up to 1.0 liter, and adjust to pH 8.5 using ammonia water or 50% sulfuric acid.

Tables 4 and 5 summarize the results.

[0149]

[Table 4]

[0150]

[Table 5]

[0151]

Embedded image

As is clear from Tables 4 and 5, the sample of the present invention has low fog and high sensitivity, and both sensitivity and fog have excellent storage stability over time.

[0153]

According to the present invention, a silver halide color photographic light-sensitive material having low fog, high sensitivity and improved storage stability can be provided.

Claims (3)

[Claims] 1. A silver halide photographic material comprising at least one compound represented by the following general formula [I] and at least one compound represented by the following general formula [II]. Embedded image [In the formula, R ¹¹ represents a hydrogen atom or a group capable of leaving by reaction with an oxidized form of an aromatic primary amine color developing agent. R ¹² represents an aryl group. R ¹³ represents a substituent, n
₁ represents an integer of ₁ to 5. When n ₁ is 2 or more, R ¹³ may be the same or different. [Chemical formula 2] [Wherein, Het represents a 5- to 6-membered nitrogen-containing heterocyclic ring having no mercapto group or a blocked mercapto group as a substituent, J represents a (m ₂ +1) valent linking group,
Represents a water-soluble group. n ₂ represents an integer of 0 to 5, m ₂ is 1
Represents the above integer. ] 2. A silver halide photographic light-sensitive material comprising at least one compound represented by the general formula [I] and at least one compound represented by the following general formula [III]. Embedded image [In the formula, R ³¹ and R ³² represent an aliphatic group, an aromatic group, or a heterocyclic group. R ³¹ and R ³² may be the same or different, and when R ³¹ and R ³² are an aliphatic group, they may combine with each other to form a ring. n ₃ represents an integer of 2 or more. ] 3. The silver halide photographic material according to claim 1, wherein the general formula [II] is represented by the general formula [IV] or the general formula [V]. Embedded image [In the general formula [IV], W represents an oxygen atom, a sulfur atom, a nitrogen atom or C (R ₄₁ ), and X represents a nitrogen atom or C
(R ₄₁ ). Z represents an atomic group necessary for forming a 5- to 6-membered nitrogen-containing aromatic heterocyclic ring having no mercapto group or a blocked mercapto group as a substituent.
R ₄₁ represents a substituent other than a mercapto group or a blocked mercapto group, or a hydrogen atom. J, Q, n ₂ , m ₂
Has the same meaning as in formula [II]. In the general formula [V],
P, Q ', R and T represent a nitrogen atom or C ( _R41 ),
J, Q, n ₂ and m ₂ have the same meanings as in the case of the general formula [II]. ]