JP3394638B2 - Silver halide photographic materials - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material. More specifically, the present invention relates to a silver halide photographic light-sensitive material having high sensitivity, less fog, and excellent storage stability.

[0002]

2. Description of the Related Art A great deal of effort has hitherto been made to increase the sensitivity of silver halide photographic light-sensitive materials. Sensitizing dyes used for spectral sensitization are known to have a great influence on the performance of silver halide photographic light-sensitive materials. With sensitizing dyes, slight differences in structure have a great influence on photographic performance such as sensitivity, fog, and storage stability, but it is difficult to predict the effect in advance, and many studies have been conducted so far. Have synthesized many sensitizing dyes and have been trying to investigate their photographic performance. For example, as described in US Pat. No. 4,975,362, having a methylthio group alone greatly improves photographic performance. Of the sensitizing dyes, those having a nitrogen-containing heterocycle having a sulfoalkyl group as a partial structure are often used. Well-known examples of the sulfoalkyl group include a 2-sulfoethyl group, a 3-sulfopropyl group, a 4-sulfobutyl group, and a 3-sulfobutyl group. However, sulfoalkyl groups other than these have hardly been studied, and it is not possible at all to predict what photographic performance various sulfoalkyl groups other than these will show.

Further, reduction sensitization attempts have been studied for a long time in order to increase the sensitivity of silver halide photographic light-sensitive materials. For example, tin compounds are useful as reduction sensitizers in US Pat. No. 2,487,850, polyamine compounds are useful in US Pat. No. 2,512,925, and thiourea dioxide compounds are useful as reduction sensitizers in British Patent 789,823. Was disclosed. Furthermore, Photographic Science and
The properties of silver nuclei produced by various reduction sensitization methods are compared in Engineering Volume 23, page 113 (1979), and dimethylamine borane, stannous chloride, hydrazine, high pH aging and low pAg aging methods are compared. Was adopted. The method of reduction sensitization is further described in US Pat. No. 2,518,698.
No. 3, No. 3,201,254, No. 3,411,91
No. 7, No. 3,779, 777, No. 3,930, 8
No. 67 is also disclosed. Regarding the improvement of the reduction sensitization method as well as the selection of the reduction sensitizer, Japanese Patent Publication No. 57-33572
No. 58-1410.

However, according to the research conducted by the present inventors, when spectral sensitization is carried out by adsorbing a sensitizing dye on reduction-sensitized silver halide grains, the spectral sensitization is carried out especially in the green and red regions. In some cases, it has been revealed that it is extremely difficult to obtain sufficient spectral sensitivity without causing an unfavorable effect on photographic performance (for example, increase in fog). In order to prevent desorption of the sensitizing dye from the silver halide grains in the light-sensitive material (especially when the humidity is high), a method of adsorbing the sensitizing dye at a high temperature (50 ° C. or higher), or for improving the sensitivity. Methods for adsorbing a sensitizing dye before chemical sensitization are widely known, but when these methods are applied to adsorb a spectral sensitizing dye in the green region or red region to a reduction sensitized emulsion, Increases fog significantly. For the above reasons, there has been a demand for a technique for spectrally sensitizing reduction-sensitized silver halide grains with high sensitivity and without causing adverse effects such as fog.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is, firstly, to provide a silver halide photographic light-sensitive material having high sensitivity, less fog and excellent storage stability. Secondly, to provide a silver halide photographic light-sensitive material using a reduction sensitized emulsion, which has high sensitivity, little fog, and excellent storage stability.

[0006]

The object of the present invention is to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, the emulsion layer being represented by the following general formula (I). It can be achieved by a silver halide photographic light-sensitive material characterized by containing at least one compound.

[0007]

[Chemical 6]

In the formula (I), Ra and Rb represent a hydrogen atom, an aliphatic group, an aryl group or a heterocyclic group. However, Ra and Rb are not hydrogen atoms at the same time.
La and Lb represent a methylene group. k ₁ represents an integer of 0 to 5 and k ₂ represents an integer of 0 to 5. However, k ₁ = 2 and k ₂ = 0 do not hold. L ₁ and L ₂ represent a methine group. p ₁ represents 0 or 1. Z ₁ represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle. M ₁
Represents a charge balancing counter ion, and m ₁ represents an integer of 0 or more necessary for neutralizing the charge of the molecule. Q represents an atomic group necessary for forming a methine dye. Furthermore, the general formula (I)
The compound represented by the following general formula (II)
I) or a compound selected from the general formula (IV),
More preferable.

[0009]

[Chemical 7]

In the formula (II), L ₃ , L ₄ , L ₅ , L ₆ and L
₇ , L ₈ and L ₉ represent a methine group. p ₂ and p ₃ represent 0 or 1. n ₁ represents 0, 1, 2, or 3. Z
₂ and Z ₃ represent an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle. M ₂ represents a charge balancing counter ion, and m ₂ represents an integer of 0 or more necessary for neutralizing the charge of the molecule. R ₁ and R ₂ represent an alkyl group. However, R
_At least one of ₁ and R ₂ is an alkyl group represented by Rz below.

[0011]

[Chemical 8]

In Rz, Ra, Rb, La, Lb,
k ₁ and k ₂ have the same meaning as in formula (I).

[0013]

[Chemical 9]

In the formula (III), L ₁₀ , L ₁₁ and
L ₁₂ and L ₁₃ represent a methine group. p ₄ is 0 or 1
Represents n ₂ represents 0, 1, 2, or 3. Z ₄ and Z
₅ represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle. M ₃ represents a charge-balancing counter ion, and m ₃ represents an integer of 0 or more necessary for neutralizing the charge of the molecule.
R ₄ represents an alkyl group, an aryl group or a heterocyclic group. R
₃ is an alkyl group represented by the above Rz.

[0015]

[Chemical 10]

In the formula (IV), L ₁₄ , L ₁₅ , L ₁₆ and
L ₁₇ , L ₁₈ , L ₁₉ , L ₂₀ , L ₂₁ and L ₂₂ represent a methine group. p ₅ and P ₆ represent 0 or 1. n ₃
And n ₄ represents 0, 1, 2, or 3. Z ₆ , Z ₇ and Z ₈ represent an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle. M ₄ represents a charge-balancing counterion, m ₄
Represents an integer of 0 or more necessary for neutralizing the charge of the molecule. R ₅ and R ₇ represent an alkyl group. R ₆ represents an alkyl group, an aryl group or a heterocyclic group. However, R ₅ and R
_At least one of ₇ is an alkyl group represented by Rz.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The compounds used in the present invention will be described in detail below. Although any methine dye can be formed by Q, cyanine dyes, merocyanine dyes, rhodacyanine dyes, trinuclear merocyanine dyes, allopolar dyes, hemicyanine dyes and styryl dyes are preferable. These methine dyes
Heterocyclic Compounds-C by FM Harmer, "Heterocyclic Compounds-Cyanine and Related Compounds"
yanine Dyes and Related Compounds, "John Wiley & Sons, Inc.-New York, London, 1964. In the general formula (I), when a cyanine dye is formed by Q, it can be expressed by the following resonance formula.

[0018]

[Chemical 11]

In the general formulas (I), (II), (III) and (IV), 5- or 6-membered compounds represented by Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₆ and Z ₈ are included. Examples of the nitrogen heterocycle include thiazoline nucleus, thiazole nucleus, benzothiazole nucleus, oxazoline nucleus, oxazole nucleus, benzoxazole nucleus, selenazoline nucleus, selenazole nucleus, benzoselenazole nucleus, 3,
3-dialkylindolenine nuclei (eg 3,3-dimethylindolenine), imidazoline nuclei, imidazole nuclei,
Benzimidazole nucleus, 2-pyridine nucleus, 4-pyridine nucleus, 2-quinoline nucleus, 4-quinoline nucleus, 1-isoquinoline nucleus, 3-isoquinoline nucleus, imidazo [4,5-b] quinoxaline nucleus, oxadiazole nucleus, Examples thereof include thiadiazole nucleus, tetrazole nucleus, and pyrimidine nucleus. Preferred are benzoxazole nucleus, benzothiazole nucleus, benzimidazole nucleus and quinoline nucleus,
More preferably, they are a benzoxazole nucleus and a benzothiazole nucleus. Z ₁ and Z ₂ in the general formula (II)
Especially preferred is a benzoxazole nucleus.

Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₆ , and Z ₈
When the above substituent is V, the substituent represented by V is not particularly limited, but for example, a halogen atom (for example, chlorine, bromine, iodine, fluorine), a mercapto group, a cyano group,
Carboxyl group, phosphoric acid group, sulfo group, hydroxy group,
A carbamoyl group having 1 to 10 carbon atoms, preferably 2 to 8 carbon atoms, and more preferably 2 to 5 carbon atoms (eg, methylcarbamoyl, ethylcarbamoyl, morpholinocarbonyl), 0 to 10 carbon atoms, preferably 2 to 8 carbon atoms. , More preferably a sulfamoyl group having 2 to 5 carbon atoms (eg, methylsulfamoyl, ethylsulfamoyl, piperidinosulfonyl), a nitro group, 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably An alkoxy group having 1 to 8 carbon atoms (eg, methoxy, ethoxy, 2-methoxyethoxy, 2-phenylethoxy), 6 to 20 carbon atoms, preferably 6 to 1 carbon atoms
2, more preferably an aryloxy group having 6 to 10 carbon atoms (for example, phenoxy, p-methylphenoxy, p-
Chlorophenoxy, naphthoxy), carbon number 1 to 20,
Preferably an acyl group having 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms (eg acetyl, benzoyl, trichloroacetyl), 1 to 20 carbon atoms, preferably 2 to 12 carbon atoms, and more preferably 2 carbon atoms. 8 acyloxy groups (eg acetyloxy, benzoyloxy), 1 to 20 carbon atoms, preferably 2 to 1 carbon atoms
2, more preferably an acylamino group having 2 to 8 carbon atoms (eg acetylamino), a sulfonyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 8 carbon atoms (eg methanesulfonyl, ethane). Sulfonyl, benzenesulfonyl, etc.), 1 to 2 carbon atoms
0, preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms sulfinyl group (eg methanesulfinyl, benzenesulfinyl), 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 carbon atoms
To 8 sulfonylamino groups (eg, methanesulfonylamino, ethanesulfonylamino, benzenesulfonylamino, etc.), amino groups,

A substituted amino group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, and more preferably 1 to 8 carbon atoms (eg, methylamino, dimethylamino, benzylamino, anilino, diphenylamino), 0 to carbon atoms. 1
5, preferably 3 to 10 carbon atoms, more preferably 3 to 6 carbon ammonium groups (eg trimethylammonium group, triethylammonium group), 0 to 15 carbon atoms, preferably 1 to 10 carbon atoms, more preferably carbon A hydrazino group having 1 to 6 carbon atoms (eg trimethylhydrazino group), 1 to 15 carbon atoms, preferably 1 carbon atom
To 10, more preferably a ureido group having 1 to 6 carbon atoms (for example, ureido group, N, N-dimethylureido group), 1 to 15 carbon atoms, preferably 1 to 1 carbon atoms.
0, more preferably an imide group having 1 to 6 carbon atoms (eg, succinimide group), an alkyl or arylthio group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, and more preferably 1 to 8 carbon atoms (eg, methylthio, Ethylthio, carboxyethylthio, sulfobutylthio,
Phenylthio, etc.), an alkoxycarbonyl group having 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms (eg methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl), 6 to 20 carbon atoms, preferably An aryloxycarbonyl group having 6 to 12 carbon atoms, more preferably 6 to 8 carbon atoms (for example, phenoxycarbonyl),

An unsubstituted alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms (eg methyl, ethyl, propyl, butyl), 1 to 18 carbon atoms, preferably 1 to 1 carbon atoms
0, more preferably a substituted alkyl group having 1 to 5 carbon atoms (hydroxymethyl, trifluoromethyl, benzyl,
Carboxyethyl, ethoxycarbonylmethyl, acetylaminomethyl, and also here an unsaturated hydrocarbon group having 2 to 18 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 3 to 5 carbon atoms (for example, vinyl group, ethynyl group, A 1-cyclohexenyl group, a benzylidine group, and a benzylidene group) are also included in the substituted alkyl group. ), 6 to 20 carbon atoms, preferably 6 to 1 carbon atoms
5, more preferably a substituted or unsubstituted aryl group having 6 to 10 carbon atoms (for example, phenyl, naphthyl, p-carboxyphenyl, p-nitrophenyl, 3,5-dichlorophenyl, p-cyanophenyl, m-fluorophenyl, p-tolyl), optionally substituted heterocyclic group having 10 to 20 carbon atoms, preferably 2 to 10 carbon atoms, and more preferably 4 to 6 carbon atoms (eg pyridyl, 5-methylpyridyl, thienyl, furyl, morpholino). , Tetrahydrofurfuryl). Further, it may have a structure in which a benzene ring or a naphthalene ring is condensed. Further, V may be further substituted on these substituents.

Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₆ , and Z ₈
Preferred as the substituent of are the above-mentioned alkyl group, aryl group, alkoxy group, halogen atom, acyl group, cyano group, sulfonyl group, and benzene ring condensation, and more preferably alkyl group, aryl group, halogen atom,
An acyl group, a sulfonyl group, and a benzene ring condensation,
Particularly preferred are methyl group, methoxy group, chlorine atom, bromine atom, iodine atom, and benzene ring condensation.

Ra and Rb in the general formula (I) represent a hydrogen atom, an aliphatic group, an aryl group or a heterocyclic group.
However, Ra and Rb are not hydrogen atoms at the same time. Specific examples include the following. As the aliphatic group having 1 or more carbon atoms, an unsubstituted alkyl group having 1 to 16 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 4 carbon atoms (eg, ethyl, butyl, pentyl), carbon Number 1 to 20, preferably 3 to 1 carbon atoms
0, and more preferably, a substituted aliphatic group having 3 to 7 carbon atoms (for example, an aliphatic group substituted with V and an unsaturated aliphatic group, which have been mentioned as the substituents such as Z _{1 and the} like described above. Is an allyl group, vinyl group, benzyl group, hydroxyethyl group, carboxyethyl group, etc.),
An unsubstituted aryl group having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, and more preferably 6 to 8 carbon atoms (eg, phenyl group, 1-naphthyl group), 6 to 20 carbon atoms,
Preferably, a substituted aryl group having 6 to 10 carbon atoms, more preferably 6 to 8 carbon atoms (for example, an aryl group substituted with V mentioned as the substituent of Z _{1 and the} like mentioned above. Specifically, p-methoxy is mentioned. A phenyl group, a p-methylphenyl group, a p-chlorophenyl group, etc.), and a carbon number of 1 to 20, preferably a carbon number of 3 to 1.
0, more preferably an unsubstituted heterocyclic group having 4 to 8 carbon atoms (eg, 2-furyl group, 2-thienyl group, 2-pyridyl group), 1 to 20 carbon atoms, preferably 3 to 1 carbon atoms.
0, and more preferably a substituted heterocyclic group having 4 to 8 carbon atoms (for example, a heterocyclic group substituted with V mentioned above as the substituent such as Z _{1 and the} like. Specifically, 5-methyl-2
Examples include -thienyl group and 4-methoxy-2-pyridyl group. The aliphatic group preferably has 2 or more carbon atoms. Ethyl group, allyl group, vinyl group and benzyl group are more preferable, and allyl group, vinyl group and benzyl group are particularly preferable. Among the aliphatic group, the aryl group and the heterocyclic group, the aryl group and the heterocyclic group are preferable. More preferably, it is a heterocyclic group. The aryl group is particularly preferably a phenyl group, and the heterocyclic group is particularly preferably a 2-thiethyl group. Although Ra and Rb are not hydrogen atoms at the same time, Ra and Rb
It is preferable that one of b is a hydrogen atom and the other is an aliphatic group, an aryl group or a heterocyclic group.

As La and Lb, an unsubstituted methylene group,
Alternatively, a substituted methylene group (for example, a V-substituted methylene group mentioned above as a substituent such as Z _{1 and the} like. Specific examples include a methyl group-substituted methylene group, an ethyl group-substituted methylene group, a phenyl group-substituted methylene group, and a hydroxy group. Examples include a group-substituted methylene group.) An unsubstituted methylene group is preferable.

K₁Is an integer from 0 to 5, k₂Is an integer from 0 to 5
Represents Where k₁= 2 and k ₂= 0 means
Absent. k₁And k₂Is preferably 1 or more and 5 or less. k
₁Is preferably 1 or 3. More preferably 3
Is. k₂Is preferably 0 or 1. Even better
It is preferably 0. Note that k₁, K₂When is 2 or more, L
Although a and Lb are repeated, they need not be the same.

Next, Ra, Rb, La, Lb, k ₁ , k ₂
Examples of the sulfoalkyl group represented by Note that Rz
Preferred examples are shown in the order of ₁ to Rz ₈ , and Ra, R
Particularly preferred are Rz ₃ , Rz ₄ , Rz ₅ , Rz ₆ , Rz ₇ , and Rz ₈ in which at least one of b has a substituent having 2 or more carbon atoms. Most preferably, it is Rz ₈ .

[0028]

[Chemical 12]

R ₁ in the general formulas (II), (III) and (IV),
R ₂ , R ₃ , R ₅ and R ₇ each represent an alkyl group. As the alkyl group represented by R ₁ and R ₂ ,
For example, an unsubstituted alkyl group having 1 to 18, preferably 1 to 7, particularly preferably 1 to 4 carbon atoms (for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl), carbon Substituted alkyl groups having 1 to 18, preferably 1 to 7, and particularly preferably 1 to 4 atoms (for example, the V-substituted alkyl groups mentioned as the above-mentioned substituents such as Z ₁ are mentioned. Preferably, aralkyl groups ( For example, benzyl, 2-phenylethyl), unsaturated hydrocarbon group (eg, allyl group), hydroxyalkyl group (eg, 2-hydroxyethyl, 3-hydroxypropyl), carboxyalkyl group (eg, 2-carboxyethyl, 3-). Carboxypropyl, 4-carboxybutyl, carboxymethyl), alkoxy Alkyl group (e.g., 2-methoxyethyl, 2- (2-methoxyethoxy) ethyl), aryloxyalkyl group (e.g., 2-phenoxyethyl, 2
-(1-naphthoxy) ethyl), an alkoxycarbonylalkyl group (eg, ethoxycarbonylmethyl, 2-benzyloxycarbonylethyl), an aryloxycarbonylalkyl group (eg, 3-phenoxycarbonylpropyl), an acyloxyalkyl group (eg, 2-acetyloxy). Ethyl), acylalkyl groups (eg 2-acetylethyl), carbamoylalkyl groups (eg 2-morpholinocarbonylethyl), sulfamoylalkyl groups (eg N, N-dimethylcarbamoylmethyl), sulfoalkyl groups (eg 2- Sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2-
[3-sulfopropoxy] ethyl, 2-hydroxy-3
-Sulfopropyl, 3-sulfopropoxyethoxyethyl), a sulfatoalkyl group (for example, 3-fluphatopropyl, 4-fluphatobutyl), a heterocyclic-substituted alkyl group (for example, 2- (pyrrolidin-2-one-1-) Ill)
Ethyl, tetrahydrofurfuryl), methanesulfonylcarbamoylmethyl group and the like). R ₁ ,
The alkyl groups of R ₂ , R ₃ , R ₅ and R ₇ are preferably the above-mentioned carboxyalkyl group, sulfoalkyl group and Rz, and more preferably the above-mentioned sulfoalkyl group and Rz.

Z ₅ represents the atomic group necessary for forming an acidic nucleus, but can take the form of the acidic nucleus of any common merocyanine dye. The acidic nucleus referred to here is, for example, "The Theory of the Ph.D. Process" edited by James.
otographic Process) 4th edition, Macmillan Publishers, 19
1977, defined by page 198. Specifically, US Pat. Nos. 3,567,719 and 3,575,869.
No. 3,804,634, 3,837,862
No. 4,002,480, 4,925,777
And JP-A-3-167546.

It is preferable that the acidic nucleus forms a 5- or 6-membered nitrogen-containing heterocycle consisting of carbon, nitrogen, and chalcogen (typically oxygen, sulfur, selenium, and tellurium) atoms. Are the following cores. 2-pyrazolin-5-one, pyrazolidine-3,5-dione, imidazolin-5-one, hydantoin, 2 or 4-thiohydantoin, 2-iminooxazolidin-4-one, 2-oxazolin-5-one, 2- Thiooxazoline-2,4-dione, isoxazoline-5-one, 2
-Thiazolin-4-one, thiazolidin-4-one, thiazolidine-2,4-dione, rhodanine, thiazolidine-2,4-dithione, isorhodanine, indane-
1,3-dione, thiophen-3-one, thiophene-
3-one-1,1-dioxide, indoline-2-one, indoline-3-one, 2-oxoindazolinium, 3-oxoindazolinium, 5,7-dioxo-
6,7-dihydrothiazolo [3,2-a] pyrimidine,
Cyclohexane-1,3-dione, 3,4-dihydroisoquinolin-4-one, 1,3-dioxane-4,6-
Dione, barbituric acid, 2-thiobarbituric acid, chroman-2,4-dione, indazoline-2-one, pyrido [1,2-a] pyrimidine-1,3-dione, pyrazolo [1,5-b ] Quinazolone, Pyrazolo [1,5-
a] benzimidazole, pyrazolopyridone, 1, 2,
3,4-tetrahydroquinoline-2,4-dione, 3-
Oxo-2,3-dihydrobenzo [d] thiophene-
1,1-dioxide, 3-dicyanomethine-2,3-
The nucleus of dihydrobenzo [d] thiophene-1,1-dioxide.

Z ₅ is preferably hydantoin, 2 or 4-thiohydantoin, 2-oxazoline-5-one, 2-thiooxazoline-2,4-dione, thiazolidine-2,4-dione, rhodanin, thiazolidine-.
2,4-dithione, barbituric acid, and 2-thiobarbituric acid, more preferably hydantoin, 2 or 4-thiohydantoin, 2-oxazolin-5-one, rhodanine, barbituric acid, and 2-thiobarbite. It is a tool acid. Particularly preferred are 2 or 4-thiohydantoin, 2-oxazolin-5-one, and rhodanine.

The 5- or 6-membered nitrogen-containing heterocycle formed by Z ₇ is a heterocycle represented by Z ₅ from which an oxo group or a thioxo group has been removed. Preferably hydantoin, 2 or 4-thiohydantoin, 2-oxazoline-5-one, 2-thiooxazoline-2,4-
Dione, thiazolidine-2,4-dione, rhodanine,
Thiazolidine-2,4-dithione, barbituric acid, 2
-Thiobarbituric acid from which an oxo group or a thioxo group has been removed, more preferably hydantoin,
2 or 4-thiohydantoin, 2-oxazoline-5
-One, rhodanine, barbituric acid, 2-thiobarbituric acid from which an oxo group or a thioxo group has been removed, particularly preferably 2 or 4-thiohydantoin,
2-Oxazolin-5-one and rhodanine from which an oxo group or a thioxo group has been removed.

Examples of the alkyl group represented by R ₄ and R ₆ include the unsubstituted alkyl groups and substituted alkyl groups mentioned above as examples of R ₁ and the like, and similar groups are preferable. Also, it has 6 to 20 carbon atoms, preferably 6 carbon atoms.
To 10, more preferably an unsubstituted aryl group having 6 to 8 carbon atoms (eg, phenyl group, 1-naphthyl group), 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, and more preferably 6 to 8 carbon atoms. A substituted aryl group (for example, an aryl group substituted with V mentioned above as a substituent such as Z _{1 and the} like. Specifically, a p-methoxyphenyl group,
Examples thereof include p-methylphenyl group and p-chlorophenyl group. ), 1 to 20 carbon atoms, preferably 3 carbon atoms
To 10, more preferably an unsubstituted heterocyclic group having 4 to 8 carbon atoms (for example, 2-furyl group, 2-thienyl group, 2-pyridyl group, 3-pyrazolyl, 3-isoxazolyl, 3
-Isothiazolyl, 2-imidazolyl, 2-oxazolyl, 2-thiazolyl, 2-pyridazyl, 2-pyrimidyl, 3-pyrazyl, 2- (1,3,5-triazolyl), 3- (1,2,4-triazolyl) , 5-tetrazolyl), a substituted heterocyclic group having 1 to 20 carbon atoms, preferably 3 to 10 carbon atoms, and more preferably 4 to 8 carbon atoms (for example, V mentioned above as a substituent group such as Z ₁ is substituted). And a heterocyclic group, specifically 5-methyl-2.
Examples include -thienyl group and 4-methoxy-2-pyridyl group. ) Is mentioned. Preferred as R ₄ and R ₆ are methyl, ethyl, 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, carboxymethyl, phenyl, 2-pyridyl and 2-thiazolyl, more preferably ethyl, 2-sulfoethyl, carboxymethyl, phenyl and 2-pyridyl.

L ₁ , L ₂ , L ₃ , L ₄ , L ₅ , L ₆ , L
_{7, L 8, L 9,} L 10, L 11, L 12, L 13, L 14,
L ₁₅ , L ₁₆ , L ₁₇ , L ₁₈ , L ₁₉ , L ₂₀ , L ₂₁ , and L ₂₂
Each independently represents a methine group. The methine group represented by L _{1 to} L ₂₂ may have a substituent, and examples of the substituent include a substituted or unsubstituted C 1 to 15, preferably C 1 to 10 and more preferably carbon. Alkyl group of the number 1 to 5 (eg methyl, ethyl, 2-carboxyethyl), substituted or unsubstituted carbon number 6 to 2
0, preferably 6 to 15, more preferably 6 to 10 carbon aryl groups (eg phenyl, o-carboxyphenyl), substituted or unsubstituted 3 to 20 carbon atoms, preferably 4 to 15 carbon atoms, More preferably, a heterocyclic group having 6 to 10 carbon atoms (for example, N, N-diethylbarbituric acid group), a halogen atom (for example, chlorine, bromine, fluorine, iodine), 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms. An alkoxy group having 10 or more preferably 1 to 5 carbon atoms (eg, methoxy, ethoxy), an alkylthio group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms (eg methylthio, ethylthio). ), An arylthio group having 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms, and more preferably 6 to 10 carbon atoms (eg, Phenylthio), from 0 carbon atoms 1
5, preferably an amino group having 2 to 10 carbon atoms, more preferably 4 to 10 carbon atoms (eg, N, N-diphenylamino, N-methyl-N-phenylamino, N-methylpiperazino) and the like. Further, it may form a ring with another methine group, or may form a ring with an auxiliary chromophore. Here, examples of the auxiliary chromophore include heterocycles represented by Z _{1 to} Z ₈ .

Each of n ₁ , n ₂ and n ₃ is preferably 0 or 1, and more preferably 1. n ₄ is preferably 0 or 1, and more preferably 0. n
_{When 1 to} n ₄ are 2 or more, the methine groups are repeated but they do not have to be the same.

M ₁ , M ₂ , M ₃ , and M ₄ are included in the formula to indicate the presence of a cation or anion when required to neutralize the ionic charge of the dye. There is. Typical cations are inorganic cations such as alkali metal ions (eg sodium ion, potassium ion, lithium ion), alkaline earth metal ions (eg calcium ion), ammonium ions (eg ammonium ion, tetraalkylammonium ion). , Pyridinium ion, ethylpyridinium ion) and the like. The anion may be either an inorganic anion or an organic anion,
Halogen anion (eg, fluorine ion, chlorine ion,
(Iodine ion), substituted aryl sulfonate ion (for example, p-toluene sulfonate ion, p-chlorobenzene sulfonate ion), aryl disulfonate ion (for example, 1,3-benzene sulfonate ion, 1,5-naphthalene disulfonate ion) , 2,6-naphthalenedisulfonate ion), alkylsulfate ion (for example, methylsulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, acetate ion, trifluoromethanesulfonate acid. Ions are mentioned. Furthermore, an ionic polymer or another dye having a charge opposite to that of the dye may be used. m ₁ , m ₂ ,
m ₃ and m ₄ represent the numbers required to balance the charge, and are 0 when forming a salt in the molecule. m ₁ ,
m ₂ , m ₃ and m ₄ are preferably 0 or more and 6 or less, more preferably 0 or more and 4 or less, and particularly preferably 0 or more and 1 or less. p ₁ , p ₂ , p ₃ , p ₄ ,
p ₅ and p ₆ each independently represent 0 or 1. It is preferably 0.

The general formulas (I), (II), and
Specific examples of the compounds (III) and (IV) are shown below, but the present invention is not limited thereto. Since the general formulas (II), (III) and (IV) are subordinate concepts of the general formula (I), specific examples of the general formula (I) include compounds excluding these subordinate compounds. Listed. Specific examples of compounds of general formula (II)

[0039]

[Chemical 13]

[0040]

[Chemical 14]

[0041]

[Chemical 15]

[0042]

[Chemical 16]

[0043]

[Chemical 17]

[0044]

[Chemical 18]

[0045]

[Chemical 19]

[0046]

[Chemical 20]

[0047]

[Chemical 21]

[0048]

[Chemical formula 22]

[0049]

[Chemical formula 23]

Specific Examples of Compounds of General Formula (III)

[0051]

[Chemical formula 24]

[0052]

[Chemical 25]

[0053]

[Chemical formula 26]

Specific examples of compounds of general formula (IV)

[0055]

[Chemical 27]

[0056]

[Chemical 28]

[0057]

[Chemical 29]

Specific Examples of Compounds of Formula (I)

[0059]

[Chemical 30]

[0060]

[Chemical 31]

The compounds represented by the general formula (I) of the present invention are described in "Heterocyclic Compounds-Cy" by FM Harmer.
anine Dyes and Related Compounds ", John Wiley & Sons-New York, London, 1964, DMSturmer," Heterocyclic Compounds-Special Topics. " Inn, Heterocyclic Compounds-Special
topics in heterocyclic chemistry ", Chapter 18, Section 14, 482-515, John Wiley & Sons-New York,
London, 1977, "Rodd's Chemistry of Ca
rbon Compounds) ”2nd.Ed.vol.IV.partB.1977,
Chapter 15, Paragraphs 369-422, Elsevier Scie Public Company, Inc.
nce Publishing Company Inc.), New York, etc.

Synthesis Example (Synthesis of Compound II-1) Compound II-1 was synthesized according to the following scheme.

[0063]

[Chemical 32]

[0064]

[Chemical 33]

A) Synthesis of 1-ethyl-1,4-butanesultone Trimethylene glycol 83.4 g (1.09 mol), propylsulfonyl chloride 343.2 g (2.406 mo)
l), and 850 ml of dichloromethane were cooled with dry ice / acetone with stirring to give triethylamine 335.4.
ml (2.406 mol) was added dropwise over 25 minutes. The internal temperature was maintained at -10 ° C or lower. Furthermore, after stirring at room temperature for 4 hours, the reaction solution was added to water 21, the dichloromethane layer was extracted, and then dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain 248 g of colorless liquid (A). Yield 79%.
210 g (0.729 mol) of (A) and tetrahydrofuran 21 were cooled to -78 ° C with stirring, and 464 ml (0.76 mol) of a solution of normal butyl lithium (1.65 mol / l) was cooled.
5 mol) was added dropwise over 30 minutes. Furthermore, -15
After stirring at 0 ° C. for 1 hour, the reaction solution was added to ethyl acetate 31 / water 1.51 and the ethyl acetate layer was extracted. Further, it was dried over magnesium sulfate, the solvent was distilled off under reduced pressure, and then the residue was distilled under reduced pressure to obtain 42 g (115-122 ° C / 2 mmHg, yield 35) of 1-ethyl-1,4-butanesaltone as a colorless liquid.
%) Was obtained.

B) Synthesis of quaternary salt 4-phenyl-2-methylbenzoxazole 4 g (0.
019 mol) and 1-ethyl-1,4-butanesaltone 3.1 g (0.019 mol) on an oil bath at 150 ° C. for 8 hours.
The mixture was heated and stirred for an hour. Ethyl acetate 5 while stirring the reaction mixture
After 0 ml was added and the reaction solution reached room temperature, the obtained crystals were filtered by absorption filtration and dried. (B) (colorless powder, yield 5.1 g, yield 72%, melting point 285-290)
℃)

C) Synthesis of compound (II-1) (B) 5 g (0.013 mol), orthopropionic acid ethyl ester 17 ml (0.0845 mol), acetic acid 15
ml and pyridine 15 ml were heated and stirred on an oil bath at 140 ° C., and triethylamine 7 ml (0.05 mo)
1) was added and the mixture was heated with stirring for 2 hours. 200 ml of ethyl acetate was added while stirring the reaction solution, and after the reaction solution reached room temperature, the obtained crystals were filtered off by suction filtration. The obtained crystals were dissolved in 50 ml of methanol, 1 g of potassium acetate / methanol (30 ml) solution was added, and the obtained crystals were separated by suction filtration. Further, 50 ml of methanol was added to this crystal to dissolve it by heating under reflux, and then naturally filtered, and about 20 ml of the solvent in the filtrate was distilled off under normal pressure, and the mixture was allowed to cool to room temperature. The precipitated crystals were filtered by suction filtration and dried. (II-1) (red powder, yield 0.2 g, yield 5.2%, λmax = 502 nm, ε = 139000).
(Methanol), decomposed above 230 ° C)

The addition amount of the spectral sensitizing dye represented by the general formula (I) is 0.5 × 10 ^-6 mol to 1 mol of silver halide.
The range of 1.0 × 10 ^-2 mol is preferred. More preferably,
It is in the range of 1.0 × 10 ⁻⁵ mol to 5.0 × 10 ⁻³ mol. The sensitizing dye may be added in the process of forming silver halide grains or in the process of chemical sensitization, or may be added at the time of coating. For the method of adding a sensitizing dye during the formation of silver halide emulsion grains, US Pat. Nos. 4,225,666 and 4,828,972 and JP-A-61-103,149 can be referred to. it can. Further, as a method of adding a sensitizing dye in a desalting step of a silver halide emulsion, European Patent 291,339-A and JP-A-64-52,137 are known.
You can refer to the issue. The method of adding a sensitizing dye in the chemical sensitization step is described in JP-A-59-48,75.
You can refer to No.6.

As a method of increasing the spectral sensitizing sensitivity with a sensitizing dye, a method of using two or more sensitizing dyes in combination is known. When two or more kinds of sensitizing dyes are used in combination, the spectral sensitivity often becomes an intermediate effect when each sensitizing dye is used alone or decreases, but when a certain special combination is used. , The spectral sensitivity may be remarkably increased as compared with the case where each sensitizing dye is used alone. This phenomenon is usually called the supersensitizing action of the sensitizing dye. TH Jam for supersensitization
It is summarized in Chapter 10 (co-authored by W. West and PB Gilman) of es edition "The Theory of the Photographic Process" (4th edition, Macmillan, New York, 1977).
When such a combination is used, the spectral sensitizing wavelength may be in the middle of the spectral sensitizing wavelength obtained when each sensitizing dye is used alone, or may be a simple bond.
In some cases, the spectral sensitization shifts to a wavelength that cannot be predicted from the spectral sensitization characteristics of the single use. By using the sensitizing dyes in combination as described above, it is possible to obtain a spectral sensitivity higher than that when each of the sensitizing dyes is used alone, and to set the sensitizing wavelength range suitable for the purpose of use of the photographic light-sensitive material. Finding a combination of sensitizing dyes has become a major problem in the spectral sensitization technology of silver halide photographic emulsions. The combination of sensitizing dyes used to obtain supersensitization requires remarkable selectivity between the dyes, and it seems that a slight difference in chemical structure is apparent in the supersensitizing action. It has a significant effect. That is, the combination of sensitizing dyes that bring about a supersensitizing effect is
It is difficult to predict simply from the chemical structural formula.

As the supersensitizer, it is possible to use a dye which does not have a spectral sensitizing effect itself or a substance which does not substantially absorb visible light. For example, anomistyryl compounds substituted with a nitrogen-containing heterocyclic group (for example, those described in US Pat. Nos. 2,933,390 and 3,635,721) and aromatic organic acid formaldehyde condensates (for example, US Pat. , 743, 510), a cadmium salt, an azaindene compound, and the like.
U.S. Patents 3,615,613 and 3,615,641
The combinations described in Nos. 3,617,295 and 3,635,721 are particularly useful.

The steps for producing a silver halide emulsion are roughly classified into steps such as grain formation, desalting and chemical sensitization. Grain formation is divided into nucleation, ripening, and growth. These steps are not performed uniformly, but the order of the steps is reversed, or the steps are repeated. The reduction sensitization preferably used in the present invention is basically performed at any step during the step of producing a silver halide emulsion. The reduction sensitization may be carried out at the initial stage of grain formation during nucleation, physical ripening, or during growth, and may be performed prior to chemical sensitization other than reduction sensitization or after this chemical sensitization. . When chemical sensitization is performed in combination with gold sensitization, it is preferable to carry out reduction sensitization prior to chemical sensitization so that unfavorable fog does not occur. Most preferred is a method of reduction sensitization during the growth of silver halide grains. The term "during growth" here also refers to a method in which silver halide grains are subjected to reduction sensitization while they are physically ripening or are being grown by the addition of a water-soluble silver salt and a water-soluble alkali halide,
It means that the method also includes a method of performing further reduction sensitization in the state where the growth is temporarily stopped during the growth and then further growing.

The reduction sensitization preferably used in the present invention is carried out by adding a known reducing agent to a silver halide emulsion,
A method of growing or aging in a low pAg atmosphere of pAg1 to 7 called silver aging, called high pH aging
A method of growing or aging in a high pH atmosphere of pH 8 to 11 is known, and 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 and used. Further, two or more kinds of compounds can be used in combination. Stannous chloride, thiourea dioxide as reduction sensitizer,
Dimethylamine borane is the preferred compound. More preferably, the alkynylamine compounds described in US Pat. No. 5,389,510 can be selected. The addition amount of the reduction sensitizer is the addition amount needs to be selected depends on emulsion manufacturing conditions, per mol of silver halide 10 ^-7 to 1
A range of 0 ^-3 mol is suitable.

Ascorbic acid and its derivatives can also be used as the reduction sensitizer of the present invention. Ascorbic acid and its derivatives (hereinafter referred to as "ascorbic acid compound")
Say. Specific examples of () include the following. (A-1) L-ascorbic acid (A-2) L-sodium ascorbate (A-3) L-potassium ascorbate (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 preferably used in a large amount as compared with the addition amount in which a reduction sensitizer is conventionally used. For example, Japanese Patent Publication Sho 57
No. 33572, "The amount of reducing agent usually does not exceed 0.75 × 10 ^-2 milliequivalent (8 × 10 ^-4 mol / AgX mol) per g of silver ion. Amount of 0.1-10 mg per kg of silver nitrate. (As ascorbic acid, 10 ^-7 to 10 ^-5 mol / AgX mol)
Is often effective. (The converted value is by the inventors). US Pat. No. 2,487,850
In the publication, "the addition amount of the tin compound that can be used as the reduction sensitizer is 1 × 10 ^{-7 to} 44 × 10 ^-6 mol" is described. Further, in JP-A-57-179835, the addition amount of thiourea dioxide is about 0.1 per mol of silver halide.
01 mg to about 2 mg, as stannous chloride about 0.01 mg to about 3 mg
Is said to be suitable. Ascorbic acid compound used in the present invention the particle size of the emulsion, the halogen composition, the temperature of 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 5 × 10 ⁻⁴ mol to 1 × 10
It is preferable to select from the range of ^-2 mol. It is particularly preferable to select from the range of 1 × 10 ⁻³ mol to 1 × 10 ⁻² mol.

The reduction sensitizer can be dissolved in water or a solvent such as alcohols, glycols, ketones, esters and amides and added during grain formation, before or after chemical sensitization. It may be added at any stage of the emulsion production process, but the method of addition during grain growth is particularly preferred. It may be added to the reaction vessel in advance, but it is preferable to add it at an appropriate time for particle formation. It is also possible to add a reduction sensitizer to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide in advance and use these aqueous solutions to form grains. Further, it is also a preferable method to add the solution of the reduction sensitizer in several times with the grain formation or to continuously add it for a long time.

During the process of producing the emulsion of the present invention, acid for silver is used.
It is preferable to use an agent. What is an oxidizing agent for silver?
Has the effect of acting on metallic silver and converting it to silver ions
Says a compound. Especially the formation process of silver halide grains and
The extremely fine silver particles produced as a by-product in the chemical sensitization process,
Compounds that can be converted to silver ions are effective. Raw here
The silver ions formed are silver halide, silver sulfide, and silver selenide.
It may form a sparingly soluble silver salt in water, such as silver nitrate.
A readily soluble silver salt may be formed in the water. Oxidizer for silver
May be an inorganic substance or an organic substance. Inorganic
Oxidants include ozone, hydrogen peroxide and its adducts
(For example, NaBO₂・ H₂O₂・ 3H₂O, 2Na₂CO₃・ 3H₂O₂, Na_FourP
₂O₇・ 2H₂O₂, 2Na₂SO_Four ・ H₂O₂・ 2H₂O), peroxy acid
Salt (eg K₂S₂O₈ , K₂C₂O₆, K₂P₂O₈), Peroxy
Complex compound {eg K₂(Ti (O₂) C ₂O_Four) ・ 3H₂O, 4K₂SO_Four・
Ti (O₂) OH ・ SO_Four ・ 2H₂O, Na₃(VO (O₂) (C₂H_Four)₂・ 6H₂O},
Permanganate (eg KMnO_Four), Chromate (eg
For example, K₂Cr₂O₇) Such as oxygenates, halo such as iodine or bromine
Gen element, perhalogenate (eg potassium periodate)
), A salt of a high valent metal (eg, hexacyano secondary)
Potassium ferrate) and thiosulfonate.
Further, as an organic oxidant, quinone such as p-quinone is used.
, Organic peroxides such as peracetic acid and perbenzoic acid, active halo
Compounds that release gen (eg, N-bromosuccinyl)
Mid, chloramine T, chloramine B) are given as examples.
Be done. EP 0627657 as a more preferable oxidizing agent
The disulfide compound described in A2 is used.

Preferred oxidizing agents of the present invention include ozone, hydrogen peroxide and its adducts, halogen elements, inorganic oxides of thiosulfonates, and organic oxidizing agents of quinones. It is a preferable embodiment to use the reduction sensitization and the oxidizing agent for silver in combination. It is possible to select and use the method of performing reduction sensitization after using an oxidizing agent, the reverse method thereof, or the method of coexisting both. These methods can be selectively used in both the grain forming step and the chemical sensitization step. The silver halide photographic light-sensitive material of the present invention preferably has the following general formula (XX), (XXI)
Alternatively, it contains at least one compound selected from the compounds represented by (XXII). General formula (XX) R ₁₀₁ -SO ₂ SM ₁₀₁ General formula (XXI) R ₁₀₁ -SO ₂ SR ₁₀₂ General formula (XXII) R ₁₀₁ -SO ₂ S- (E) _a -SSO ₂ -R _{103 101} , R ₁₀₂ and R ₁₀₃ represent an alkyl group, an aryl group or a heterocyclic group, M ₁₀₁ represents a cation, and E
Represents a divalent linking group, and a is 0 or 1.

The compound of the general formula (XX), (XXI) or (XXII) will be described in more detail. R ₁₀₁ , R ₁₀₂ , and R ₁₀₃
When is an aliphatic group, it is preferably an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or an alkynyl group, which may have a substituent.
Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, isopropyl and t-butyl. Examples of the alkenyl group include allyl and butenyl. Examples of the alkynyl group include propargyl and butynyl. The aromatic group for R ₁₀₁ , R ₁₀₂ , and R ₁₀₃ preferably has 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. These may be substituted.

The heterocyclic group for R ₁₀₁ , R ₁₀₂ , and R ₁₀₃ is a 3- to 15-membered ring having at least one element selected from nitrogen, oxygen, sulfur, selenium, and tellurium, for example, a pyrrolidine ring, Piperidine ring, pyridine ring, tetrahydrofuran ring, thiophene ring, oxazole ring, thiazole ring, imidazole ring, benzothiazole ring, benzoxazole ring, benzimidazole ring,
Examples thereof include selenazole ring, benzoselenazole ring, tellurazole ring, triazole ring, benzotriazole ring, tetrazole ring, oxadiazole ring and thiadiazole ring.

Substituents for R ₁₀₁ , R ₁₀₂ , and R ₁₀₃ include, for example, alkyl groups (eg, methyl, ethyl, hexyl), alkoxy groups (eg, methoxy, ethoxy,
Octyloxy), aryl groups (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, benzamino), sulfonylamino group (eg methanesulfonylamino, benzenesulfonylamino),
Examples thereof include an acyloxy group (eg acetoxy, benzoxy), a carboxyl group, a cyano group, a sulfo group, an amino group and the like. E is preferably a divalent aliphatic group or a divalent aromatic group. Examples of the divalent aliphatic group of E include-(C
H ₂ ) _n- (n = 1 to 12), -CH ₂ -CH = CH-CH _2- ,

[0082]

[Chemical 34]

Examples thereof include a xylylene group. Examples of the divalent aromatic group of E include phenylene and naphthylene. These substituents may be further substituted with the substituents such as V _{1 to} V ₄ described above. M
₁₀₁ is preferably a metal ion or an organic cation. Examples of metal ions include lithium ions, sodium ions, and potassium ions. As the organic cation, ammonium ions (for example, ammonium,
Examples thereof include tetramethylammonium, tetrabutylammonium), phosphonium ions (tetraphenylphosphonium), and guanidine groups. General formula (XX), (X
Specific examples of the compound represented by XI) or (XXII) are shown below, but the invention is not limited thereto.

[0084]

[Chemical 35]

[0085]

[Chemical 36]

[0086]

[Chemical 37]

[0087]

[Chemical 38]

[0088]

[Chemical Formula 39]

[0089]

[Chemical 40]

[0090]

[Chemical 41]

[0091]

[Chemical 42]

[0092]

[Chemical 43]

[0093]

[Chemical 44]

The compound of the general formula (XX) is described in JP-A-54-1.
It can be easily synthesized by the method described in 019 and British Patent No. 972,211. The compound represented by formula (XX), (XXI) or (XXII) is preferably added in an amount of 10 ^-7 to 10 ^-1 mol per mol of silver halide. Further, the addition amount of 10 ⁻⁶ to 10 ⁻² mol, particularly 10 ⁻⁵ to 10 ⁻³ mol is preferable. The addition of the compound represented by the general formula (XX), (XXI) or (XXII) during the production process can be applied by a method usually used when adding an additive to a photographic emulsion. For example, a water-soluble compound is made into an aqueous solution having an appropriate concentration, and a water-insoluble or sparingly-soluble compound is a suitable organic solvent miscible with water, such as alcohols, glycols, ketones, esters, amides, etc. At home,
It can be added as a solution by dissolving it in a solvent that does not adversely affect the photographic characteristics.

The compound represented by formula (XX), (XXI) or (XXII) may be added at any stage during grain formation of the silver halide emulsion, before or after chemical sensitization. . Preferred is a method of adding the compound before or during the reduction sensitization. Particularly preferred is the method of addition during grain growth. It may be added to the reaction vessel in advance, but it is preferable to add it at an appropriate time for particle formation. Alternatively, the compound of the general formula (XX), (XXI), or (XXII) 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 solution of the compound of the general formula (XX), (XXI), or (XXII) in several batches or continuously for a long time as the particles are formed. General formula (XX), (X
Among the compounds represented by XI) or (XXII), the most preferable compound for the present invention is the compound represented by the general formula (XX).

The light-sensitive material of the present invention is not particularly limited, and examples thereof include color negative, color positive, white / black light-sensitive material, movie negative, movie positive and the like. That is, at least one photosensitive layer may be provided on the support. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. 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 light-sensitive material, the arrangement of the unit photosensitive layers is generally The red color-sensitive layer, the green color-sensitive layer and the blue color-sensitive layer are arranged in this order from the support side.
However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers. A non-photosensitive layer may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. These may contain a coupler, a DIR compound, a color mixing inhibitor, etc., which will be described later. The multiple silver halide emulsion layers constituting each unit photosensitive layer are DE 1,121,470 or GB 9
As described in 23,045, it is preferable to arrange two layers of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer so that the photosensitivity becomes lower toward the support. In addition, JP-A-57-112751,
As described in JP-A-62-200350, JP-A-62-206541 and JP-A-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 a specific example, from the side farthest from the support,
Low sensitivity blue photosensitive layer (BL) / High sensitivity blue photosensitive layer (BH) / High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (GL) / High sensitivity red photosensitive layer (RH) / Low sensitivity red photosensitive layer (RL) order, or BH / BL / GL / GH / RH / RL order, or BH / BL / GH /
It can be installed in the order of GL / RL / RH. In addition,
As described in JP-A-55-34932, the blue-sensitive layer / GH / RH / GL / RL may be arranged in this order from the side farthest from the support. Further, as described in JP-A-56-25738 and JP-A-62-63936, blue-sensitive layers / GL / RL / GH / RH may be arranged in this order from the side farthest from the support. In addition, 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 the 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. Also, in the case of four or more layers, the arrangement may be changed as described above. U.S. Patent (US) 4,66 to improve color reproduction
3,271, 4,705,744, 4,707,436, JP 62-16044
8, Donor layer (CL) with a multilayer effect, which has a spectral sensitivity distribution different from that of the main photosensitive layers such as BL, GL and RL described in the specification of 63-89850.
Is preferably arranged adjacent to or in proximity to the main photosensitive layer.

The preferred silver halide used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide, which contains about 30 mol% or less of silver iodide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide. The silver halide grains in a photographic emulsion are those having regular crystals such as cubes, octahedra and tetradecahedrons, those having irregular crystal shapes such as spheres and plates, twin planes, etc. It may have a crystal defect of, or a composite form thereof. The grain size of silver halide may be fine grains of about 0.2 μm or less, or large grains having a projected area diameter of about 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).
Mon., pp. 22-23, "I. Emulsion preparati
on and types) ", and No. 18716 (November 1979), 6
Page 48, ibid.No. 307105 (November 1989), pages 863-865,
And Graphide, "Physics and Chemistry of Photography", published by Paul Montel (P. Glafkides, Chemie et PhisiquePhotogra
Phique, Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin. Photog.
raphic Emulsion Chemistry, Focal Press, 1966), "Production and coating of photographic emulsions" by Zelikman et al., published by Focal Press (VL Zelikman, et al., Making and Coati
ng Photographic Emulsion, Focal Press, 1964) and the like.

Monodisperse emulsions described in US Pat. Nos. 3,574,628 and 3,655,394 and British Patent (GB) 1,413,748 are also preferred.
Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and Engineering.
Vol. 14, pp. 248-257 (1970); US 4,434,226, ibid.
4,414,310, 4,433,048, 4,439,520 and GB 2,1
It can be easily prepared by the method described in 12,157. The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. Silver halides having different compositions may be joined by epitaxial joining, and may be joined with a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used. The above emulsion may be either a surface latent image type which forms a latent image mainly on the surface, an internal latent image type which forms a latent image inside the grain, or a type which has a latent image both on the surface and inside, but a negative type emulsion. It is necessary to be. Among the internal latent image type emulsions, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used, and the preparation method thereof is described in JP-A-59-1.
33542. Although the thickness of the shell of this emulsion varies depending on the development process and the like, it is preferably 3 to 40 nm, and 5
-20 nm is particularly preferred.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such a process are RD No. 17643 and RD No. 17643.
18716 and No. 307105, and the relevant parts are summarized in the table below. The light-sensitive material of the present invention includes a light-sensitive silver halide emulsion having a grain size, a grain size distribution,
Two or more kinds of emulsions having different characteristics of at least one of halogen composition, grain shape, and sensitivity can be mixed and used in the same layer. US Pat. No. 4,082,553, the surface of which is covered with a silver halide grain, US Pat.
It is preferable to apply the internally fogged silver halide grains and colloidal silver described in -214852 to the photosensitive silver halide emulsion layer and / or the substantially non-photosensitive 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 inner core of a core / shell type silver halide grain having a fogged inside may have a different halogen composition. As the silver halide whose inside or surface is 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.
.mu.m, especially 0.05 to 0.6 .mu.m is preferred. The grain shape may be regular grain or polydisperse emulsion, but monodispersity (at least 95% of the weight or number of silver halide grains has a grain size within ± 40% of the average grain size). It is preferable that

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a fine grain of silver halide which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the development process, and it is preferable that it is not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may optionally contain silver chloride and / or silver iodide. Preferably, it contains 0.5 to 10 mol% of silver iodide. The fine grain silver halide preferably has an average grain size (average diameter of circles in the projected area) of 0.01 to 0.5 μm, and 0.02 to 0.2 μm.
Is more preferable. The fine grain silver halide can be prepared by a method similar to that for ordinary photosensitive silver halide. The surface of the silver halide grain does not need to be optically sensitized nor spectrally sensitized. However, prior to adding this to the coating solution, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzodiazolium-based, mercapto-based compound or zinc compound in advance. Colloidal silver can be contained in the fine silver halide grain-containing layer. The silver coating amount of the light-sensitive material of the present invention is preferably 6.0 g / m ² or less, and 4.5 or less.
Most preferred is g / m ² or less.

The photographic additives that can be used in the present invention are also described in RD, and the relevant portions are shown in the table below.

[0103]

[Table 1]

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 568,037A A coupler represented by the formula (I) of claim 1; a coupler represented by the general formula (I) in columns 45 to 55 of column 1, US 5,066,576; represented by the general formula (I) in paragraph 0008 of JP-A-4-274425. Coupler; coupler described in claim 1 of EP 498,381A1 on page 40 (especially D-35 on page 18); coupler represented by formula (Y) on page 4 of EP 447,969A1 (especially Y-1 (page 17), Y-54 (41
)); US 4,476,219, column 7, lines 36-58, formulas (II)-(I
V) couplers (especially II-17, 19 (column 1
7), II-24 (column 19)). Magenta coupler: JP-A-3-39737 (L-57 (page 11, lower right),
L-68 (bottom right of page 12), L-77 (bottom right of page 13); [A of EP 456,257
-4] -63 (134 pages), [A-4] -73, -75 (139 pages); EP486,965
M-4, -6 (page 26), M-7 (page 27); EP 571,959A M-45 (1
(Page 9); (M-1) of JP-A-5-204106 (page 6); JP-A-4-3626
31 paragraph 0237 M-22. Cyan coupler: CX-1, 3, 4, 5 of JP-A-4-204843,
11, 12, 14, 15 (pages 14 to 16); JP-A-4-43345, C-7,
10 (page 35), 34, 35 (page 37), (I-1), (I-17) (42 to 43)
Page); a coupler represented by formula (Ia) or (Ib) of claim 1 of JP-A-6-67385. Polymer coupler: P-1 and P-5 of JP-A-2-44345 (page 11)
.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US 4,366,237, GB 2,125,570, EP 96,873B,
Those described in DE 3,234,533 are preferred. The coupler for correcting the unnecessary absorption of the coloring dye is a yellow color cyan dye represented by the formulas (CI), (CII), (CIII) and (CIV) described on page 5 of EP 456,257A1 (especially on page 84). YC-8
6), the yellow colored magenta coupler Ex described in the EP
M-7 (page 202), EX-1 (page 249), EX-7 (page 251), US 4,83
Magenta color cyan coupler CC-9 described in 3,069
(Column 8), CC-13 (column 10), US 4,837,136 (2)
(Column 8), colorless masking couplers represented by formula (A) of claim 1 of WO92 / 11575 (in particular, exemplified compounds on pages 36 to 45) are preferable. Examples of the compound (including a coupler) which releases a photographically useful compound residue by reacting with an oxidized product of a developing agent include the following. Development inhibitor-releasing compounds: Formulas (I), (II), described in EP 378,236A1, page 11
(III), a compound represented by (IV) (especially T-101 (page 30)),
T-104 (page 31), T-113 (page 36), T-131 (page 45), T-144 (51
Page), T-158 (page 58)), and the formula described on page 7 of EP 436,938A2.
Compounds represented by (I) (especially D-49 (page 51)), EP 568,0
Compounds represented by formula (I) of 37A (particularly (23) (page 11)),
Formulas (I), (II) and (III) described on pages 5 and 6 of EP 440,195A2
A compound represented by formula (I- (1) on page 29); a bleaching accelerator releasing compound: a compound represented by formula (I) or (I ') on page 5 of EP 310,125A2 (particularly (60) on page 61) , (61)) and a compound represented by the formula (I) of claim 1 of JP-A-6-59411 (particularly (7) (page 7); a ligand-releasing compound: LIG-X described in claim 1 of US Pat. No. 4,555,478. Compounds represented (especially compounds in columns 12, lines 21-41); Leuco dye releasing compounds:
Compounds 1-6 of columns 3-8 of US 4,749,641; Fluorophore releasing compounds: compounds represented by COUP-DYE of claim 1 of US 4,774,181 (especially compounds 1-11 of column 7-10);
Development accelerator or fogging agent releasing compound: Compounds represented by the formulas (1), (2) and (3) of column 3, US Pat. No. 4,656,123 (particularly (I-22) of column 25) and EP 450, 637 A2, p. 75 36 ExZK-2 on line -38; compounds that release a dye group for the first time after leaving; compounds represented by formula (I) of claim 1 of US Pat. No. 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 of JP-A-62-215272,
5, 16, 19, 25, 30, 42, 49, 54, 55, 66, 81, 85, 8
6, 93 (pages 140 to 144); Latex for impregnation of oil-soluble organic compounds: Latex described in US 4,199,363; Oxidizing agent scavenger: US 4,978,606, column 2, 54 to 62.
Compounds represented by formula (I) in the row (especially I-, (1), (2),
(6), (12) (columns 4-5), column 2, US 4,923,787
5-10 lines (especially compound 1 (column 3); stain inhibitor: EP 298321A, page 4, lines 30-33 formulas (I)-(III),
Especially I-47, 72, III-1, 27, (pages 24-48); Anti-fading agent: EP298321A, A-6, 7, 20, 21, 23, 24, 25, 26, 3
0, 37, 40, 42, 48, 63, 90, 92, 94, 164 (pages 69 to 118)
, US 5,122,444 columns 25-38 II-1 to III-23, especially I
II-10, EP 471347A, pages 1-12, I-1 to III-4, especially II-
2, US 5,139,931 columns 32-40 A-1 to 48, especially A-3
9, 42; Materials that reduce the amount of color-enhancing agent or color-mixing inhibitor used: I-1 to II-15 on pages 5 to 24 of EP 411324A, especially
I-46; Formalin Scavenger: 24 of EP 477932A
SCV-1 to 28 on page 29, especially SCV-8; Hardener: JP-A 1-21
4845, page 17, H-1, 4, 6, 8, 14, US 4,618,573, columns 13 to 23, compounds represented by formulas (VII) to (XII) (H-
1 to 54), compounds represented by the formula (6) at the lower right of page 8 of JP-A-2-214852 (H-1 to 76), particularly H-14, the compound described in claim 1 of US 3,325,287; Agent precursor: P-24, 37, 39 of JP-A-62-168139 (pages 6 to 7); US 5,019,4
Compound as claimed in claim 1 of 92, especially column 7, 28, 2
9; Antiseptic, antifungal agent: US 4,923,790 column 3 to 15 I-1
~ III-43, especially II-1, 9, 10, 18, III-25; stabilizers,
Antifoggant: US 4,923,793, columns 6-16, I-1 ~
(14), in particular I-1, 60, (2), (13), compounds 1 to 65 in columns 25 to 32 of US 4,952,483, especially 36: chemical sensitizer: triphenylphosphine selenide, JP-A-5-40324. Compound 50; dyes: a-1 to b-2 on pages 15 to 18 of JP-A-3-156450
0, especially a-1, 12, 18, 27, 35, 36, b-5, V on pages 27-29
-1 to 23, especially V-1, FI-1 to F on pages 33 to 55 of EP 445627A
-II-43, in particular FI-11, F-II-8, EP 457153A, pages 17-28 III-1 to 36, especially III-1, 3, WO 88/04794 8-26.
Dye-1 to 124 microcrystalline dispersions, compounds 31 to 22 on page 6 to 11 of EP 319999A, particularly compound 1, compounds D-1 to 87 () represented by formulas (1) to (3) of EP 519306A. 3 to 28), US
Compounds 1 to 22 (columns 3 to 10) represented by formula (I) of 4,268,622, compounds represented by formula (I) of US 4,923,788
(1) to (31) (columns 2 to 9); UV absorber: JP-A-46-333
Compounds (18b) to (18r) represented by formula (I) of 5 and 101 to
427 (pages 6 to 9), compounds (3) to (66) represented by formula (I) of EP 520938A (pages 10 to 44) and compounds HBT-1 to 10 (page 14) represented by formula (III). , Compounds (1) to (31) represented by the formula (1) of EP 521823A (columns 2 to 9).

Suitable supports that can be used in the present invention are described in, for example, RD. No. 17643, page 28, No. 18716, 64
Right column from page 7 to left column on page 648, and 879 of the same No. 307105
Page. 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, further preferably 18 μm or less, particularly preferably 16 μm or less. 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 until the film thickness reaches 1/2 when 90% of the maximum swollen film thickness reached when the film is processed with a color developer at 30 ° C. for 3 minutes and 15 seconds is a saturated film thickness. It is defined as The film thickness means a film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days), and T _1/2
Is a member of A. Green et al.'S Photographic Science and Engineering (Photogr.
Sci. Eng.), Vol. 19, 2, 124-129. T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging condition after coating. Also, the swelling rate is 150 to
400% is preferable. The swelling rate is calculated from the maximum swollen film thickness under the conditions described above by the formula: (maximum swollen film thickness-film thickness) /
It can be calculated by the film thickness. The light-sensitive material of the present invention has a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer.
It is preferable to provide the hydrophilic colloid layer (referred to as a back layer). The back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, and surface active agent. The swelling ratio of this back layer is preferably 150 to 500%.

The light-sensitive material of the present invention has the RD. No. 17
Development can be carried out by a usual method described on pages 28 to 29 of 643, page 651, left column to right column of No. 18716, and pages 880 to 881 of No. 307105. The color developing solution used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used. Typical examples and preferred examples thereof are the compounds described on page 28, lines 43 to 52 of EP 556700A. Is mentioned. Two or more of these compounds can be used in combination depending on the purpose. The color developing solution is a developing agent such as a pH buffering agent such as an alkali metal carbonate, borate or phosphate, a chloride salt, a bromide salt, an iodide salt, benzimidazoles, benzothiazoles or a mercapto compound. It is common to include an inhibitor or an antifoggant. If necessary, hydroxylamine,
Diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, various preservatives such as phenylsemicarbazides, triethanolamine and catecholsulfonic acid, organic solvents such as ethylene glycol and 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, amino polycarboxylic acids, amino poly Various chelating agents represented by phosphonic acid, alkylphosphonic acid and phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyl Iminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo -N, N,
N-trimethylenephosphonic acid, ethylenediamine-N,
Add N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof.

When the reversal process is carried out, black and white development is usually carried out and then color development is carried out. In this black-and-white developer, a known black-and-white developing agent such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol is used alone. Alternatively, they can be used in combination. The pH of these color developing solution and black-and-white developing solution is generally 9 to 12.
The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but it is generally 3 liters or less per 1 square meter of the light-sensitive material. You can also do it. When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area of the treatment tank with the air. The processing effect of the contact between the photographic processing liquid and air in the processing tank can be evaluated by the aperture ratio (= [contact area between processing liquid and air cm ² ] / [volume of processing liquid cm ³ ]). The aperture ratio is preferably 0.1 or less, and more preferably 0.001 to 0.05. As a method of 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 not limited to both color development and black and white development,
Subsequent steps, such as bleaching, bleach-fixing, fixing, washing,
It is preferable to reduce it in all steps such as stabilization. Further, the amount of replenishment can be reduced by using means for suppressing the volume of bromide ions in the developing solution. The color development processing time is usually set between 2 and 5 minutes, but the processing time can be further shortened by using a high temperature, high pH and using a high concentration of the color developing agent.

The photographic emulsion layer of the color developer is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out 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. As a typical bleaching agent, an organic complex salt of iron (III),
For example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, or other aminopolycarboxylic acids or complex salts of citric acid, tartaric acid, malic acid, etc. Etc. 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 both the bleaching solution and the 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.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleaching 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, ibid 53-141623, ibid 53-28426, RD No. 17129 (1978
July)) having a mercapto group or a disulfide group; a thiazolidine derivative described in JP-A-50-140129; JP-B-45-8506, JP-A-52-20832, and JP-A-53-3273.
5, thiourea derivatives described in US 3,706,561; DE 1,127,71
5, iodide salts described in JP-A-58-16,235; DE 966,410,
Polyoxyethylene compounds described in JP-A-2,748,430; polyamine compounds described in JP-B-45-8836;
49-40,943, 49-59,644, 53-94,927, 54-35,72
7, the compounds described in 55-26,506 and 58-163,940; bromide ions can be used. Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large accelerating effect, and in particular, US 3,893,858, DE 1,290,812, JP-A-53-9.
The compounds described in 5,630 are preferred. In addition, US 4,552,834
The compounds described in 1 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 light-sensitive material for photography. In addition to the above compounds, the bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. Particularly preferred organic acid has an acid dissociation constant (pKa) of 2 to 5
Specifically, acetic acid, propionic acid, hydroxyacetic acid and the like are preferable.

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. Use of thiosulfates is preferred. It is common and in particular ammonium thiosulfate can be used most widely. Further, it is also preferable to use a combination of thiosulfate, thiocyanate, thioether compound and thiourea. As a preservative for the fixing solution and the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in EP 294769A are preferable. Furthermore, for the purpose of stabilizing the solution, it is preferable to add aminopolycarboxylic acids or organic phosphonic acids to the fixing solution or the bleach-fixing 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, imidazole, 1-methylimidazole,
It is preferable to add 0.1-10 mol of imidazole such as 1-ethylimidazole and 2-methylimidazole 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 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C.
In the preferable temperature range, the desilvering rate is improved, and the stain generation after the processing is effectively prevented. In the desilvering process, it is preferable that the stirring is strengthened as much as possible. As a concrete method for strengthening stirring, Japanese Patent Laid-Open No. 62-183
460, a method of impinging a jet of a processing solution on the emulsion surface of the light-sensitive material, a method of increasing the stirring effect by using the rotating means of JP-A-62-183461, and a wiper blade and emulsion provided in the solution. Move the photosensitive material while contacting the surfaces,
Examples include a method of further improving the stirring effect by making the emulsion surface turbulent, and a method of increasing the circulation flow rate of the entire processing solution. Such a stirring improving means is effective in 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, as a result, increases the desilvering rate. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting action of the bleaching accelerator. The automatic processor used for the light-sensitive material of the present invention is disclosed in JP-A-60-191257.
60-191258 and 60-191259. JP-A-60-191
As described in 257, such a transfer means can significantly reduce the carry-in of the processing liquid from the front bath to the post-bath, and is highly effective in preventing the deterioration of the performance of the processing liquid. It is particularly effective in reducing the liquid replenishment amount.

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 process depends on the characteristics of the light-sensitive material (for example, depending on the material used such as coupler), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment method such as countercurrent and forward flow, and various other conditions. Can be set in a wide range. 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
It can be determined by the method described in rs Vol. 64, pp. 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 due to the increase in the residence time of water in the tank, bacteria propagate and the suspended matter produced 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 Antibacterial and Antifungal Society, "Encyclopedia of Antibacterial and Antifungal Agents" (1986) The disinfectants described can also be used. The pH of washing water in the processing of the light-sensitive material of the present invention is 4 to 9, preferably 5 to 8.
The washing water temperature and washing time can also be set depending on the characteristics of the light-sensitive material and the application, but generally 15 to 45 ° C. and 20 seconds to 10 seconds.
Minutes, preferably at 25-40 ° C. for 30 seconds-5 minutes. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilization treatment, JP-A-57-8543 and JP-A-58-148
The publicly known method described in 34, 60-220345 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 Aldehydes such as formalin and glutaraldehyde, N
Mention may be made of methylol compounds, hexamethylenetetramine or aldehyde sulfite adducts. Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow solution accompanying the above washing with water and / or replenishment of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic processor, etc., when the above processing solutions are concentrated by evaporation,
It is preferable to correct the concentration by adding water. The photographic material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use a precursor of a color developing agent. For example US 3,34
2,597 described indoaniline compounds, 3,342,599,
Research Disclosure No. 14,850 and No. 1
Examples thereof include Schiff base type compounds described in 5,159, aldol compounds described in 13,924, metal salt complexes described in US 3,719,492, and urethane compounds described in JP-A-53-135628. The light-sensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones in order to accelerate color development, if necessary. A typical compound is JP-A-56-643.
39, 57-144547, and 58-115438. The processing liquid used for processing the light-sensitive material of the present invention is 10
Used at temperatures between 50 ° C and 50 ° C. Usually 33 ° C to 38 ° C
Although the temperature is standard, the temperature can be raised to accelerate the treatment to shorten the treatment time, and conversely, the temperature can be lowered to improve the image quality and the stability of the treatment liquid.

The present invention can be preferably used in a silver halide photographic light-sensitive material having a transparent magnetic recording layer. The silver halide sensitive material carrying the magnetic recording layer used in the present invention is
A thin layer support of preheated polyester described in detail in JP-A-6-35118, JP-A-6-17528, and JIII Journal of Technical Disclosure No. 94-6023, for example, a polyethylene aromatic dicarboxylate polyester support,
50 μm to 300 μm, preferably 50 μm to 200 μm
More preferably, 80 to 115 μm, and particularly preferably 85 to 105 μm are heat-treated (annealed) at a temperature of 40 ° C. or higher and a glass transition temperature or lower for 1 to 1500 hours. Kosho 45
UV irradiation described in -3828, JP-B-48-5043,
Surface treatment such as corona discharge described in JP-A-51-131576, glow discharge described in JP-B-35-7578 and JP-B-46-43480, and undercoating described in US Pat. The undercoat layer described in JP-A-761,791 may be provided and the ferromagnetic particles described in JP-A-59-23505, JP-A-4-195726 and JP-A-6-59357 may be applied. The magnetic layer described above may have the stripe shape described in JP-A-4-124642 and JP-A-4-124645.

Further, if necessary, Japanese Patent Laid-Open No. 4-62543.
The antistatic treatment is applied, and finally the product coated with a silver halide emulsion is used. The silver halide emulsions used here are those disclosed in JP-A-4-166932, JP-A-3-41436, and JP-A-3-14336.
41437 is used. The sensitivity of the material is 4-8
Manufactured by the manufacturing control method described in 6817, Japanese Patent Publication No. 6-87
It is preferable to record the manufacturing data by the method described in 146. After that, or before that, JP-A-4-125560.
The film is cut narrower than the conventional 135 size and perforated with 2 holes per side per small format screen to match the smaller format screen according to the method described in (1).

The film thus prepared is described in JP-A-4-15.
7459 cartridge package and Japanese Patent Laid-Open No. 5-21020
2 embodiment of the cartridge shown in FIG. 9 or US Pat.
21,479 Film Patrone and US 4,834,
306, US 4,834,366, US 5,226,6
13, used in the cartridge described in US Pat. No. 4,846,418. The film cartridge or film cartridge used here is US 4,848,693, US
A type in which a tongue can be housed, such as No. 5,317,355, is preferable from the viewpoint of light shielding properties. Furthermore, US 5,296,
Cartridge with lock mechanism like 886 or US
Cartridges in which the usage statuses described in 5, 347 and 334 are displayed, and cartridges having a double exposure prevention function are preferable. Further, as described in JP-A-6-85128, a cartridge in which the film is easily attached by simply inserting the film into the cartridge may be used.

The film cartridge thus manufactured can be used for the purpose of photographing, developing, and enjoying various photographs by using a camera, a developing machine, and a laboratory device described below.
For example, a simple loading type camera described in JP-A-6-8886 or 6-99908, an automatic roll-up type camera described in JP-A-6-57398 or 6-101135, or a shooting process described in JP-A-6-205690. A camera in which the type of film can be taken out and exchanged with JP-A-5-29313
8. A camera capable of magnetically recording information on photographing, such as panoramic photographing, high-vision photographing, and normal photographing (magnetic recording with selectable print aspect ratio), as described in JP-A-5-283382, and JP-A-6-1011.
If the camera having the double exposure prevention function described in 94 or the camera having the use state display function of the film described in JP-A-5-150577 is used, the function of the film cartridge (patrone) can be sufficiently exhibited. The film thus photographed is processed by the automatic developing machine described in JP-A-6-222514 and JP-A-6-222545, or before, during, or after the processing. The method of utilizing magnetic recording on a film described in -123054 may be used, or the aspect ratio selection function described in JP-A-5-19364 may be used. In the case of cine type development, splicing is performed by the method described in JP-A-5-119461. In addition, during or after the development process, the attach / detach process described in JP-A-6-148805 is performed. After the processing in this way, Japanese Patent Laid-Open No. 2-184
835, JP-A-4-186335, JP-A-6-7996.
Back printing on color paper by the method described in 8.
Film information may be converted into prints through front printing. Furthermore, JP-A-5-11353 and JP-A-5-11353
It may be returned to the customer together with the index print and return cartridge described in 232594.

[0120]

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 (Preparation of seed emulsion) Gelatin having an average molecular weight of 15,000 0.7
1500 ml of an aqueous solution containing 5 g was kept at 35 ° C. and stirred. The silver potential was adjusted to -10 mV against saturated calomel electrode and the pH was adjusted to 1.90. AgNO ₃ (0.85
g) Aqueous solution and KBr (0.95 g) aqueous solution were added by the double jet method over 15 seconds. After raising the temperature 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 against saturated calomel electrode. An AgNO ₃ (227.1 g) aqueous solution and a 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 and pAg 8.8 at 40 ° C to prepare a seed emulsion. This seed emulsion contains 1 mol of Ag and 80 g of gelatin per kg of emulsion, and has an average equivalent circle diameter of 0.7 μm.
It was a tabular grain having a coefficient of variation 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, K
1200 ml of an aqueous solution containing 1.9 g Br and 38 g gelatin
Was kept at 65 ° C. and stirred. After adding thiourea dioxide (0.9 × 10 ^-5 mol per mol of silver), AgNO ₃ (43.9
g) The 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, KBr containing an aqueous solution of AgNO ₃ (43.9 g) and KI.
An aqueous solution (containing 28 mol% of KI with respect to KBr) was added over 19 minutes while accelerating the flow rate by the double jet method. At this time, the silver potential is -2 with respect to the saturated calomel electrode.
It was kept at 0 mV.

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

(Formation of Third Shell) After the formation of the second shell, 1.1 × 10 ⁻⁴ mol of sodium benzenethiosulfonate was added per mol of silver, and an aqueous KBr solution was added to bring the silver potential to −80 mv. It was adjusted. Average circle equivalent diameter 0.025μ
A silver iodide fine grain emulsion having a coefficient of variation of m and an equivalent circle diameter of 18% was rapidly added within 5 seconds in terms of AgNO ₃ in an amount of 8.5 g.

(Formation of Fourth Shell) 30 seconds after the above silver iodide fine grain emulsion was added, AgNO ₃ (66.4 g)
The aqueous solution was added over 4 minutes with flow rate slowing. On the way, potassium iridium hexachloride was 4.8 × 1 per mol of silver.
^0-7 mol was added. The silver potential after the addition of the AgNO ₃ aqueous solution was −10 mV. Normal washing was carried out, gelatin was added, and the pH was adjusted to 5.8 and pAg 8.8 at 40 ° C. This emulsion was designated as emulsion Em-1. Emulsion Em-1 had an average equivalent circle diameter of 1.40 μm, a coefficient of variation of equivalent circle diameter of 19%, and an average thickness of 0.
159 μm, average aspect ratio 8.8, average sphere equivalent diameter 0.7
The tabular grains had a size of 8 μm. Further, grains having an aspect ratio of 8 or more occupied about 90% of the total projected area. Further, from the observation of the grains with a 200 KV transmission electron microscope at a liquid N ₂ temperature, 50 or more dislocation lines on average per grain were present near the outer periphery of the tabular grains. To the emulsion Em-1 thus produced, the following compound Y-1 was added at 40 ° C. at 1 × 10 ⁻³ mol per mol of silver, and the sensitizing dyes shown in Table 2 were added. Amount was added at 40 ° C. Subsequently, potassium thiocyanate, chloroauric acid, sodium thiosulfate and N, N-dimethylselenourea were added,
Emulsion 10 was prepared by optimally sensitizing gold-sulfur selenium by raising the temperature to ℃.
1-122 were created. A tabular silver iodobromide emulsion (Em-2) prepared by removing the step of adding thiourea dioxide and sodium benzenethiosulfonate from the above emulsion formulation
Similarly, the sensitizing dyes shown in Table 3 were added to the emulsion 151.
~ 172 was created. Samples 1001 to 1072 were prepared by coating an emulsion layer and a protective layer on a triacetyl cellulose support having an undercoat layer in the coating amounts shown in Table-4.
It was created.

[0126]

[Chemical formula 45]

[0127]

[Table 2] Table 2 Prepared emulsions ─────────────────────────────────── Emulsion number Sensitizing dye Remarks (Reduction) 101 SD-1 (4.8 × 10 ^-4 mol / mol Ag) Comparison 102 SD-2 (〃) 〃 103 SD-3 (〃) 〃 104 SD-6 (〃) 〃 105 SD-7 (〃 ) 〃 106 SD-8 (〃) 〃 107 II-26 Present invention 108 II-1 〃 109 II-2 〃 110 II-4 〃 111 II-35 〃 112 II-6 〃 113 II-7 〃 114 II-19 〃 115 II-22 〃 116 II-49 〃 117 II-53 〃 118 SD-1 (3.4 × 10 ^-4 mol / mol Ag) Comparison SD-4 (1.0 × 10 ^-4 mol / mol Ag) SD-5 (0.4 × 10 ⁻⁴ mol / mol Ag) 119 II-26 (3.4 × 10 ⁻⁴ mol / mol Ag) The present invention SD-4 (1.0 × 10 ⁻⁴ mol / mol Ag) SD-5 (0.4 × 10 ^{− 4} mol / mol Ag) 120 II-1 (3.4 × 10 ^-4 mol / mol Ag) 〃 SD-4 (1.0 × 10 ^-4 mol / mol Ag) SD-5 (0.4 × 10 ^-4 mol / mol Ag) 121 II-2 (3.4 10 ^-4 mol / mol Ag) 〃 II-41 (1.0 × 10 ^-4 mol / mol Ag) SD-5 (0.4 × 10 -4 mol / mol Ag) 122 II-35 (3.4 × 10 -4 mol / mol Ag) 〃 II-41 (1.0 × 10 ^-4 mol / mol Ag) II-40 (0.4 × 10 ^-4 mol / mol Ag)

[0128]

[Table 3] Table 3 Emulsions prepared ──────────────────────────────────── Emulsion number Sensitizing dye Consideration (unreduced) 151 SD-1 (4.8 × 10 ^-4 mol / mol Ag) Comparison 152 SD-2 (〃) 〃 153 SD-3 (〃) 〃 154 SD-6 (〃) 〃 155 SD-7 (〃) 〃 156 SD-8 (〃) 〃 157 II-26 The present invention 158 II-1 〃 159 II-2 〃 160 II-4 〃 161 II-35 〃 162 II-6 〃 163 II-7 〃 164 II -19 〃 165 II-22 〃 166 II-49 〃 167 II-53 Invention 168 SD-1 (3.4 × 10 ^-4 mol / mol Ag) Comparison SD-4 (1.0 × 10 ^-4 mol / mol Ag) SD-5 (0.4 × 10 ^-4 mol / mol Ag) 169 II-26 (3.4 × 10 ^-4 mol / mol Ag) The present invention SD-4 (1.0 × 10 ^-4 mol / mol Ag) SD-5 (0.4 × 10 ^-4 mol / mol Ag) 170 II-1 (3.4 × 10 ^-4 mol / mol Ag) 〃 SD-4 (1.0 × 10 ^-4 mol / mol Ag) SD-5 (0.4 × 10 ^-4 mol / mol) Mol Ag) 171 II-2 (3.4 × 10 ^-4 mol / mol Ag) 〃 II-41 (1.0 × 10 ^-4 mol / mol Ag) SD-5 (0.4 × 10 ^-4 mol / mol Ag) 172 II-35 (3.4 × 10 ^-4 mol / mol Ag) 〃 II-41 (1.0 × 10 ^-4 mol / mol Ag) II-40 (0.4 × 10 ^-4 mol / mol Ag)

[0129]

[Chemical formula 46]

[0130]

[Chemical 47]

[0131]

[Table 4]

These samples were exposed to sensitometry for 1/100 seconds through a continuous wedge and a gelatin filter SC-50 manufactured by Fuji Photo Film Co., Ltd. at a color temperature of 4800 ° K, and the following color development processing was performed. The developing treatment used here was carried out at 38 ° C. under the following conditions.

[0133]                                 Processing method   Process processing time Processing temperature Replenishment amount Tank capacity Color development 2 minutes 45 seconds 38 ° C 33ml 20L Bleach 6 minutes 30 seconds 38 ℃ 25ml 40L Washing with water 2 minutes 10 seconds 24 ° C 1200ml 20L Fixing 4 minutes 20 seconds 38 ℃ 25ml 30L Washing with water (1) 1 minute 05 seconds 24 ° C From (2) to (1) 10L                                         Countercurrent piping system Washing with water (2) 1 minute 00 seconds 24 ° C 1200ml 10L Stable (3) 1 minute 05 seconds 38 ° C 25ml 10L Drying 4 minutes 20 seconds 55 ° C   Replenishment amount is 35mm width 1m per length

Next, the composition of the processing liquid will be described. (Color developer)                                   Mother liquor (g) Replenisher (g)   Diethylenetriamine pentaacetic acid 1.0 1.1   1-Hydroxyethylidene-3.0 3.2     1,1-diphosphonic acid   Sodium sulfite 4.0 4.4   Potassium carbonate 30.0 37.0   Potassium bromide 1.4 0.7   Potassium iodide 1.5mg-   Hydroxylamine sulfate 2.4 2.8   4- [N-ethyl-N-β-4.5 5.5     Hydroxyethylamino]-     2-methylaniline sulfate   Add water to add 1.0L 1.0L   pH 10.05 10.10 (Bleaching solution)                                   Mother liquor (g) Replenisher (g)   Ethylenediaminetetraacetic acid second 100.0 120.0     Sodium iron trihydrate   Ethylenediaminetetraacetic acid dina 10.0 11.0     Thorium salt   Ammonium bromide 140.0 160.0   Ammonium nitrate 30.0 35.0   Ammonia water (27%) 6.5 ml 4.0 ml   Add water to add 1.0L 1.0L   pH 6.0 5.7

[0135] (Fixer)                                     Mother liquor (g) Replenisher (g)   Ethylenediaminetetraacetic acid 0.5 0.7     Sodium salt   Sodium sulfite 7.0 8.0   Sodium bisulfite 5.0 5.5   Ammonium thiosulfate aqueous solution 170.0 ml 200.0 ml     (70%)   Add water to add 1.0L 1.0L   pH 6.7 6.6 (Stabilizer)                                     Mother liquor (g) Replenisher (g)   Formalin (37%) 2.0 ml 3.0 ml   Polyoxyethylene-p-mono 0.3 0.45     Nonyl phenyl ether     (Average degree of polymerization 10)   Ethylenediaminetetraacetic acid di-0.05 0.08     Sodium salt   Add water to add 1.0L 1.0L   pH 5.8-8.0 5.8-8.0   The concentration of the processed sample was measured.

Regarding the sensitivity, the relative value of the reciprocal of the exposure amount required for the optical density to be higher than the fog by 0.2 was shown as the fresh sensitivity. In addition, after exposing the unexposed film to a relative humidity of 60%, 55 ° C. for 3 days, the same exposure,
After development, sensitivity and fogging were evaluated in the same manner. The results thus obtained are shown in Tables 5 and 6. The sample number 1001 was used as the sensitivity standard (100).

[0137]

[Table 5] ────────────────────────────────── Fresh sample number after emulsion emulsion fog relative sensitivity fog relative Sensitivity 1001 (Comparison) 101 0.46 100 (Reference) 1.21 38 1002 (〃) 102 0.45 85 1.31 38 1003 (〃) 103 0.48 83 1.11 30 1004 (〃) 104 0.46 83 1.22 35 1005 (〃) 105 0.45 85 1.25 632 32 (〃) 106 0.47 84 1.23 37 1007 (present invention) 107 0.28 119 0.50 90 1008 (〃) 108 0.24 125 0.48 93 1009 (〃) 109 0.20 133 0.39 106 1010 (〃) 110 0.19 152 0.33 122 1011 (〃) 0.19 152 0.28 138 1012 (〃) 112 0.23 125 0.33 90 1013 (〃) 113 0.21 133 0.30 98 10 14 (〃) 114 0.20 135 0.30 112 1015 (〃) 115 0.20 133 133 0.30 110 1016 (〃) 116 0.23 168 0.35 140 1017 (〃) 117 0.21 193 0.30 181 1018 (Comparison) 118 0.63 110 1 28 (48) 119 0.29 142 0.50 110 1020 (〃) 120 0.25 155 0.40 132 1021 (〃) 121 0.19 166 0.32 148 1022 (〃) 122 0.19 166 0.28 157

[0138]

[Table 6] ────────────────────────────────── Fresh sample number after emulsion emulsion fog relative sensitivity fog relative Sensitivity 1051 (Comparison) 151 0.33 92 0.59 77 1052 (〃) 152 0.33 92 0.59 77 1053 (〃) 153 0.30 92 0.55 80 1054 (〃) 154 0.34 92 0.58 75 1055 (〃) 155 0.35 56 〃 757 〃 156 0.32 92 0.54 77 1057 (Invention) 157 0.22 108 0.38 91 1058 (〃) 158 0.20 108 0.35 95 1059 (〃) 159 0.18 108 0.31 102 1060 (〃) 160 0.18 116 0.28 102 1061 16 (1 0.18) 108 1062 (〃) 162 0.22 108 0.33 91 1063 (〃) 163 0.20 116 0.28 102 10 4 (〃) 164 0.18 118 0.31 104 1065 (〃) 165 0.18 116 0.31 102 1066 (〃) 166 0.19 122 0.29 110 1067 (〃) 167 0.18 128 0.28 115 1068 (Comparison) 168 0.33 106 110 0.61 77 169 0.21 133 0.38 110 1070 (〃) 170 0.18 146 0.28 128 1071 (〃) 171 0.18 146 0.27 135 1072 (〃) 172 0.18 146 0.25 140

As is clear from Tables 5 and 6, the sensitizing dye of the present invention has high sensitivity and low fog in both emulsions subjected to reduction sensitization and emulsions not subjected to reduction sensitization. I understand. Further, it can be seen that fogging fluctuation and sensitivity fluctuation during storage are small and storage stability is excellent. From the comparison of Table-5 and Table-6, it can be seen that the sensitizing dye of the present invention is more effective in the reduction-sensitized emulsion than in the non-reduction-sensitized emulsion. Further, among the sensitizing dyes of the present invention, the degree of the effect is different, and Ra or Rb of the compound represented by the general formula (I) of the present invention is an aliphatic group having 2 or more carbon atoms, an aryl group or a hetero group. It can be seen that the effect is remarkable when it is a cyclic group.

Example 2 1) Support The support used in this example was prepared by the following method. Polyethylene-2,6-naphthalate polymer 10
After drying 0 part by weight and 2 parts by weight of Tinuvin P.326 (manufactured by Ciba-Geigy) as an ultraviolet absorber,
After melting at 300 ℃, extrude from T-die, 140 ℃
The film was longitudinally stretched 3.3 times at 130 ° C., then laterally stretched 3.3 times at 130 ° C., and further heat-set at 250 ° C. for 6 seconds to obtain a PEN film having a thickness of 90 μm. The PEN film contains blue dye, magenta dye, and yellow dye (I-1 and I-in Public Technical Report No. 94-6023).
4, I-6, I-24, I-26, I-27, II-5)
Was added in an appropriate amount. Furthermore, by winding it around a stainless steel core with a diameter of 20 cm, and giving it a thermal history of 110 ° C. for 48 hours,
The support is one that does not tend to curl.

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
m ² , using a bar coater), an undercoat layer was provided on the high temperature side during stretching. Drying was performed at 115 ° C. for 6 minutes (the temperature of the rollers and the conveying device in the drying zone are 115 ° C.).

3) Coating of Back Layer On one surface of the above-mentioned support after undercoating, an antistatic layer having the following composition, a magnetic recording layer and a sliding layer were coated as a back layer. 3-1) Application of antistatic layer A tin oxide-antimony oxide composite having an average particle size of 0.005 μm has a specific resistance of 5 Ω · cm and is a dispersion of fine particle powder (secondary agglomerated particle size of about 0.08 μm). .2 g / m ² , gelatin 0.05 g /
m ² , (CH ₂ = CHSO ₂ CH ₂ CH ₂ NHCO) ₂ CH ₂ 0.02 g / m ² , poly (degree of polymerization 10) oxyethylene-p-nonylphenol 0.0
05 g / m ² and resorcin were applied. 3-2) Coating of magnetic recording layer 3-Cobalt-γ-iron oxide coated with poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by weight) (specific surface area 43 m ² / g, Long axis 0.14
μm, minor axis 0.03 μm, saturation magnetization 89emu / g, Fe ^{+ 2} / Fe
⁺³ = 6/94, the surface is aluminum oxide, silicon oxide, and iron oxide is 2
0.06 g / m ² of diacetyl cellulose 1.2 g / m ² (iron oxide was dispersed in an open kneader and a sand mill), and C ₂ H ₅ C (CH ₂ OCONH) as a curing agent. -C
₆ H ₃ (CH ₃ ) NCO) 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 magnetic recording layer having a thickness of 1.2 μm. Silica particles (0.3 μm) and 3-poly (degree of polymerization 1 as matting agent)
5) Abrasive aluminum oxide (0.15 μm) treated and coated with oxyethylene-propyloxytrimethoxysilane (15% by weight) was added so as to be 10 mg / m ² . Drying was carried out at 115 ° C. for 6 minutes (all the rollers and the conveying device in the drying zone were 115 ° C.). The increase in D ^B color density of the magnetic recording layer by X-light (blue filter) is about 0.1, and the saturation magnetization moment of the magnetic recording layer is 4.2.
The emu / g, coercive force was 7.3 × 10 ⁴ A / m, and the squareness ratio was 65%. A sample without a magnetic recording layer was also prepared for comparison.

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
_{A 2} O) ₁₆ H (compound b, 9 mg / m ² ) mixture was applied. In addition,
This mixture was melted in xylene / propylene monomethyl ether (1/1) at 105 ° C. and poured into propylene monomethyl ether (10 times volume) at room temperature to prepare a dispersion, which was then dispersed in acetone (average particle size). The diameter was adjusted to 0.01 μm) before adding. Silica particles as matting agent (0.3 μm
) And an abrasive 3-poly (degree of polymerization of 15) oxyethylene-propyloxytrimethoxysilane (15% by weight of aluminum oxide (0.15 μm) coated at 15 mg / each)
It was added so as to be m ² . Drying was carried out at 115 ° C for 6 minutes (all the 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 ball of 5 mmφ, load 100 g, speed of 6 cm / min), static friction coefficient of 0.07 (clip method), and the dynamic friction coefficient of the emulsion surface and the sliding layer described later is 0.12. It had excellent characteristics.

4) Coating of Photosensitive Layer Next, on the opposite side of the back layer obtained above, each layer having the composition shown below was multilayer coated to prepare a multilayer color photosensitive material. (Photosensitive layer composition) The main materials used for each layer are classified as follows: ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling organic solvent ExY: Yellow coupler H: Gelatin Hardener ExS: Sensitizing dye The numeral corresponding to each component indicates the coating amount expressed in g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount per mol of silver halide in the same layer is shown in mol unit.

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 M 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 A Silver 0.25 Silver Iodobromide Emulsion B 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 Milk-Sensitive Layer) Silver Iodobromide Emulsion C Silver 0.70 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 0.007 Cpd-2 0.023 HBS-1 0 .10 gelatin 0.75

Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion D Silver 1.40 ExS-1 1.5 × 10 ⁻⁴ ExS-2 1.3 × 10 ⁻⁵ ExS-3 3.0 × 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 HBS-2 0.050 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 E silver 0.15 Silver iodobromide emulsion F silver 0.10 Silver iodobromide emulsion G 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 H Silver 0.80 ExS-4 3.2 × 10 ⁻⁴ 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 ExY-5 0.040 HBS-1 0.13 HBS-3 4 0.0 × 10 ^-3 gelatin 0.80

Ninth layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion I Silver 1.25 Sensitizing dyes shown in Table 7 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

Tenth 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

11th layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion J Silver 0.09 Silver iodobromide emulsion K 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 L Silver 1.00 ExS-7 4.0 × 10 ^-4 ExY-2 0.10 ExY-3 0.10 ExY-4 0 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

Fourteenth layer (second protective layer) Silver iodobromide emulsion M Silver 0.10 H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1 0.7 μm) 0.15 B-3 0.05 S-1 0.20 Gelatin 0.70

[0159]

[Table 7] ─────────────────────────────────── Sample No. Sensitizing dye used for the 9th layer (Quantity) Presence or absence of magnetic recording layer 2001 (Comparison) SD-1 2.7 × 10 ^-4 mol / mol Ag No SD-4 0.8 × 10 ^-4 〃 SD-5 0.3 × 10 ^-4 〃 2002 (Comparison) SD-1 2.7 × 10 ^-4 〃 Yes SD-4 0.8 × 10 ^-4 〃 SD-5 0.3 × 10 ^-4 〃 2003 (Invention) II-26 2.7 × 10 ^-4 〃 None II-41 0.8 × 10 ^-4 〃 II -40 0.3 × 10 ^-4 〃 2004 (invention) II-26 2.7 × 10 ^-4 〃 Yes II-41 0.8 × 10 ^-4 〃 II-40 0.3 × 10 ^-4 〃 2005 (invention) II-35 2.7 × 10 ^-4 〃 None II-41 0.8 × 10 ^-4 〃 II-40 0.3 × 10 ^-4 〃 2006 (Invention) II-35 2.7 × 10 ^-4 〃 Yes II-41 0.8 × 10 ^-4 〃 II- 40 0.3 × 10 ⁻⁴ 〃 2001A (comparison); A sample prepared in exactly the same manner except that thiosulfonic acid (XX-16) was changed to P-quinone during the preparation of the emulsion of Sample 2001. 2003A (invention): A sample prepared in exactly the same manner except that thiosulfonic acid (XX-16) was changed to P-quinone during the preparation of the emulsion of sample 2003. Furthermore, storability, processability, pressure resistance, anti-mold,
To improve antibacterial property, antistatic property and coating property, W-
1 to W-3, B-4 to B-6, F-1 to F
-17, and iron salt, lead salt, gold salt, platinum salt, palladium salt, iridium salt, and rhodium salt.

[0160]

[Table 8] ─────────────────────────────────── Average Agl Interparticle Agl Average particle size Related projected diameter Diameter / content (%) Content-related spherical equivalent diameter variation coefficient Circle equivalent diameter thickness ratio variation coefficient (%) (μm) (%) (μm) Emulsion A 1.7 10 0.46 15 0.56 5.5 B 3.5 7 0.57 20 0.78 4.0 C 8.9 18 0.66 17 0.87 5.8 D 8.9 18 0.84 26 1.03 3.7 E 1 .7 10 0.46 15 0.56 5.5 F 3.5 15 0.57 13 0.78 4.0 G 8.8 13 0.61 17 0.77 4.4 H 8.8 25 0. 61 23 0.77 4.4 I 8.9 18 0.84 18 1.03 3.7 J 1.7 10 0.46 15 0.50 4.2 K 8.8 15 0.64 19 0.85 5.2 L 14.0 18 0.28 19 1.46 3.5 M 1.0 ── 0.07 15 ── 1

In Table 8, (1) Emulsions D and IL were subjected to reduction sensitization at the time of grain preparation using thiourea dioxide and thiosulfonic acid (XX-16) according to the examples of JP-A-2-191938. . (2) Emulsions A to L were subjected to gold sensitization, sulfur sensitization and 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. ing. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. (4) Dislocation lines as described in JP-A-3-237450 are observed in the tabular grains by using a high voltage electron microscope. (5) Emulsion L is a double structure grain containing an internal high iodine core described in JP-A-60-143331.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 shown below was dispersed by the following method. That is, 21.7 ml of water and 3 ml of 5% aqueous solution of sodium p-octylphenoxyethoxyethanesulfonate and 5%
% Aqueous p-octylphenoxypolyoxyethylene ether (degree of polymerization 10) 0.5g into a 700ml pot mill, add dye ExF-2 5.0g and zirconium oxide beads (diameter 1mm) 500ml. The contents were dispersed for 2 hours. This dispersion is made by Chuo Koki
A BO type vibration ball mill was used. After the dispersion, the contents were taken out, 8 g of a 12.5% gelatin aqueous solution was added, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the fine dye particles was 0.44 μm.

Similarly, solid dispersions of ExF-3, ExF-4 and ExF-6 were obtained. The average particle size of the fine dye particles is
They were 0.24 μm, 0.45 μm and 0.52 μm. ExF-5
Is the microprecipitation (Micropreci) described in Example 1 of EP 549,489A.
It was dispersed by the dispersion method. Average particle size is 0.06
It was μm.

[0164]

[Chemical 48]

[0165]

[Chemical 49]

[0166]

[Chemical 50]

[0167]

[Chemical 51]

[0168]

[Chemical 52]

[0169]

[Chemical 53]

[0170]

[Chemical 54]

[0171]

[Chemical 55]

[0172]

[Chemical 56]

[0173]

[Chemical 57]

[0174]

[Chemical 58]

[0175]

[Chemical 59]

[0176]

[Chemical 60]

[0177]

[Chemical formula 61]

[0178]

[Chemical formula 62]

[0179]

[Chemical formula 63]

The light-sensitive material prepared as described above is set to 24 mm.
The width of the photosensitive material is cut into 160 cm, and two 2 mm square perforations are provided at a distance of 5.8 mm at a position 0.7 mm from one widthwise side of the photosensitive material. 32 of these two sets
Created at the interval of mm, and FIG. 1 of US 5,296,887 ~
It was stored in the plastic film cartridge described in FIG.7. An FM signal was recorded on this sample at a feed rate of 1,000 / s during the above-mentioned perforation of the light-sensitive material using a head having a head gap of 5 μm and a turn count of 2,000 capable of inputting / outputting from the coated surface side of the magnetic recording layer. This sample was exposed in the same manner as in Example 1 (with the exception of the SC50 filter), and then subjected to the following treatment (running treatment), and evaluated in the same manner as in Example 1. Each processing was carried out by the following using an automatic processor FP-360B manufactured by Fuji Photo Film Co., Ltd. The overflow solution of the bleaching bath was reflowed to the waste solution tank without flowing into the post-bath. This FP-360B is equipped with the evaporation correction means described in JIII Journal of Technical Disclosure No. 94-4992. The treatment process and the treatment liquid composition are shown below.

(Processing step) Processing time Processing temperature Replenishment amount ^* Tank capacity Color development 3 minutes 5 seconds 37.8 ° C. 20 ml 11.5 l Bleaching 50 seconds 38.0 ° C. 5 ml 5 l Fixing (1) 50 seconds 38.0 ° C-5 liters Fixing (2) 50 seconds 38.0 ° C 8 ml 5 liters Water wash 30 seconds 38.0 ° C 17 ml 3 liters Stable (1) 20 seconds 38.0 ° C-3 liters Stable (2) 20 Seconds 38.0 ° C 15 ml 3 liters Dry 1 minute 30 seconds 60 ° C * Replenishment amount per 35 m width of photosensitive material 1.1 m width (equivalent to 24 Ex. 1) Stabilizer and fixer from (2) to (1) It was a countercurrent system, and the overflow liquid of washing water was all introduced into the fixing 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.
It was 5 ml, 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 was about 100 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   Catechol-3,5-disulfonic acid     Disodium 0.3 0.3   Sodium sulfite 3.9 5.3   Potassium carbonate 39.0 39.0   Disodium-N, N-bis (2-sulfo     Natoethyl) hydroxylamine 1.5 2.0   Potassium bromide 1.3 0.3   Potassium iodide 1.3mg-   4-hydroxy-6-methyl-1,3,0.05-     3a, 7-tetrazaindene   Hydroxylamine sulfate 2.4 3.3   2-methyl-4- [N-ethyl-N-     (Β-hydroxyethyl) amino]     Aniline sulfate 4.5 6.5   1.0 liter with water added   pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.18

[0183] (Bleaching solution) Tank solution (g) Replenisher solution (g)   1,3-Diaminopropanetetraacetic acid secondary     Ammonium iron monohydrate 113 170   Ammonium bromide 70 105   Ammonium nitrate 14 21   Succinic acid 34 51   Maleic acid 28 42   1.0 liter with water added   pH [prepared with ammonia water] 4.6 4.0

(Fixing (1) Tank Liquid) A 5:95 (volume ratio) mixture of the above bleaching tank liquid and the following fixing tank liquid. (PH
6.8) (Fixing (2)) Tank solution (g) Replenisher solution (g) Ammonium thiosulfate aqueous solution 240 ml 720 ml (750 g / l) Imidazole 7 21 Ammonium methanethiosulfonate 5 5 15 Ammonium methanesulfinate 10 30 Ethylenediamine 4 Acetic acid 13 39 Add water 1.0 liter 1.0 liter pH [Prepared with ammonia water and acetic acid] 7.4 4.45

(Washing water) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-120 manufactured by Rohm and Haas).
B) and 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, followed by dichloride. Sodium isocyanurate 20
mg / l and sodium sulfate 150 mg / l were added. The pH of this liquid was in the range of 6.5 to 7.5.

[0186] (Stabilizer) Common for tank liquid and replenisher (unit: g)   Sodium p-toluenesulfinate 0.03   Polyoxyethylene-p-monononylphenyl ether     (Average degree of polymerization 10) 0.2   1,2-benzisothiazolin-3-one sodium 0.10   Ethylenediaminetetraacetic acid disodium salt 0.05   1,2,4-triazole 1.3   1,4-bis (1,2,4-triazole-1-     Ilmethyl) piperazine 0.75   1.0 liter with water added   pH 8.5

[0187]

[Table 9] ────────────────────────────────── Fresh (magenta) Sample number Fogging after aging (magenta) Relative sensitivity Fog Relative sensitivity 2001 (Comparison) 0.35 100 (Reference) 0.55 51 2002 (Comparison) 0.38 92 0.87 38 2003 (Invention) 0.23 133 0.29 119 2004 (Invention) 0.25 133 0.33 119 2005 (Invention) 0.20 147 0.26 133 2006 (invention) 0.20 147 0.26 133 2001A (comparative) 0.36 98 0.56 49 2003A (invention) 0.25 129 0.31 115

The evaluation results are shown in Table 9. As is clear from Table 9, the multilayer color light-sensitive material using the sensitizing dye of the present invention has high sensitivity and low fog. Further, it can be seen that fogging fluctuation and sensitivity fluctuation during storage are small and storage stability is excellent. Further, it can be seen that the above-mentioned effects are remarkably maintained in the multilayer color light-sensitive material using the sensitizing dye of the present invention regardless of the presence or absence of the magnetic recording layer. Further, it can be seen that 2001 and 2003 using thiosulfonic acid are superior to 2001A and 2003A using p-quinone as an oxidant at the time of preparing a reduction sensitized emulsion.

[0189]

According to the present invention, it is possible to obtain a silver halide photographic light-sensitive material having high image quality, high sensitivity, and excellent storage stability, in which fogging is suppressed.

─────────────────────────────────────────────────── --- Continuation of the front page (56) Reference JP-A-4-355748 (JP, A) JP-A-5-313284 (JP, A) JP-A-6-273873 (JP, A) JP-A-7- 230140 (JP, A) JP-A-6-186663 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03C 1/12 G03C 1/08

Claims (8)

(57) [Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
A silver halide photographic light-sensitive material characterized in that the emulsion layer contains at least one compound represented by the following general formula (I). [Chemical 1] In formula (I), Ra and Rb are each a hydrogen atom or a carbon number of 2 or more.
Represents an aliphatic group , an aryl group, or a heterocyclic group. However, Ra and Rb are not hydrogen atoms at the same time.
La and Lb represent a methylene group. k ₁ represents an integer of 0 to 5 and k ₂ represents an integer of 0 to 5. However, k ₁ = 2 and k ₂ = 0 do not hold. L ₁ and L ₂ represent a methine group. p ₁ represents 0 or 1. Z ₁ represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle. M ₁
Represents a charge balancing counter ion, and m ₁ represents an integer of 0 or more necessary for neutralizing the charge of the molecule. Q represents an atomic group necessary for forming a methine dye. 2. The compound represented by the general formula (I) is a compound selected from the following general formula (II), general formula (III) or general formula (IV). The described silver halide photographic light-sensitive material. [Chemical 2] In formula (II), L ₃ , L ₄ , L ₅ , L ₆ , L ₇ , L ₈ and L ₉ represent a methine group. p ₂ and p ₃ represent 0 or 1. n ₁ represents 0, 1, 2, or 3. Z ₂ and Z ₃ represent an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle. M ₂ represents a charge balancing counter ion, and m ₂ represents an integer of 0 or more necessary for neutralizing the charge of the molecule. R ₁
And R ₂ represents an alkyl group. However, at least one of R ₁ and R ₂ is an alkyl group represented by the following Rz. [Chemical 3] In Rz, Ra, Rb, La, Lb, k ₁ and k ₂
Has the same meaning as in claim 1. [Chemical 4] In formula (III), L ₁₀ , L ₁₁ , L ₁₂ , and L ₁₃ represent a methine group. p ₄ represents 0 or 1. n ₂ is 0, 1, 2 or 3
Represents Z ₄ and Z ₅ represent an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle. M ₃ represents a charge-balancing counterion, and m ₃ is 0 necessary to neutralize the charge of the molecule.
Represents the above integers. R ₄ represents an alkyl group, an aryl group or a heterocyclic group. R ₃ is an alkyl group represented by Rz above. [Chemical 5] In the formula (IV), L ₁₄ , L ₁₅ , L ₁₆ , L ₁₇ , L ₁₈ , L ₁₉ , and L
₂₀ , L ₂₁ and L ₂₂ represent a methine group. p ₅ and p ₆ represent 0 or 1. n ₃ and n ₄ represent 0, 1, 2, or 3. Z ₆ , Z ₇ and Z ₈ represent an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle. M ₄ represents a charge balancing counter ion, and m ₄ represents an integer of 0 or more necessary for neutralizing the charge of the molecule. R ₅ and R ₇ represent an alkyl group. R ₆ represents an alkyl group, an aryl group or a heterocyclic group. However, at least one of R ₅ and R ₇ is the alkyl group represented by Rz. 3. In the general formula (I), k1 is 1 or
3. The silver halide photographic light-sensitive material according to claim 1, which is 3 . 4. The silver halide photographic light-sensitive material according to claim 2, wherein k1 is 1 or 3 in the general formulas (II), (III) and (IV). 5. Ra is an aryl group or a heterocyclic group,
2. The silver halide photographic light-sensitive material according to claim 1, wherein Rb is a hydrogen atom. 6. A silver halide grain in an emulsion layer containing a compound represented by formula (I), (II), (III) or (IV), which is subjected to reduction sensitization. The silver halide photographic light-sensitive material according to claim 1 or 2. 7. A silver halide grain in an emulsion layer containing a compound represented by formula (I), (II), (III) or (IV), which is subjected to reduction sensitization. The silver halide photographic light-sensitive material according to claim 3 or 4. 8. The silver halide photographic light-sensitive material according to claim 1, which has a transparent magnetic recording layer.