JP3425467B2 - Silver halide photographic materials - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a photographic light-sensitive material containing a silver halide photographic emulsion which has an improved spectral sensitivity in the green short wavelength region and is excellent in storage stability. Is.

[0002]

2. Description of the Related Art Increasing the spectral sensitivity in the green short wavelength region of a silver halide photographic light-sensitive material is an important technical target for improving the color reproducibility of the light-sensitive material. As a technique for increasing the spectral sensitivity in the green wavelength region, a conventional combination of oxacarbocyanine and benzimidazolocarbocyanine (for example, JP-A-59-116646, 59-116647, 59-140443,
59-149346, etc.) or a combination of oxacarbocyanine and oxathiacarbocyanine (eg Japanese Patent Publication No. 46-11627).
No. 60-42750) and photographic emulsions in which two or more kinds of oxacarbocyanines are used in combination (for example, JP-A No. 52-23931).
The spectral sensitivity in the short wavelength region of green of 5 nm was low, which caused problems in color reproduction. Therefore, it is conceivable to additionally use a sensitizing dye having a maximum spectral sensitivity at 520 to 545 nm. However, the maximum value of the spectral sensitivity is 520 nm or more and 545
As sensitizing dyes having a wavelength of less than nm, conventional benzimidazolo oxazolocarbocyanines (for example, JP-B-44-14030) and dimethine merocyanine (for example, US Pat. No. 249374) have been used.
No. 8, No. 2519001, No. 3480439, etc.) are known, but emulsions to which benzimidazolo oxazolocarbocyanine and dimethine merocyanine have been added should be prepared at high temperature or high temperature and high humidity after coating. Increased fog,
Alternatively, the stability over time after coating the emulsion is poor and the sensitivity is decreased, and it is considered not suitable for combined use.

Further, it is known that oxacarbocyanine alone, which has less of the above problems, has a maximum value of spectral sensitivity in the range of 520 nm to 545 nm, for example, US Pat. No. 2521705.
No. 2521959, No. 2647054, and Japanese Patent Laid-Open No. 63-1673.
Although those described in No. 48 are mentioned, the spectral sensitivity of these dyes was not sufficient. Further, the sensitizing dyes represented by the general formulas (I) and (II) used in the present invention have a substituent at the 5-position phenyl group of the benzoxazole nucleus constituting the dye. For dyes having a phenyl group, British Patent Nos. 1,031,483 and 675,
No. 654 and U.S. Pat. No. 2,592,243, which have very limited substituents and substitution positions, and are often insufficient in photographic performance. On the other hand, monomethinecyanine containing a 2-quinoline skeleton has a maximum value of spectral sensitivity at 520 nm to 545 nm, but since it has low sensitivity when used alone, it is used in combination with benzimidazolocarbocyanine or oxacarbocyanine. (Japanese Patent Publication Sho 56-2
4939, 56-38936, 56-38940, British Patent No. 1219
However, these combined methods cannot obtain good color reproducibility because the spectral sensitivity region shifts to long waves. Therefore, in order to obtain faithful color reproducibility of the color light-sensitive material, there has been a demand for a technique for increasing the spectral sensitivity in the green short wavelength region.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a photographic light-sensitive material which has a high spectral sensitivity in the green short wavelength region and is excellent in stability over time.

[0005]

The object of the present invention is to provide a silver halide photographic light-sensitive material characterized by containing at least one of the following general formula (I), or the following general formula (I
Achieved by a silver halide photographic light-sensitive material characterized by containing at least one of I). General formula (I)

[0006]

[Chemical 5]

R in the general formula (I)₁₁And R₁₂Is it
Each represents an alkyl group. R₁₃Is a hydrogen atom, an alkyl group or
Represents an aryl group. V₁, V₂, V₃, V_Four, V_Five, V₆, V₇, V
₈, V ₉, V_Ten, V₁₁And W₀₁Are hydrogen atom or substitution
Represents a group, V₇And V₁₁At least one of them is a substituent
Is. X₁Represents a charge-balancing counterion, and m is in the molecule
It is a number of 0 or more required to neutralize the charge. General formula
(II)

[0008]

[Chemical 6]

In the general formula (II), R_{twenty one}, R_{twenty two},
R_{twenty three}, X₂And n are in the above general formula (I), respectively.
R₁₁, R₁₂, R₁₃, X₁And m are synonymous. V_4A,
V_5A, V _6AAnd W₀₂Are hydrogen atoms or substituents, respectively.
And then W_{twenty one}Represents a substituent having 2 or more carbon atoms.

Among the sensitizing dyes represented by the above general formula (I), those represented by the following general formula (III) are preferable. General formula (III)

[0011]

[Chemical 7]

In the general formula (III), R ₁₁ and R ₁₂ represent an alkyl group. R ₁₃ is a hydrogen atom, an alkyl group or an aryl group.
Represents a radical. _{V 1, V 2, V 3} , V 4, V 5, V 6, V 7, V 8, V 9, V
₁₀ , V ₁₁ , V ₁₂ , V ₁₃ , V ₁₄ , V ₁₅ and V ₁₆ each represent a hydrogen atom or a substituent, at least one of V ₇ and V ₁₁ is a substituent, and V ₁₂ and V ₁₆ At least one
One is a substituent. X ₁ represents a charge-balancing counterion, m
Is a number of 0 or more necessary for neutralizing the charge in the molecule. Among the sensitizing dyes represented by the above general formula (II), those represented by the following general formula (IV) are preferable. General formula (IV)

[0013]

[Chemical 8]

In the general formula (IV), R ₂₁ , R ₂₂ ,
R ₂₃ , X ₂ and n have the same meanings as R ₁₁ , R ₁₂ , R ₁₃ , X ₁ and m in the general formula (I). W ₂₂ represents a substituent, and W ₂₁ represents a substituent having 2 or more carbon atoms.

The present invention is described in detail below. In each general formula, R ₁₁ and R ₁₂ each represent an alkyl group having 1 to 10 carbon atoms and may have a substituent. Specifically, an unsubstituted alkyl group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group) Etc.), an unsubstituted aralkyl group having 7 to 10 carbon atoms (eg, benzyl group, phenethyl group, 3-phenylpropyl group, etc.), and a substituent such as hydroxyl group, carboxyl group, sulfo group, cyano group, halogen atom (eg, Fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), alkoxycarbonyl group having 2 to 8 carbon atoms (eg methoxycarbonyl group, ethoxycarbonyl group, benzyloxycarbonyl group, etc.), alkoxy group having 1 to 8 carbon atoms (eg, Methoxy group, ethoxy group, propoxy group, butyloxy group, benzyloxy group, phenethyloxy group, etc.), 6 carbon atoms 8 aryloxy groups (for example, phenoxy group, p-tritoxy group, etc.), C2-C8 acyloxy groups (for example, acetyloxy group, propionyloxy group, benzoyloxy group, etc.), C2-C8 acyl groups (Eg, acetyl group, propionyl group, benzoyl group, 4-fluorobenzoyl group, etc.), carbamoyl group having 1 to 6 carbon atoms (eg, carbamoyl group,
N, N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group, etc.), sulfamoyl group having 0 to 6 carbon atoms (for example, sulfamoyl group, N, N-dimethylsulfamoyl group, morpholinosulfonyl group, Alkyl substituted with an aryl group having 6 to 10 carbon atoms (eg, phenyl group, p-fluorophenyl group, p-carboxyphenyl group, p-hydroxyphenyl group, p-sulfophenyl group, etc.) Examples thereof include an alkyl group having 1 to 6 carbon atoms in the chain.

The alkyl group represented by R ₁₁ and R ₁₂ is preferably a sulfoethyl group, a sulfopropol group, a sulfobutyl group, a carboxymethyl group or a carboxyethyl group, and more preferably a sulfoethyl group or a sulfobutyl group.

R ₁₃ is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms (eg, methyl, ethyl, propyl, butyl, hydroxyethyl, trifluoromethyl, 2-chloroethyl, chloromethyl, methoxymethyl, 2 -Methoxyethyl, benzyl), 3 to 1 carbon atoms
0 unsubstituted or substituted aryl groups (eg phenyl, o
-Carboxyphenyl, p-tolyl, m-tolyl). R ₁₃ is preferably a hydrogen atom or an unsubstituted alkyl group, more preferably a methyl group, an ethyl group or a propyl group.

V ₁ , V ₂ , V ₃ , V ₄ , V ₅ , V ₆ , V ₇ , V ₈ , V ₉ , V
₁₀ , V ₁₁ , V ₁₂ , V ₁₃ , V ₁₄ , V ₁₅ , V ₁₆ , V _4A ,
As the substituents represented by V _5A , V _6A , W ₀₁ and W ₀₂ ,
Hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms (for example, methyl, ethyl, propyl, butyl, hydroxyethyl, trifluoromethyl, benzyl, sulfopropyl, diethylaminoethyl, cyanopropyl,
p-chlorophenethyl, ethoxyethyl, ethylthioethyl, phenoxyethyl, carbamoylethyl, carboxyethyl, ethoxycarbonylmethyl, acetylaminoethyl), an unsubstituted or substituted alkenyl group having 3 to 10 carbon atoms (eg, allyl, styryl), 6 to 1 carbon atoms
0 unsubstituted or substituted aryl groups (eg phenyl, naphthyl, p-carboxyphenyl, 3,5-dicarboxyphenyl, m-sulfophenyl, p-acetamidophenyl, 3-caprylamidophenyl, p-sulfamoylphenyl) , M-hydroxyphenyl, p-nitrophenyl, 3,5-dichlorophenyl, p-anisyl, o
-Anisyl, p-cyanophenyl, p-N-methylureidophenyl, m-fluorophenyl, p-tolyl, m
-Tolyl), optionally substituted heterocyclic residue having 1 to 10 carbon atoms (eg pyridyl, 5-methyl-2-pyridyl, thienyl), halogen atom (eg chlorine, bromine, fluorine), mercapto group, cyano group , A carboxyl group, a sulfo group, a hydroxy group, a carbamoyl group having 1 to 8 carbon atoms, a sulfamoyl group having 1 to 8 carbon atoms, an amino group, a nitro group, an optionally substituted alkoxy group having 1 to 10 carbon atoms (for example, Methoxy, ethoxy, 2-methoxyethoxy, 2-phenylethoxy), an optionally substituted aryloxy group having 6 to 10 carbon atoms (for example, phenoxy, p-methylphenoxy, p-chlorophenoxy),
Acyl group having 1 to 8 carbon atoms (eg acetyl, benzoyl), acylamino group having 1 to 8 carbon atoms (eg acetylamino, caproylamino), sulfonyl group having 1 to 8 carbon atoms (eg methanesulfonyl, benzenesulfonyl) , A sulfonylamino group having 1 to 8 carbon atoms (eg methanesulfonylamino, benzenesulfonylamino), a substituted amino group having 2 to 8 carbon atoms (eg diethylamino, hydroxyamino), an alkyl or arylthio group having 1 to 10 carbon atoms (eg Methylthio, carboxyethylthio, sulfobutylthio, phenylthio), an alkoxycarbonyl group having 1 to 8 carbon atoms (eg, methoxycarbonyl), an aryloxycarbonyl group having 6 to 10 carbon atoms (eg, phenoxycarbonyl), and the like.

Further, on these substituents, an alkyl group, an alkenyl group, an aryl group, a hydroxy group, a carboxyl group, a sulfo group, a nitro group, a cyano group, a halogen atom, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, An acyl group, an acylamino group, a sulfonamino group, a carbamoyl group, a sulfamoyl group, etc. may be substituted.

V ₁ , V ₂ , V ₃ , V ₄ , V ₅ , V ₆ , V ₇ , V ₈ , V ₉ , V
₁₀ , V ₁₁ , V ₁₂ , V ₁₃ , V ₁₄ , V ₁₅ , V ₁₆ , V _4A ,
V _5A , V _6A , W ₀₁ and W ₀₂ are preferably hydrogen atoms,
An alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an aryloxy group having 1 to 10 carbon atoms, a halogen atom or a trifluoromethyl group, more preferably a hydrogen atom, a methyl group or an ethyl group. , A propyl group, a methoxy group, an ethoxy group, a phenoxy group, a chloro group or a trifluoromethyl group. V ₁ , V ₂ , V ₃ , V ₄ , V ₅ ,
As V ₆ , V _4A , V _5A and V _6A , a hydrogen atom is particularly preferable, and as V ₇ and V ₁₂ , a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a phenoxy group, a chloro atom or The trifluoromethyl group is particularly preferred.

X ₁ represents a charge balancing counterion. The ion that cancels the charge in the molecule is selected from anion and cation. Anions are inorganic or organic acid anions (such as p-toluenesulfonate, p-nitrobenzenesulfonate, methanesulfonate, methylsulfate, ethylsulfate, perchlorate, etc.), halogen ions (such as chloride, bromide, iodide, etc.), etc. Represents Cations include inorganic and organic ones,
Specifically, hydrogen ion, alkali metal ion, (for example, each ion of lithium, sodium, potassium, cesium, etc.), alkaline earth metal ion (for example, each ion of magnesium, calcium, strontium, etc.), ammonium ion, organic ammonium , Triethanolammonium, pyridinium and the like) and the like. m represents the number necessary for neutralizing the charge in the molecule, and m is 0 when forming an intramolecular salt.

In the general formulas (II) and (IV), R ₂₁ ,
R ₂₂ , R ₂₃ , X ₂ and n are R ₁₁ in the general formula (I),
It is synonymous with R ₁₂ , R ₁₃ , X ₁ and m. The substituent represented by W ₂₁ and W ₂₂ is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms (for example, ethyl, propyl, butyl, hydroxyethyl, benzyl, sulfopropyl, diethylaminoethyl, cyanopropyl, p -Chlorophenethyl, ethoxyethyl, ethylthioethyl, phenoxyethyl, carbamoylethyl, carboxyethyl, ethoxycarbonylmethyl, acetylaminoethyl), an unsubstituted or substituted alkenyl group having 3 to 10 carbon atoms (eg, allyl, styryl), carbon An unsubstituted or substituted aryl group of the formulas 6 to 10 (eg phenyl, naphthyl, p
-Carboxyphenyl, 3,5-dicarboxyphenyl, m-sulfophenyl, p-acetamidophenyl,
3-caprylamidophenyl, p-sulfamoylphenyl, m-hydroxyphenyl, p-nitrophenyl,
3,5-dichlorophenyl, p-anisyl, o-anisyl, p-cyanophenyl, p-N-methylureidophenyl, m-fluorophenyl, p-tolyl, m-tolyl), substituted with 1 to 10 carbon atoms A heterocyclic residue (eg, pyridyl, 5-methyl-2-pyridyl, thienyl), an optionally substituted alkoxy group having 1 to 10 carbon atoms (eg, methoxy, ethoxy, 2-methoxyethoxy, 2-phenylethoxy). ), An optionally substituted aryloxy group having 6 to 10 carbon atoms (eg, phenoxy, p-methylphenoxy, p-chlorophenoxy),
An acyl group having 1 to 8 carbon atoms (eg acetyl, benzoyl), an alkyl or arylthio group having 1 to 10 carbon atoms (eg ethylthio, phenylthio), an alkoxycarbonyl group having 1 to 8 carbon atoms (eg methoxycarbonyl), 6 carbon atoms To 10 aryloxycarbonyl groups (eg, phenoxycarbonyl) and the like. W
_At least one of ₂₁ and W ₂₂ represents a substituent having 2 or more carbon atoms.

W ₂₁ and W ₂₂ are preferably an alkyl group having 2 to 5 carbon atoms, an alkoxy group having 2 to 5 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms, and more preferably an ethyl group or a propyl group. , A methoxy group, an ethoxy group, an n-butyl group and a phenoxy group.

Among the sensitizing dyes represented by the general formula (I), those represented by the following general formula (III) are preferable, and a preferable combination of each substituent in the general formula (III) is as follows. V ₁ ,
V ₂ , V ₃ , V ₄ , V ₅ , and V ₆ are hydrogen atoms, and at least one of V ₇ and V ₁₁ and at least one of V ₁₂ and V ₁₆ have 1 carbon atoms.
To the alkyl group or alkoxy group of 3 to R ₁₁ ,
R ₁₂ is a sulfoalkyl group having 2 to 4 carbon atoms, and R ₁₃ is a case where a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is combined, and among these, more preferred are V ₇ and V _11. At least one of V ₁₂ , and at least one of V ₁₆
One is a methyl group or a methoxy group, and R ₁₁ and R ₁₂ have 3 carbon atoms
To 4 of sulfoalkyl groups, n is 1, R ₁₃
Is a methyl group or an ethyl group.

Among the sensitizing dyes represented by the general formula (II),
Those represented by the following general formula (IV) are preferable, but
As a preferred combination of each substituent in the formula (IV),
W_{twenty one}, W _{twenty two}Is an alkyl group having 2 to 5 carbon atoms or an alcohol
Xy group, R_{twenty one}, R_{twenty two}Is a sulfoalkyl having 2 to 4 carbon atoms
Group and R_{twenty three}Is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
When W is combined, and more preferably W_{twenty one},
W_{twenty two}Is ethyl, n-propyl, n-butyl, t-butyl
Group, ethoxy group, R_{twenty one}, R_{twenty two}Is a sulfo having 3 to 4 carbon atoms
Alkyl group, m is 1, R_{twenty three}Is a methyl group or an ethyl group
This is the case. Represented by general formulas (I) and (II) below
Specific examples of the sensitizing dye are shown below, but the present invention is not limited to these.
It is not something that can be done. In addition, Me, Et,^tAm,ⁿPr,
ⁿBu and^tBu is methyl group, ethyl group, tert
-Amyl group, n-propyl group, n-butyl group and tert-
It represents a butyl group.

[0026]

[Chemical 9]

[0027]

[Chemical 10]

[0028]

[Chemical 11]

[0029]

[Chemical 12]

[0030]

[Chemical 13]

[0031]

[Chemical 14]

The compounds represented by the general formulas (I) and (II) of the present invention are those described by FM Hamer, "Heterocyclic Compounds-Cyanine Soybean and Relative Compounds (Heterocycli).
c Compounds-Cyanine Dyes and Related Compounds)
(John Wiley & S
ons-New York, London, 1964).
DMSturmer, "Heterocyclic Compounds ---- Special topics in he
terocyclic chemistry ----) '', Chapter 18, Section 14, Section 4
82-515, John Willy and Sons (Jo
hn Wiley & Sons), New York, London, (1977), "Rodd's Chemistry of Carbon Compounds",
(2nd.Ed.vol.IV, part B, 1977), Chapter 15, pp. 369-422; (2nd.Ed.vol.IV, part B, 1985), 15th
Chapter, pp. 267-296, Elsevier Science P.
ublishing Company Inc.), published by New York, and the like.

(Synthesis Example) The sensitizing dye I-5 in the specific example was synthesized by the route shown in the following scheme 1.

[0034]

[Chemical 15]

(Synthesis of Compound A) Orthobromotoluene
(51.3 g, 0.3 mol) and magnesium (10.2 g) were reacted in 70 ml of tetrahydrofuran to prepare a Grignard reagent. Trimethyl borate (31.2 g, 0.3 mol) and diethyl ether (150 ml) were charged in another container, and the internal temperature was adjusted to -6 under a nitrogen stream.
The temperature was kept at 0 ° C. or lower, and the Grignard reagent was added dropwise to this solution over 10 minutes. After stirring as such for 3 hours, 15 ml of water was added dropwise and the temperature was raised to room temperature. Next, an aqueous solution containing 8 ml of concentrated sulfuric acid 10
0 ml was added dropwise and the mixture was further stirred at room temperature for 1 hour. The reaction solution was extracted with 500 ml of diethyl ether, and the diethyl ether layer was concentrated under reduced pressure to give crude crystals of compound A. 24.5 g (yield) of Compound A was obtained by heating the crude crystals with hexane.
60%) obtained.

(Synthesis of Compound B) Compound A (4.1 g, 0.03 m
ol) and 5-bromo-2-methylbenzoxazole (4.2
g, 0.02 mol) was dissolved in dimethylformamide (65 ml), tetrakistriphenylphosphine palladium (0.7 g, 0.6 mmol) and potassium carbonate (8.3 g, 0.06 mol) were added under a nitrogen stream, and the internal temperature was raised to 90 ° C. The temperature was raised and the mixture was stirred as it was for 8 hours.
After the reaction was completed, the temperature was returned to room temperature, 20 ml of water was added, and the mixture was further stirred for 10 minutes. The reaction solution was extracted with methylene chloride, the organic layer was dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained residue was purified with a silica gel column to give an oily compound B (4.1 g, yield 92%).

(Synthesis of Compounds C and I-5) Compound B (3.8
g, 17 mmol) and butanesultone (4.6 g, 34 mmol) were reacted at 150 ° C. for 6 hours. The internal temperature was lowered to 60 ° C., ethyl acetate was added and the mixture was stirred at room temperature for 20 minutes, and then ethyl acetate was decanted off to obtain a resinous compound C. This was used for the next dyeing reaction immediately without further purification. Compound C (5.
4g, 15mmol) in a mixed solvent of acetic acid 15ml-pyridine 27ml, triethyl orthopropionate (10.6g, 60mmol)
Was added to bring the internal temperature to 60 ° C., and then triethylamine (2.8 m
l) was added and the mixture was heated under reflux for 2 hours. 200 reaction solution
The mixture was poured into ml of ethyl acetate and stirred at room temperature for 2 hours to obtain a resinous mixture containing the triethylamine salt of I-1. This was dissolved in 20 ml of methanol, heated under reflux, further added with a methanol solution of sodium acetate (1.7 g), and refluxed for 30 minutes. A few drops of isopropanol were added to this solution and left overnight at room temperature for crystallization. The crystals were separated by filtration and washed with ice-cold methanol to obtain a dye I-5.
(3.2g, 55% yield) λmax = 500.0nm mp = 177 ℃ (decomp.)

Next, synthetic examples of the compound shown in Chemical formula 16 will be shown.

[0039]

[Chemical 16]

(Example of Synthesis of Phenylboric Acid Derivative) An example of synthesis of the phenylboric acid derivative shown in Table 1 is shown below. (Synthesis of I-4B) 1-bromo-2,4-dimethylbenzene (37.0 g, 0.2 mol), magnesium (6.6 g), tetrahydrofuran 40 ml, trimethyl borate (20.8 g, 0.2 mol), diethyl ether (100 ml) In the same manner as compound A
I got I-4B. Yield 9.0g (yield 30%). (Synthesis of I-7B) 1-Bromo-2-methoxybenzene (56.
1g, 0.3mol), magnesium (10.2g), tetrahydrofuran 70ml, trimethyl borate (31.2g, 0.3mol), diethyl ether (150ml) with the same treatment as for compound A
Got Yield 25.1 g (55% yield). (Synthesis of I-10B) 1-Bromo-2-trifluoromethylbenzene (22.5 g, 0.1 mol), magnesium (3.2 g), tetrahydrofuran 60 ml, trimethyl borate (12.5 g, 0.12 mol)
I-10B was obtained by the same treatment as for compound A using diethyl ether (200 ml). Yield 5.3g (yield 28%).

(Synthesis of II-1B) 1-Bromo-4-ethoxybenzene (50.0 g, 0.25 mol), magnesium (7.9 g), tetrahydrofuran 70 ml, trimethyl borate (26.0 g, 0.25 m)
II-1B was obtained by the same treatment as for compound A using ol) and diethyl ether (150 ml). Yield 19.2 g (yield 46%). (Synthesis of II-4B) 1-Bromo-4-propylbenzene (3
0.0g, 0.15mol), magnesium (4.8g), tetrahydrofuran 40ml, trimethyl borate (17.0g, 0.16mol), diethyl ether (70ml) in the same manner as for compound A II
I got -4B. Yield 6.7g (25% yield).

(Synthesis of benzoxazole derivative) (Synthesis of I-4A) Compound I-4B (3.9 g, 26 mmol), 5-bromo-2-methylbenzoxazole (4.2 g, 20 mmol) was dissolved in dimethylformamide (65 ml). Then, under a nitrogen stream, tetrakistriphenylphosphine palladium (0.7g, 0.6mmo
l) and potassium carbonate (8.3 g, 0.06 mol) were added, and the internal temperature was adjusted to 100
The temperature was raised to ℃ and the mixture was stirred as it was for 7 hours. After the reaction was completed, the temperature was returned to room temperature, 20 ml of water was added, and the mixture was further stirred for 10 minutes. The reaction solution was extracted with methylene chloride, the organic layer was dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained residue was purified by a silica gel column to give oily compound I-4A.
Got (Yield 4.1g, Yield 86%) mp = 82 ℃

(Synthesis of I-7A) Compound I-7B (4.0 g, 26 mmo
l) 5-bromo-2-methylbenzoxazole (4.2
g, 20 mmol) in dimethylformamide (65 ml), add tetrakistriphenylphosphine palladium (0.7 g, 0.6 mmol) and potassium carbonate (8.3 g, 0.06 mol) under a nitrogen stream, and raise the internal temperature to 100 ° C. It was heated and stirred as it was for 9 hours. After the reaction was completed, the temperature was returned to room temperature, 20 ml of water was added, and the mixture was further stirred for 10 minutes. The reaction solution was extracted with methylene chloride, the organic layer was dried over magnesium sulfate, filtered and concentrated under reduced pressure, and the obtained residue was purified by a silica gel column to obtain an oily compound I-7A. (Yield 2.1g, Yield 44%) mp
= 60 ℃

(Synthesis of I-10A) Compound I-10B (4.9 g, 26
mmol) 5-bromo-2-methylbenzoxazole
(4.2 g, 20 mmol) was dissolved in dimethylformamide (65 ml), and tetrakistriphenylphosphine palladium (0.7 g, 0.6 mmol) and potassium carbonate (8.3 g, 0.06 mol) were added under a nitrogen stream.
l) was added, the internal temperature was raised to 100 ° C., and the mixture was stirred as it was for 9 hours. After the reaction was completed, the temperature was returned to room temperature, 20 ml of water was added, and the mixture was further mixed.
Stir for 0 minutes. The reaction solution was extracted with methylene chloride, the organic layer was dried over magnesium sulfate, filtered and concentrated under reduced pressure, and the obtained residue was purified with a silica gel column.
An oily compound I-10A was obtained. (Yield 2.1g, Yield 38%
) Mp = 55 ℃

(Synthesis of II-1A) Compound II-1B (19.0 g,
0.11mol) 5-bromo-2-methylbenzoxazole (18.7g, 88mmol) was dissolved in dimethylformamide (240ml), and tetrakistriphenylphosphine palladium (3.1g, 2.6mmol) and potassium carbonate (36.5g, 0.2
6 mol), and the internal temperature was raised to 100 ° C, and then 8.5
Stir for hours. After the reaction was completed, the temperature was returned to room temperature, 80 ml of water was added, and the mixture was further stirred for 10 minutes. The reaction solution was extracted with methylene chloride, the organic layer was dried over magnesium sulfate, filtered and concentrated under reduced pressure, and the obtained residue was purified by a silica gel column to obtain white crystalline compound II-1A. (Yield 12.8g
, Yield 57%) mp = 98 ℃

(Synthesis of II-4A) Compound II-4B (5.6g, 34m
mol), 5-bromo-2-methylbenzoxazole (5.3
g, 25 mmol) in dimethylformamide (70 ml), add tetrakistriphenylphosphine palladium (0.9 g, 0.8 mmol) and potassium carbonate (10.3 g, 0.07 mol) under a nitrogen stream, and raise the internal temperature to 100 ° C. It was warmed and stirred as it was for 8 hours. After the reaction was completed, the temperature was returned to room temperature, 30 ml of water was added, and the mixture was further stirred for 10 minutes. The reaction solution was extracted with methylene chloride, the organic layer was dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained residue was purified by a silica gel column to obtain white crystalline compound II-4A. (Yield 5.3g, Yield 84%) mp
= 112 ° C

(Synthesis of Cyanine Dye) (Synthesis of Compound I-4) Compound I-4A (3.5 g, 15 mmol) was reacted with butanesultone (5.1 g, 37 mmol) at 140 ° C. for 5.5 hours. The internal temperature was lowered to 60 ° C., ethyl acetate was added and the mixture was stirred at room temperature for 20 minutes, and then ethyl acetate was decanted off to obtain a resinous benzoxazole quaternary salt. This was used for the next dyeing reaction immediately without further purification. The quaternary salt was dissolved in a mixed solvent of 10 ml of acetic acid-16 ml of pyridine, triethylorthopropionate (10.3 g, 58 mmol) was added, and the mixture was heated under reflux for 2 hours. The reaction mixture was poured into 70 ml of ethyl acetate and stirred at room temperature for 2 hours to obtain a mixture containing slurry-like I-4. After decanting the solvent, remove the residue
Crystallization was performed from 20 ml of a mixed solvent of methanol, isopropanol and pyridine. The crystals collected by filtration were recrystallized from methanol to obtain dye I-4. (Yield 1.7g, Yield 29%) λmax = 503.9nm mp = 167 ° C (decomp.)

(Synthesis of Compound I-7) Compound I-7A (3.6 g, 15
mmol) and butanesultone (4.1g, 30mmol) at 150 ℃ 9
Reacted for hours. The internal temperature was lowered to 60 ° C., ethyl acetate was added and the mixture was stirred at room temperature for 20 minutes, and then ethyl acetate was decanted off to obtain a resinous benzoxazole quaternary salt. This was used for the next dyeing reaction immediately without further purification.
The quaternary salt was dissolved in a mixed solvent of 6 ml of acetic acid-8 ml of pyridine, triethylorthopropionate (10.0 g, 57 mmol) was added to bring the internal temperature to 60 ° C, and then triethylamine (2.5 ml).
Was added and the mixture was heated under reflux for 2 hours. The reaction mixture was poured into 70 ml of ethyl acetate and stirred at room temperature for 5 hours to obtain a slurry.
A mixture containing a triethylamine salt of I-7 was obtained. After removing the solvent by decanting, the residue was dissolved in 20 ml of methanol and heated under reflux for further sodium acetate.
A solution of (1.2 g) in methanol was added and refluxed for 30 minutes. Sephadex LH-20 (Pharmacia)
Was purified by a column packed with to give Dye I-7. (Yield 1.4
g, yield 23%) λmax = 505.7nm mp = 132 ℃ (decomp.)

(Synthesis of Compound I-10) Compound I-10A (4.1 g, 1
5 mmol) and bromoacetic acid (2.1 g, 15 mmol) were dissolved in 1,1,2,2-tetrachloroethylene and reacted at 140 ° C. for 5 hours. The solvent was removed by decantation to obtain a resinous benzoxazole quaternary salt. This was used for the next dyeing reaction immediately without further purification. Quaternary salt of acetic acid 10ml-pyridine 16ml
The resulting mixture was dissolved in the mixed solvent of, and triethylorthopropionate (10.3 g, 58 mmol) was added to adjust the internal temperature to 60 ° C., triethylamine (2.8 ml) was added, and the mixture was heated under reflux for 2 hours. The reaction mixture was poured into 70 ml of ethyl acetate and stirred at room temperature for 2 hours to obtain a mixture containing a slurry of I-10 carboxylic acid free form. After the solvent was decanted off, the residue was dissolved in 20 ml of methanol, heated under reflux, and a methanol solution of sodium acetate (1.2 g) was added, followed by refluxing for 30 minutes. This mixture was added to Sephadex LH-20 (Ph
(manufactured by armacia) and purified by a column packed to give Dye I-10. (Yield 0.8g, Yield 12%) λmax = 504.6nm mp = 140 ℃ (decomp.)

(Synthesis of Compound II-1) Compound II-1A (7.8 g, 3
0 mmol) and butanesultone (9.0 g, 66 mmol) at 155 ° C. 5.
The reaction was carried out for 5 hours. The internal temperature was lowered to 60 ° C., ethyl acetate was added and the mixture was stirred at room temperature for 20 minutes, and then ethyl acetate was decanted off to obtain a resinous benzoxazole quaternary salt. This was used for the next dyeing reaction immediately without further purification. The quaternary salt was dissolved in a mixed solvent of 12 ml of acetic acid-18 ml of pyridine, and triethyl orthopropionate (21.1 g, 0.12 mo
l) was added to bring the internal temperature to 60 ° C., and then triethylamine (5.
0 ml) was added and the mixture was heated under reflux for 2 hours. One hour after the start of reflux, dye crystals start to precipitate. 3 ml of ethyl acetate and 5 ml of acetone were added to the reaction solution, and the mixture was crystallized under ice cooling for 1 hour. The dye crystals collected by filtration are dissolved in 40 ml of methanol, heated under reflux, and a solution of sodium acetate (2.5 g) in methanol is added to precipitate II-1. The crystals were collected by filtration and washed with ice-cold methanol to obtain dye II-1. (Yield 6.3
g, yield 46%) λmax = 506.7nm mp = 197 ° C (decomp.)

(Synthesis of Compound II-4) Compound II-4A (5.0 g, 2
0 mmol) and 1-methylpropane sultone (5.4 g, 40 mmol)
The reaction was carried out at 130 ° C for 3 hours. The internal temperature was lowered to 60 ° C., ethyl acetate was added, and the mixture was stirred at room temperature for 20 minutes to precipitate crystals of quaternary benzoxazole salt. The crystals were collected by filtration and immediately used in the next pigmentation reaction. Dissolve the quaternary salt in a mixed solvent of 8 ml of acetic acid-12 ml of pyridine, and add triethylorthopropionate.
(10.6 g, 60 mmol) was added to bring the internal temperature to 60 ° C., triethylamine (4.0 ml) was added, and the mixture was heated under reflux for 2 hr. To the reaction solution were added 5 ml of ethyl acetate and 10 ml of acetone, and the mixture was stirred for 1 hour under ice cooling to precipitate dye crystals. The dye crystals collected by filtration are dissolved in 20 ml of methanol, heated under reflux, and a solution of sodium acetate (1.2 g) in methanol is added to precipitate II-4. The crystals were separated by filtration and washed with ice-cold methanol to obtain dye II-4. (Yield 2.7g, yield
33%) λmax = 505.0nm mp = 216 ℃ (decomp.)

To incorporate the spectral sensitizing dyes of the present invention in a silver halide emulsion, they may be dispersed directly in the emulsion, or water, methanol, ethanol,
It may be added to the emulsion by dissolving it in a solvent such as propanol, methyl cellosolve, 2,2,3,3-tetrafluoropropanol or the like alone or in a mixed solvent. In addition, Japanese public examination 4
No. 4,223,389, JP-B-44-27555, JP-B-57-22089 and the like, an acid or a base is allowed to coexist to form an aqueous solution, or US Pat.
As described in U.S. Pat. No. 4,060,025, an aqueous solution or a colloidal dispersion in which a surfactant coexists may be added to the emulsion. Alternatively, the emulsion may be dissolved in a solvent which is substantially immiscible with water, such as phenoxyethanol, and then dispersed in water or a hydrophilic colloid to be added to the emulsion. JP-A-53-102733, JP-A-58-105
It may be directly dispersed in a hydrophilic colloid as described in No. 141, and the dispersion may be added to the emulsion. Further, as described in JP-B-46-24185, a method of dispersing a water-insoluble dye in a water-soluble solvent without dissolving it, and adding this dispersion to an emulsion, described in JP-B-61-45217. As described above, a method of mechanically pulverizing and dispersing a water-insoluble dye in a water-soluble solvent and adding the dispersion to an emulsion may be performed.

The photographic emulsion used in the present invention is a photographic emulsion of the present invention.
Spectral sensitization with other methine dyes and other compounds
May be done. The dyes used are cyanine dyes,
Russianine dye, complex cyanine dye, complex merocyanine
Dye, holopolar cyanine dye, hemicyanine dye,
Including styryl dyes and hemioxonol dyes
It Particularly useful dyes are cyanine dyes and merocyanine dyes.
It is a pigment belonging to the elementary and complex merocyanine pigments.
These dyes have a cyanine color as a basic heterocyclic nucleus.
Any of the nuclei normally used for the primes can be applied. sand
That is, pyrroline nucleus, oxazoline nucleus, thiozoline nucleus,
Roll nucleus, oxazole nucleus, thiazole nucleus, selenazo
Le nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus
A; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and
A nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, that is,
Ndrenine nucleus, benzoindolenine nucleus, indole nucleus,
Benzoxazole nucleus, naphthoxazole nucleus, benzo
Thiazole nucleus, naphthothiazole nucleus, benzoselenazo
Applicable to le nucleus, benzimidazole nucleus, quinoline nucleus, etc.
Wear. These nuclei may be substituted on carbon atoms. Me
Ketome for cyanine dyes or complex merocyanine dyes
Pyrazolin-5-one as a nucleus having a thylene structure
Nucleus, thiohydantoin nucleus, 2-thiooxazolidine-
2,4-dione nucleus, thiazolidine-2,4-dione nucleus,
5 to 6 member differences such as Rhodanine nucleus and Thiobarbituric acid nucleus
A nodal ring nucleus can be applied. The compound of the invention is alone
However, a combination of them may be used, and
Combinations of dyes are often used especially for the purpose of supersensitization.
To be A typical example thereof is US Pat. No. 2,688,545.
Issue 2, Issue 2,977,229, Issue 3,397,060
No. 3,522,052, No. 3,527,641
Issue 3, Issue 3,617,293, Issue 3,628,964
Issue 3, Issue 3,666,480, Issue 3,672,898
Issue No. 3,679,428 Issue 3,303,377
Issue No. 3,769,301 Issue No. 3,814,609
No. 3,837,862, 4,026,707
No., British Patents 1,344,281 and 1,507,8
No. 03, Japanese Patent Publication No. 43-49336, No. 53-12, 3
No. 75, JP-A Nos. 52-110,618 and 52-10.
No. 9,925. With the compound of the present invention
, A dye that does not have spectral sensitizing effect itself or visible
A substance that does not substantially absorb light and exhibits supersensitization.
The substance may be included in the emulsion. Compound of the invention in emulsion
It has been known to be useful when added to
It may be at any stage of emulsion preparation. Most common
Is performed after the completion of chemical sensitization and before application.
, U.S. Pat. Nos. 3,628,969 and 4,225,
At the same time as the chemical sensitizer as described in No. 666.
It is also possible to add a spectral image at the same time as chemical sensitization.
Chemistry as described in Sho 58-113,928
It can also be done prior to sensitization, and also silver halide grains
It is also possible to add it before the completion of particle precipitation to start spectral sensitization.
I can. In addition, teach in U.S. Pat. No. 4,225,666.
Add these compounds separately as shown.
That is, prior to chemical sensitization of some of these compounds
It is also possible to add the remainder after chemical sensitization
And taught in US Pat. No. 4,183,756
When the silver halide grains are being formed
It may be a period. The amount of the compound of the present invention added is
4 x 10 per mol of silver halide^-6~ 8 × 10 ^-3Used in moles
However, a more preferred silver halide grain size
Approx. 5 x 10 for 0.2 to 1.2 μm^-Five~ 2 x 10
^-3Mole is more effective. Silver halide used in the present invention
The emulsion may have any grain size distribution, but the maximum
Included within ± 20% particle size range centered on particle size (average) r
The weight of silver halide contained is 6 of the total weight of silver halide grains.
It is preferably 0% or more, and 80% or more
Is more preferable. The silver halide used in the present invention has an odor.
With silver iodide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride
is there. The silver halide grains used in the present invention are cubic, octagonal
Those with regular crystals such as tetrahedrons and tetradecahedrons, spheres
Having irregular crystal shape such as plate-like and plate-like, twin plane
Having crystal defects such as
But it's okay. The grain size of silver halide is about 0.2 μm or less.
Even fine particles have a projected area diameter of up to about 10 μm
Iz grains, either polydisperse emulsions or monodisperse emulsions
Yes. The silver halide photographic emulsion usable in the present invention is, for example,
For example, Research Disclosure (RD) No. 176
43 (Dec. 1978), pp. 22-23, "I. Emulsion
"Emulsion preparation and types" ", No. 187
16 (November 1979), p. 648, ibid., No. 3071.
05 (November 1989), pages 863-865, graph
Kide, "Physics and Chemistry of Photography," published by Paul Montel (P.
Glafkides.Chemie et Phisique Photographique, Paul
Montel, 1967), "Photoemulsion Chemistry" by Duffin, Ph.
Published by Cal Press (G.F.Duffin, Photographic Emulsion
Chemistry, Focal Press, 1966), and Zeri Kumann et al.
"Manufacturing and coating of photographic emulsion", published by Focal Press (V.
L. Zelikman et al., Making and Coating Photographic
 Emulsion, Focal Press, 1964) etc.
Can be prepared using. US Pat. No. 3,57
4,628, 3,655,394 and British patents
Monodisperse emulsions described in No. 1,413,748 are also available.
preferable. Also, the aspect ratio (equivalent to the circle of AgX particles
AgX grains having a diameter / grain thickness of about 3 or more are all A in the emulsion.
An emulsion having 50% (area) or more of gX grains is also included in the present invention.
Can be used. Tabular grains, Gatov, photography
Guc San Ens and Engineering (Gutof
f, Photographic Science and Engineering), 14th
Vol. 248-257 (1970), U.S. Pat. No. 4,
No. 434, 226, No. 4,414, 310, No. 4, 4
33,048, 4,439,520 and the British special
Easy according to the method described in No. 2,112,157
Can be prepared. Halo consisting of regular particles
The silver genide emulsion has a double jet while keeping the pAg constant.
Degree of supersaturation that does not cause re-nucleation by the Stott method
Nucleation and grain growth while maintaining
Particles of a size can be obtained. In addition, JP-A-54-
Applying the method described in Japanese Patent No. 48521
You can In the method, as a preferred embodiment, iodide is used.
Potassium-gelatin aqueous solution and ammonium silver nitrate aqueous solution
Solution and gelatin solution containing silver halide grains.
By adding acceleration by changing the acceleration as a function of time
To manufacture. At this time, the time function of the addition rate, pH, p
By appropriately selecting Ag, temperature, etc.,
A dispersible silver halide emulsion can be obtained. For more information,
For example, Photographic Science and En
Genialing (Photographic Scienceand Engineerin
g), Vol. 6, 159-165 (1962); Journal.
Le of Photographic Science (Journal
of Photographic Science), Volume 12, pp. 242-251
(1964), US Pat. No. 3,655,394 and
It is described in British Patent No. 1,413,748. Conclusion
Even if the crystal structure is uniform, the inside and outside are different halogen
It may have a layered structure.
Yes. These emulsion grains are described in British Patent No. 1,027,14.
6, British Patent Nos. 3,505,068 and 4,44
Opened in 4,877 and JP-A-60-222845.
It is shown. Also, the composition by epitaxial junction
Different silver halides may be bonded, and
For example, compounds other than silver halide such as rhodan silver and lead oxide
May be joined with. The silver halide emulsion of the present invention is
Distribution or structure related to halogen composition in the grain
It is preferable to have The typical one is Shokoku Sho 4
JP-A-3-13162, JP-A-61-215540, JP-A-61-215540
JP-A-60-222845 and JP-A-61-75337.
The inside of the particle and the surface layer are different as disclosed in
Core-shell type or double structure type having a rogen composition
Particles. Further, it is not a simple double structure, but is disclosed in JP-A-60
A triple structure as disclosed in US Pat.
Or more multilayer structure, core-shell
Halogenation with different composition on the surface of double-structured particles
You can use thin silver. Structure inside the particle
In addition to the wrapping structure described above,
Particles having a so-called bond structure can be produced.
Examples of these are JP-A-59-133540 and JP-A-58.
-108526, EP199290A2, Japanese Patent Publication 58
Disclosed in JP-A-24772 and JP-A-59-16254.
Has been done. The crystal to be bonded is different from the host crystal
Depending on the composition, the edges and corners of the host crystal, or
Can be produced by bonding to the surface portion. like this
The host crystal of the junction crystal is uniform with respect to the halogen composition.
Or having a core-shell type structure
Can be formed. In the case of a joint structure,
Of course, it is possible to combine silver rogenide comrades, but Roda
Halogenated silver salt compounds that do not have a rock salt structure, such as silver and silver carbonate.
It can be combined with silver halide to form a joint structure. Also P
Non-silver salt compounds such as bO are also used if a junction structure is possible.
You may stay. In the case of silver iodobromide grains having these structures
In the case of core-shell type particles, the core part is
High silver iodide content and low silver iodide content in the shell
On the contrary, on the contrary, the silver iodide content of the core part is low and the shell part is
It may be high particles. Particles with a similar bonding structure
Also, the host crystal has a high silver iodide content,
, Even if the grains have a relatively low silver iodide content.
Particles may be used. Also, grains having these structures
Borders with different halogen composition of the child are clear boundaries.
However, due to the difference in composition, mixed crystals are formed and there is an unclear boundary.
Maybe, and also positively made continuous structural changes
Can be The silver halide emulsion used in the present invention is EP-
0096727B1, EP-0064412B1 etc.
There is a treatment that imparts roundness to the particles, as disclosed.
DE 2306447C2, JP-A-60-2213
The surface may be modified as disclosed in No. 20.
Yes. The silver halide emulsion used in the present invention preferably has a surface latent image type.
However, it is disclosed in JP-A-59-133542.
By selecting the developing solution or developing conditions so that
Partial latent image type emulsions can also be used. In addition, JP-A-63
-Shallow internal latent covering the thin shell described in No. 264740
Image type emulsions are also preferably used. Ha to accelerate aging
A silver rogenide solvent is useful. For example to accelerate aging
Excessive halogen ions in the reactor.
Is known. Therefore, react the halide salt solution
It is clear that introduction into the vessel can accelerate ripening
is there. Other ripening agents can be used and these ripening agents
Agent is in reactor before adding silver and halide salts
It is possible to mix the entire amount in the dispersion medium of
One or more halide salts, silver salts or peptizers
Can also be added and introduced into the reactor. another
Alternatively, the ripening agent may be a halide salt and a silver salt addition.
It can also be introduced independently at additional stages. Halogen Io
Ammonia or amines as ripening agents other than
Compounds, thiocyanate salts, such as alkali metal thiosalts
Anate salts, especially sodium and potassium thiocyanate
Salt and ammonium thiocyanate salt
You can In the present invention, sulfur sensitization and gold sensitization are representative.
It is extremely important to carry out chemical sensitization. Polyvalent metal
1 x 10 ions^-FourMol / mol Ag or more doped particles
Has no characteristics in the unripe state and was chemically sensitized.
Occasionally, a remarkable effect is exhibited. Place for chemical sensitization
Depending on the composition, structure, and shape of the emulsion particles,
It depends on the intended use of the agent. Inside the particle
When chemically sensitized nuclei are embedded in the
When embedded or when chemically sensitized nuclei are formed on the surface
is there. In any case, the effect of the present invention is effective,
Preferred is when chemically sensitized nuclei are formed near the surface.
It In other words, surface latent image type emulsion is more effective than internal latent image type emulsion.
Is. Chemical sensitization by T.H.James, The
Photographic Process, 4th Edition, Macmillan
, 1977 (T.H. James, The Theory of the Photo
graphic Process, 4 th ed, Macmillan, 1977) 67-7
Doing with activated gelatin as described on page 6
You can also do Research Disclosure 120
Volume, April 1974, 12008; Research Disc
Roger, Volume 34, June 1975, 13452, US
National Patent Nos. 2,642,361 and 3,297,446
No. 3,772,031, No. 3,857,711
Issue 3, Issue 3,901,714, Issue 4,266,018
No. 3,904,415 and British Patent No.
PAg5-1 as described in No. 1,315,755.
Sulfur at 0, pH 5-8 and temperature 30-80 ° C,
Selenium, tellurium, gold, platinum, palladium, iridium
Alternatively, multiple combinations of these sensitizers can be used.
Wear. Optimum for chemical sensitization is gold compound and thiocyanate
In the presence of the compound and also in US Pat. No. 3,857,711.
Nos. 4,266,018 and 4,054,45
Sulfur-containing compounds described in No. 7 or hypo, thio
Sulfur-containing compounds such as urea compounds and rhodanin compounds
Do in the presence of things. Chemical sensitization in the presence of a chemical sensitization aid
You can also do it. The chemical sensitization aid used is azai
, Azapyrididine, azapyrimidine, etc.
Those that suppress fog and increase sensitivity in the process of academic sensitization
The compound known as is used. Chemical sensitization aid improvement
Examples of agents include U.S. Pat. Nos. 2,131,038 and 3,4.
11,914, 3,554,757, JP-A-58.
-126526 and Duffin, "Photoemulsification"
Gaku ”, pp. 138-143. According to the invention
The silver halide emulsion prepared by
It can be used for any of black and white photographic light-sensitive materials.
As color photographic light-sensitive materials, especially color paper and color
-Shooting film, color reversal film, black and white
Films for X-ray and general shooting films are used as true light-sensitive materials.
Examples thereof include films and films for printing sensitive materials.
Regarding Additives of Photographic Photosensitive Material to which the Emulsion of the Present Invention is Applied
Is not particularly limited, for example, Research Disclosure
ー Magazine (Research Disclosure) Volume 176 Item 1764
3 (RD17643) and 187 volumes Item 1871
6 (RD18716) can be referred to
It Various additions in RD17643 and RD18716
Listed below are the locations where the additives are listed.

[0054]

[Table 1]

The dye will be described in more detail. Colloidal silver or a dye is used in the light-sensitive material of the present invention for preventing irradiation and halation, particularly for separating the spectral sensitivity distribution of each light-sensitive layer and ensuring safety against safelight. Examples of such dyes include US Pat. Nos. 506,385, 1,177,429, and 1,
131,884, 1,338,977, 1,3
85,371, 1,467,214, 1,43
8,102, 1,553,516, JP-A-48-
No. 85, 130, No. 49-114, 420, No. 52-
117, 123, 55-161, 233, 59.
-111,640, Japanese Patent Publication Nos. 39-22,069, 43-13,168, 62-273527, and U.S. Pat. Nos. 3,247,127 and 3,469,985.
Oxonol dyes having a pyrazolone nucleus, a parbitur nucleus and a parbituric acid nucleus described in U.S. Pat. No. 4,078,933 and the like, US Pat.
379,533, British Patent 1,278,621,
Other oxonol dyes described in JP-A-1-134447 and 1-183652, and British Patent No. 57.
5,691, 680,631, 599,623
No. 786, 907, 907, 125, 1,
045,609, U.S. Pat. No. 4,255,326,
Azo dyes described in JP-A-59-211,043, JP-A-50-100,116 and JP-A-54-118,
247, British Patent Nos. 2,014,598 and 75
Azomethine dyes described in US Pat. No. 0,031, anthraquinone dyes described in US Pat. No. 2,865,752, US Pat. Nos. 2,538,009 and 2,688,
No. 541, No. 2,538,008, British Patent No. 58
4,609, 1,210,252, JP-A-50-
40,625, 51-3,623, 51-1
No. 0,927, No. 54-118,247, Japanese Patent Publication No. 48
No. 3,286, No. 59-37, 303 and the like, arylidene dyes, JP-B Nos. 28-3, 082 and 4;
4-16,594, 59-28,898 and the like, styryl dyes, British Patents 446,538, 1,335,422 and JP-A-59-228,250. Triarylmethane dyes, such as British Patent Nos. 1,075,653, 1,153,341, 1,284,730, 1,475,228 and 1,542,807. Described merocyanine dyes, U.S. Pat. Nos. 2,843,486, 3,294,294
539, cyanine dyes described in JP-A-1-291247, and the like. In order to prevent the diffusion of these dyes, the following methods can be mentioned. For example, a ballast group is added to the dye to make it resistant to diffusion. Further, for example, a method in which a hydrophilic polymer having a charge opposite to that of the dissociated anionic dye is allowed to coexist in a layer as a mordant and the dye is localized in a specific layer by interaction with dye molecules is disclosed in US Pat.
48,564, 4,124,386, 3,62
No. 5,694 and the like. Further, a method of dyeing a specific layer using a water-insoluble dye solid is disclosed in Japanese Patent Laid-Open No.
6-12639, 55-155350, 55-
No. 155351, No. 63-27838, No. 63-19.
7943, European Patent No. 15,601, and the like. Also, a method of dyeing a specific layer using fine particles of a metal salt having a dye adsorbed thereon is disclosed in US Pat.
No. 2,496,841, No. 2,496,843, and JP-A No. 60-45237. Among the additives, antifoggants and stabilizers are azoles (for example, benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, veromobenzimidazoles, nitroindazoles, benzotriazoles). , Aminotriazoles, etc .; mercapto compounds {for example, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines, Mercaptotriazines and the like}; thioketo compounds such as oxazolinethione; azaindenes {eg triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted ( , 3, 3a, 7) tetraazaindenes), pentaazaindenes such like}; benzenethiosulfonate benzenesulfinate, can be preferably used benzenesulfonic acid amide. As the color coupler, a non-diffusible type having a hydrophobic group called a ballast group in the molecule, or a polymerized oyster is preferable. The coupler has 4 equivalents or 2 with respect to silver ion.
Either equivalence may be used. Further, a colored coupler having a color correcting effect or a coupler releasing a development inhibitor upon development (so-called DIR coupler) may be contained. It may also include a colorless DIR coupling compound that is colorless in the product of the coupling reaction and releases a development inhibitor. A preferred example is JP-A-62-21.
No. 5272, page 91, upper right column, line 4 to page 121, upper left column, line 6; JP-A-2-33144, page 3, upper right column, line 14 to 18
Page top left column last line and page 30 top right column line 6 to page 35 bottom right column 1
1st line, European Patent 96570, page 4, lines 15-27, page 5, lines 30-28, last line, page 45, lines 29-3
1st line, page 47, line 23 to page 63, line 50. For example, magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, pyrazolotetrazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, and the like, and yellow couplers include acylacetamide couplers (for example, benzoyl). Acetanilides, pivaloylacetanilides), and the like, and cyan couplers include naphthol couplers, phenol couplers, and the like. As cyan couplers, U.S. Pat. Nos. 3,772,002 and 2,772,162;
No. 3768308, No. 4126396, No. 433
No. 4011, No. 4327173, No. 3446622
No. 4333999, No. 4451559, No. 44
No. 27767, etc., a phenolic coupler having an ethyl group at the meta position of the phenol nucleus, a 2,5-diacylamino-substituted phenolic coupler, a phenolic coupler having a phenylureido group at the 2nd position and an acylamino group at the 5th position. A coupler in which sulfonamide, amide or the like is substituted at the 5-position of naphthol is preferable because of excellent image fastness. The couplers and the like can be used in combination of two or more kinds in the same layer in order to satisfy the characteristics required for the light-sensitive material, and the same compound can be added to two or more different layers, as a matter of course. Hydroquinones, 6-hydroxychromans, 5-
Hydroxyl coumarans, spirochromans, p-alkoxyphenols, bisphenols and other hindered phenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines and the phenolic hydroxyl groups of these compounds are silylated. A typical example thereof is a modified or alkylated ether or ester derivative. Further, a metal complex represented by (bissalicylaldoximato) nickel complex and (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used. Any known method can be used for the photographic processing of the light-sensitive material using the present invention, and a known processing solution can be used. The processing temperature is usually selected from 18 ° C to 50 ° C.
The temperature may be lower than 8 ° C or higher than 50 ° C. Depending on the purpose, either a development process for forming a silver image (black and white photographic process) or a color photographic process including a development process for forming a dye image can be applied. The black-and-white developer contains dihydroxybenzenes (for example, hydroquinone), 3-pyrazolidones (for example, 1-phenyl-3-pyrazolidone), aminophenols (for example, N).
-Methyl-p-aminophenol) and other known developing agents can be used alone or in combination. The color developing solution generally comprises an alkaline aqueous solution containing a color developing agent. Color developing agents are known primary aromatic amine developers such as phenylenediamines (eg 4-amino-N, N-diethylaniline, 3-methyl-4-amino-N, N-diethylaniline, 4-amino-N). -Ethyl-N-β-hydroxyethylachiline, 3-methyl-4
-Amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-
Methanesulfoamidoethylaniline, 4-amino-3-
Methyl-N-ethyl-N-β-methoxyethylaniline and the like) can be used. In addition, L. F. A. 226, published by Focal Press (1966), "Photographic Processing Chemistry" by Meson.
229, U.S. Pat. Nos. 2,193,015 and 2,59
Those described in 2,364, JP-A-48-64933 and the like may be used. The developer should also have a pH such as alkali metal sulfites, carbonates, borates, and phosphates.
Development inhibitors such as buffers, bromides, iodides, and organic antifoggants, or antifoggants can be included. If necessary, a water softener, a preservative such as hydroxylamine, an organic solvent such as benzyl alcohol or diethylene glycol, a polyethylene glycol, a quaternary ammonium salt, a development accelerator such as amines, a dye-forming coupler, a competitive coupler, Fogging agents such as sodium boron hydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting agents, US Pat. No. 4,083,7.
The polycarboxylic acid type chelating agent described in No. 23, the antioxidant described in West German Publication (OLS) 2,622,950 and the like may be included. When color photographic processing is performed, the photographic light-sensitive material of the color developing solution is usually bleached. The bleaching process may be performed simultaneously with the fixing process or may be performed individually. Examples of bleaching agents include iron (III), cobalt
Compounds of polyvalent metals such as (III), chromium (VI) and copper (II), peracids, quinones, nitrone compounds and the like are used. For example, ferricyanide, dichromate, iron (II
I) or cobalt (III) organic complex salts, for example, ethylenediaminetetracomplex salt, aminopolycarboxylic acids such as nitrilotriacetic acid and 1,3-diamino-2-propanoltetraacetic acid, or complex salts of organic acids such as citric acid, tartaric acid and malic acid Persulfates, permanganates, nitrosophenols and the like can be used. Of these, potassium ferricyanide, ethylenediaminetetracomplex iron (III) sodium salt and ethylenediaminetetracomplex iron (III) ammonium salt are particularly useful. The ethylenediaminetetracomplex iron (III) complex salt is useful both in the independent bleaching solution and in the one-bath bleach-fixing solution. For bleaching or bleach-fixing solutions, US Pat.
2,520, 3,241,966, Japanese Patent Publication No. 45-
Various additives may be added in addition to the bleaching accelerators described in JP-A No. 8506 and JP-B-45-8836, the thiol compound described in JP-A No. 53-65732, and the like. Further, after bleaching or bleaching / fixing treatment, washing treatment may be carried out or only stabilizing bath treatment may be carried out. As the support used in the present invention, a transparent film such as a cellulose naphtholate film or polyethylene terephthalate, which is usually used in a photographic light-sensitive material, or a reflective support can be used. The "reflective support" used in the present invention means one that enhances the reflectivity and makes the dye image formed in the silver halide emulsion layer clear.
Such a reflective support is coated with a hydrophobic resin containing a light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, or calcium sulfate dispersed therein in order to increase the reflectance in the visible light wavelength region. And those using a hydrophobic resin containing a light-reflecting substance dispersed therein as a support. For example, baryta paper, polyethylene-coated paper, polypropylene-based synthetic paper, a transparent support provided with a reflective layer or in combination with a reflective material, such as a glass plate, polyethylene terephthalate, a polyester film such as cellulose triacetate or cellulose nitrate, There are a polyamide film, a polycarbonate film, a polystyrene film, a vinyl chloride resin and the like, and these supports can be appropriately selected depending on the purpose of use. The exposure for obtaining a photographic image may be performed using a usual method. That is, natural light (sunlight), tungsten electric lamp, fluorescent lamp, mercury lamp, xenon arc lamp,
Carbon arc lamp, xenon flash lamp, laser, LE
Any of various known light sources such as D and CRT can be used. Exposure time is 1/10 that is usually used in cameras
Exposure time from 00 seconds to 1 second, as well as exposure shorter than 1/1000 seconds, for example, 1/10 ⁴ with xenon flash lamp
Exposures of 1/10 ⁶ seconds can be used or exposures longer than 1 second can be used. The spectral composition of the light used for exposure can be adjusted with a color filter as needed. Laser light can also be used for the exposure. Further, it may be exposed by light emitted from a phosphor excited by an electron beam, X-ray, γ-ray, α-ray or the like. Examples of the present invention will be shown below, but the scope of the present invention is not limited thereto.

[0056]

【Example】

Example 1 Preparation of emulsion 30 g of gelatin and 6 g of potassium bromide were added to 1 liter of water, and potassium bromide containing an aqueous solution of silver nitrate (5 g as silver nitrate) and 0.15 g of potassium iodide was stirred in a container kept at 60 ° C. The aqueous solution was added by the double jet method over 1 minute. Further, a silver nitrate aqueous solution (145 g as silver nitrate) and a potassium bromide aqueous solution containing 4.2 g of potassium iodide were added by the double jet method. At this time, the flow rate of the addition was accelerated so that the flow rate at the end of the addition was 5 times that at the start of the addition. After the addition was completed, the soluble salts were removed at 35 ° C by the precipitation method, the temperature was raised to 40 ° C, and 75 g of gelatin was added to adjust the pH.
Was adjusted to 6.7. The obtained emulsion was tabular grains having a projected area diameter of 0.98 μm and an average thickness of 0.138 μm, and the silver iodide content was 3 mol%. Gold,
Chemical sensitization was carried out in combination with sulfur sensitization. Preparation of photographic material 101 As a surface protective layer, in addition to gelatin, an average molecular weight of 8,000
An aqueous gelatin solution containing polyacrylamide, sodium styrene sulfonate, fine particles of polymethylmethacrylate (average particle size 3.0 μm), polyethylene oxide, a hardener, etc. was used. Dye A as a sensitizing dye was added to the above emulsion at a ratio of 500 mg / 1 mol Ag, and potassium iodide was added at a ratio of 200 mg / 1 mol Ag.

[0057]

[Chemical 17]

Next, the sample 102 in which the sensitizing dye used in the sample 101 is replaced by the sensitizing dye shown in Table 1
~ 109 were created. Further, as stabilizers, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine and nitrone, dried fog Trimethylolpropane as an inhibitor, coating aid,
A photographic material was prepared by adding a hardening agent as a coating solution and coating and drying the coating solution on both sides of a polyethylene terephthalate support simultaneously with the protective layers. The coated silver amount of this photographic material is 2 g / m ² per side. Preparation of Development Processing Kit A development processing kit (concentrated liquid) consisting of the following parts (A), (B) and (C) was prepared. Part (A) For 10 liters of developing solution (use solution) Potassium hydroxide 291 g Potassium sulfite 442 g Sodium hydrogencarbonate 75 g Boric acid 10 g Diethylene glycol 120 g Ethylenediaminetetraacetic acid 17 g 5-Methylbenzotriazole 0.6 g Hydroquinone 300 g 1-phenyl-4,4 -Dimethyl-3-pyrazolidone 20 g Water was added to adjust the pH to 2.5 liters at 11.0. Part (B) For 10 liter developer (use solution) Triethylene glycol 20 g 5-Nitroindazole 2.5 g Glacial acetic acid 3 g 1-Phenyl-3-pyrazolidone 15 g Water added 250 ml Part (C) Developer (use solution) For 10 liters Glutaraldehyde 99 g Sodium metabisulfite 126 g Water was added to 250 ml Also, a starter having the following composition was prepared. Starter Glacial acetic acid 720 g Potassium bromide 300 g Water was added to prepare a 1.5-liter developer. Part (A) 2.5 liter, part (B) 250 ml, part (C) 250 ml were sequentially stirred into about 6 liters of water. While adding and dissolving, the total volume was finally adjusted to 10 liters with water. Then, a starter was added at a ratio of 20 ml to 1 liter of this working solution. Fuji F (manufactured by Fuji Photo Film Co., Ltd.) was used for fixing. For washing with water, ethylenediaminetetraacetic acid, disodium salt, dihydrate (antifungal agent)
Water containing 0.5 g / l was used. Next, development processing was carried out as follows with a roller-conveying type automatic developing machine system.

[0059]

[Table 2]

Fresh photographic sensitivity after processing (S-1 = 1
(Relative sensitivity when set to 00), 50 ° C., 80% RH, 3
Table 1 shows the sensitivity after day storage.

[0061]

[Table 3]

As shown in Table 1, the compounds of the present invention
The emulsions containing are all sensitized and have a sensitivity after aging.
It can be seen that the decrease is small. Example 2 Preparation of sample 201 Undercoated 127µm thick cellulose triacetate fill
Multi-layer color feeling consisting of each layer of the following composition on the substrate
An optical material was produced and used as a sample 201. Number is m ²Hit
Indicates the amount added. The effects of the added compounds are described
Not limited to use.

[0063] First layer: antihalation layer     Black colloidal silver 0.20g     Gelatin 1.9 g     UV absorber U-1 0.1 g     UV absorber U-3 0.04g     UV absorber U-4 0.1 g     High boiling organic solvent Oil-1 0.1 g     Microcrystalline solid dispersion of Dye E-1 0.1 g

[0064] Second layer: Middle layer     Gelatin 0.40g     Compound Cpd-C 5 mg     Compound Cpd-J 5 mg     Compound Cpd-K 3 mg     High boiling organic solvent Oil-3 0.1 g     Dye D-4 0.4mg

[0065] Third layer: Middle layer     Surface and internal fogged fine grain silver iodobromide emulsion (average       Particle size 0.06 μm, coefficient of variation 18%, AgI content 1       Mol%) Silver amount 0.05g     Gelatin 0.4 g

[0066] Fourth layer: low-sensitivity red-sensitive emulsion layer     Emulsion A Silver amount 0.1 g     Emulsion B Silver amount 0.4 g     Gelatin 0.8 g     Coupler C-1 0.15g     Coupler C-2 0.05g     Coupler C-3 0.05g     Coupler C-9 0.05g     Compound Cpd-C 10 mg     High boiling organic solvent Oil-2 0.1 g     Additive P-1 0.1 g

[0067] Fifth layer: Medium sensitivity red-sensitive emulsion layer     Emulsion B Silver amount 0.2 g     Emulsion C Silver amount 0.3 g     Gelatin 0.8 g     Coupler C-1 0.2 g     Coupler C-2 0.05g     Coupler C-3 0.2 g     High boiling organic solvent Oil-2 0.1 g     Additive P-1 0.1 g

[0068] Sixth layer: High-sensitivity red-sensitive emulsion layer     Emulsion D Silver amount 0.4 g     Gelatin 1.1 g     Coupler C-1 0.3 g     Coupler C-2 0.1 g     Coupler C-3 0.7 g     Additive P-1 0.1 g

[0069] 7th layer: Middle layer     Gelatin 0.6 g     Additive M-1 0.3 g     Anti-color mixing agent Cpd-I 2.6 mg     UV absorber U-1 0.01g     UV absorber U-2 0.002g     Ultraviolet absorber U-5 0.01g     Dye D-1 0.02g     Compound Cpd-C 5 mg     Compound Cpd-J 5 g     Compound Cpd-K 5 g     High boiling organic solvent Oil-1 0.02 g

[0070] 8th layer: Middle layer     Surface and interior fogged silver iodobromide emulsion (average grain size       0.06 μm, coefficient of variation 16%, AgI content 0.       3 mol) Silver amount 0.02g     Gelatin 1.0 g     Additive P-1 0.2 g     Color mixing inhibitor Cpd-A 0.1 g

[0071] Ninth layer: low-sensitivity green-sensitive emulsion layer     Emulsion E Silver amount 0.1 g     Emulsion F Silver amount 0.2 g     Emulsion G Silver amount 0.2 g     Gelatin 0.5 g     Coupler C-4 0.1 g     Coupler C-7 0.05g     Coupler C-8 0.20g     Compound Cpd-B 0.03 g     Compound Cpd-C 10 mg     Compound Cpd-D 0.02 g     Compound Cpd-E 0.02 g     Compound Cpd-F 0.02 g     Compound Cpd-G 0.02 g     High boiling organic solvent Oil-1 0.1 g     High boiling organic solvent Oil-2 0.1 g

[0072] 10th layer: Medium sensitivity green sensitive emulsion layer     Emulsion G Silver amount 0.3 g     Emulsion H Silver amount 0.1 g     Gelatin 0.6 g     Coupler C-4 0.1 g     Coupler C-7 0.2 g     Coupler C-8 0.1 g     Compound Cpd-B 0.03 g     Compound Cpd-D 0.02 g     Compound Cpd-E 0.02 g     Compound Cpd-F 0.05 g     Compound Cpd-G 0.05 g     High boiling organic solvent Oil-2 0.01 g

[0073] 11th layer: High sensitivity green sensitive emulsion layer     Emulsion I Silver amount 0.5 g     Gelatin 1.0 g     Coupler C-4 0.3 g     Coupler C-7 0.1 g     Coupler C-8 0.1 g     Compound Cpd-B 0.08 g     Compound Cpd-C 5 mg     Compound Cpd-D 0.02 g     Compound Cpd-E 0.02 g     Compound Cpd-F 0.02 g     Compound Cpd-G 0.02 g     Compound Cpd-J 5 mg     Compound Cpd-K 5 mg     High boiling organic solvent Oil-1 0.02 g     High boiling organic solvent Oil-2 0.02 g

[0074] 12th layer: Middle layer     Gelatin 0.6 g

[0075] 13th layer: Yellow filter layer     Yellow colloidal silver Silver amount 0.07g     Gelatin 1.1 g     Color mixing inhibitor Cpd-A 0.01 g     High boiling organic solvent Oil-1 0.01 g     Microcrystalline solid dispersion of Dye E-2 0.05 g

[0076] 14th layer: Middle layer     Gelatin 0.6 g

[0077] Fifteenth layer: low-sensitivity blue-sensitive emulsion layer     Emulsion J Silver amount 0.2 g     Emulsion K Silver amount 0.3 g     Emulsion L Silver amount 0.1 g     Gelatin 0.8 g     Coupler C-5 0.2 g     Coupler C-6 0.1 g     Coupler C-10 0.4 g

[0078] 16th layer: Medium sensitivity blue-sensitive emulsion layer     Emulsion L Silver amount 0.1 g     Emulsion M Silver amount 0.4 g     Gelatin 0.9 g     Coupler C-5 0.3 g     Coupler C-6 0.1 g     Coupler C-10 0.1 g

[0079] 17th layer: High-sensitivity blue-sensitive emulsion layer     Emulsion N Silver amount 0.4 g     Gelatin 1.2 g     Coupler C-5 0.3 g     Coupler C-6 0.6 g     Coupler C-10 0.1 g

[0080] 18th layer: 1st protective layer     Gelatin 0.7 g     UV absorber U-1 0.2 g     UV absorber U-2 0.05g     UV absorber U-5 0.3 g     Formalin Scavenger Cpd-H 0.4 g     Dye D-1 0.1 g     Dye D-2 0.05g     Dye D-3 0.1 g

[0081] 19th layer: 2nd protective layer     Colloidal silver Silver amount 0.1 mg     Fine grain silver iodobromide emulsion (average grain size 0.06 μm, AgI       Content 1 mol%) Silver content 0.1 g     Gelatin 0.4 g

[0082] 20th layer: 3rd protective layer     Gelatin 0.4 g     Polymethylmethacrylate (average particle size 1.5 μm) 0.1 g     Methyl methacrylate and acrylic acid 4: 6       Copolymer (average particle size 1.5 μm) 0.1 g     Silicone oil 0.03g     Surfactant W-1 3.0 mg     Surfactant W-2 0.03g

In addition to the above composition, additives F-1 to F-8 were added to all emulsion layers. In addition to the above composition, gelatin hardener H-1 and coating and emulsifying surfactants W-3, W-4, W-5 and W-6 were added to each layer. Further, phenol, 1,2-benzisothiazotan-3-one, 2-phenoxyethanol and phenethyl alcohol were added as antiseptic and antifungal agents.

[0084]

[Table 4]

[0085]

[Table 5]

[0086]

[Table 6]

[0087]

[Chemical 18]

[0088]

[Chemical 19]

[0089]

[Chemical 20]

[0090]

[Chemical 21]

[0091]

[Chemical formula 22]

[0092]

[Chemical formula 23]

[0093]

[Chemical formula 24]

[0094]

[Chemical 25]

[0095]

[Chemical formula 26]

[0096]

[Chemical 27]

[0097]

[Chemical 28]

[0098]

[Chemical 29]

[0099]

[Chemical 30]

[0100]

[Chemical 31]

Preparation of Samples 202 to 217 Sensitizing dye S of emulsions E to G used in Sample 201
-202 by replacing -3 as shown in Table 2
09 was created. The sample piece thus obtained was
After performing white exposure through a gray wedge with an exposure time of / 100 seconds and an exposure amount of 20 CMS, sensitometry was performed by the following processing steps.

[0102]

[Table 7]

[0103] Treatment process time Temperature First development 6 minutes 38 ° C Washing with water 2 minutes 38 ° C Inversion 2 minutes 38 ℃ Color development 6 minutes 38 ℃ Adjustment 2 minutes 38 ℃ Bleach 6 minutes 38 ℃ Stationary 4 minutes 38 ℃ Washing with water 4 minutes 38 ° C Stability 1 minute 25 ℃

The composition of each processing liquid was as follows. [First developer]     Nitrilo-N, N, N-trimethylenephosphonic acid-5 nato       Lithium salt 2.0g     Sodium sulfite 30g     Hydroquinone / potassium monosulfonate 20g     33 g of potassium carbonate     1-phenyl-4-methyl-4-hydroxymethyl-3-       Pyrazolidone 2.0g     2.5 g potassium bromide     Potassium thiocyanate 1.2g     2.0 mg of potassium iodide     Add 1000 ml of water       pH 9.60       The pH was adjusted with hydrochloric acid or potassium hydroxide.

[0105] [Reversal liquid]     Nitrilo-N, N, N-trimethylenephosphonic acid-5 nato       Lithium salt 3.0g     Stannous chloride / dihydrate 1.0 g     p-aminophenol 0.1 g     Sodium hydroxide 8g     Glacial acetic acid 15 ml     Add 1000 ml of water       pH 6.00       The pH was adjusted with hydrochloric acid or potassium hydroxide.

[0106] [Color developer]     Nitrilo-N, N, N-trimethylenephosphonic acid-5 nato       Lithium salt 2.0g     Sodium sulfite 7.0 g     Trisodium phosphate dodecahydrate 36g     Potassium bromide 1.0g     90 mg of potassium iodide     Sodium hydroxide 3.0g     Citrazinic acid 1.5g     N-ethyl- (β-methanesulfonamidoethyl) 3-methyl       Ru-4-aminoaniline sulfate 11g     1.0 g of 3,6-dithiaoctane-1,8-diol     Add 1000 ml of water       pH 11.80       The pH was adjusted with hydrochloric acid or potassium hydroxide.

[0107] [Preparation liquid]     Ethylenediaminetetraacetic acid ・ sodium salt ・ dihydrate 8.0 g     Sodium sulfite 12g     1-thioglycerin 0.4 ml     Add 1000 ml of water       pH 6.20       The pH was adjusted with hydrochloric acid or sodium hydroxide.

[0108] [Bleaching solution]     Ethylenediamine tetraacetic acid / disodium salt / dihydrate 2.0 g     Ethylenediaminetetraacetic acid / Fe (III) / Ammonium / dihydrate 120g     100 g potassium bromide     Ammonium nitrate 10g     Add 1000 ml of water       pH 5.70       The pH was adjusted with hydrochloric acid or sodium hydroxide.

[0109] [Fixer]     Ammonium thiosulfate 80g     Sodium sulfite 5.0g     Sodium bisulfite 5.0g     Add 1000 ml of water       pH 6.60       The pH was adjusted with hydrochloric acid or aqueous ammonia.

[Stabilizer] Formalin (37%) 5.0 ml Polyoxyethylene-p-monononyl 0.5 ml Phenyl ether (average degree of polymerization 10) 1000 ml by adding water pH not adjusted Table 3 below. The evaluation results of sensitometry and residual color are shown in FIG. The relative sensitivity was compared on the basis of the relative exposure amount from the minimum density to the density 1.0 higher.

[0111]

[Table 8]

As is clear from the results shown in Table 3, the use of the compounds and emulsions of the present invention makes it possible to obtain a light-sensitive material having high GL sensitivity and less deterioration in sensitivity over time.

Example 3 On a subbed cellulose triacetate film support,
A sample 301, which is a multi-layer color light-sensitive material composed of layers having the following compositions, was prepared. The amount coated amount (Composition of photosensitive layer) is represented in units of g / m ² of silver for silver halide and colloidal silver, also couplers, the amount for the additives and gelatin, expressed in units of g / m ^2, The sensitizing dye is shown by the number of moles per mole of silver halide in the same layer.

First Layer (Antihalation Layer) Black Colloidal Silver 0.15 Gelatin 1.90 ExM-1 5.0 × 10 ⁻³

Second Layer (Intermediate Layer) Gelatin 2.10 UV-1 3.0 × 10 ^-2 UV-2 6.0 × 10 ^-2 UV-3 7.0 × 10 ^-2 ExF-1 4.0 × 10 ^-3 Solv-2 7.0 × 10 ^-2

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide emulsion (Agl 2 mol%, internal high Agl type, sphere equivalent diameter 0.3 μm, variation coefficient of sphere equivalent diameter 29%, normal crystal, twin Crystal mixed particles, diameter / thickness ratio 2.5) Silver coating amount 0.50 Gelatin 1.50 ExS-10 4.1 × 10 ^-4 ExC-1 0.11 ExC-3 0.11 ExC-4 3.0 × 10 ^-2 ExC-7 1.0 × 10 ^-2 Solv-1 7.0 × 10 ^-3

Fourth Layer (Medium-Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide emulsion (Agl 4 mol%, internal high Agl type, sphere equivalent diameter 0.5 5 μm, variation coefficient of sphere equivalent diameter 20%, normal crystal, twin Crystal mixed particles, diameter / thickness ratio 1.0) Silver coating amount 0.85 Gelatin 2.00 ExS-10 4.1 × 10 ^-4 ExC-1 0.16 ExC-2 8.0 × 10 ^-2 ExC -3 0.17 ExC-7 1.5 × 10 -2 ExY-1 2.0 × 10 -2 ExY-2 1.0 × 10 -2 Cpd-10 1.0 × 10 -4 Solv-1 0. 10

Fifth Layer (High Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide emulsion (Agl 10 mol%, internal high Agl type, spherical equivalent diameter 0.7 μm, variation coefficient of spherical equivalent diameter 30%, twin mixed particles, Diameter / thickness ratio 2.0) Silver coating amount 0.70 Gelatin 1.60 ExS-10 4.1 × 10 ⁻⁴ ExC-5 7.0 × 10 ⁻² ExC-6 8.0 × 10 ⁻² ExC− 7 1.5 × 10 ^-2 Solv-1 0.15 Solv-2 8.0 × 10 ^-2

Sixth Layer (Intermediate Layer) Gelatin 1.10 P-2 0.17 Cpd-1 0.10 Cpd-4 0.17 Solv-1 5.0 × 10 ^-2

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide emulsion (Agl 2 mol%, internal high Agl type, sphere equivalent diameter 0.3 μm, variation coefficient of sphere equivalent diameter 28%, normal crystal, twin Crystal mixed particles, diameter / thickness ratio 2.5) Silver coating amount 0.30 Gelatin 0.50 ExS-1 5.0 × 10 ^-4 ExS-5 2.0 × 10 ^-4 ExS-2 0.3 × 10 ^{-4 ExM-1 3.0 × 10 -2} ExM-2 0.20 ExY-1 3.0 × 10 -2 Cpd-11 7.0 × 10 -3 Solv-1 0.20

Eighth Layer (Medium-Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide emulsion (Agl 4 mol%, internal high Agl type, sphere equivalent diameter 0.5 5 μm, variation coefficient of sphere equivalent diameter 20%, normal crystal, twin Crystal mixed particles, diameter / thickness ratio 4.0) Silver coating amount 0.70 Gelatin 1.00 ExS-1 5.0 × 10 ^-4 ExS-5 2.0 × 10 ^-4 ExS-2 3.0 × 10 ⁻⁵ ExM-1 3.0 × 10 ⁻² ExM-2 0.25 ExM-3 1.5 × 10 ⁻² ExY-1 4.0 × 10 ⁻² Cpd-11 9.0 × 10 ⁻³ Solv -1 0.20

Ninth Layer (High-Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide emulsion (Agl10 mol%, internal high Agl type, sphere equivalent diameter 0.7 μm, variation coefficient of sphere equivalent diameter 30%, normal crystal, twin crystal) mixed particles, diameter / thickness ratio 2.0) silver coverage 0.50 gelatin ^{0.90 ExS-1 2.0 × 10 -4} ExS-5 2.0 × 10 -4 ExS-2 2.0 × 10 - ⁵ ExS-7 3.0 × 10 ⁻⁴ ExM-1 1.0 × 10 ⁻² ExM-4 3.9 × 10 ⁻² ExM-5 2.6 × 10 ⁻² Cpd-2 1.0 × 10 ^{− 2} Cpd-9 2.0x10 ^-4 Cpd-10 2.0x10 ^-4 Solv-1 0.20 Solv-2 5.0x10 ^-2

10th layer (yellow filter layer) Gelatin 0.90 Yellow colloid 5.0 × 10 ^-2 Cpd-1 0.20 Solv-1 0.15

Eleventh Layer (Low Sensitivity Blue Sensitive Emulsion Layer) Silver iodobromide emulsion (Agl 4 mol%, internal high Agl type, sphere equivalent diameter 0.5 5 μm, variation coefficient of sphere equivalent diameter 15%, octahedral grains) Silver coating amount 0.40 Gelatin 1.00 ExS-4 2.0 × 10 ^-4 ExY-1 9.0 × 10 ^-2 ExY-3 0.90 Cpd-2 1.0 × 10 ^-2 Solv-10 .30

Twelfth layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (Agl10 mol%, internal high Agl type, sphere equivalent diameter 1.3 μm, variation coefficient of sphere equivalent diameter 25%, normal crystal, twin crystal Mixed particles, diameter / thickness ratio 4.5) Silver coating amount 0.50 Gelatin 0.60 ExS-4 1.0x10 ^-4 ExY-3 0.12 Cpd-2 1.0x10 ^-3 Solv-1 4.0 x 10 ^-2

Thirteenth Layer (First Protective Layer) Fine grain silver iodobromide (average particle size 0.07 μm, Ag1 mol%) 0.20 gelatin 0.80 UV-2 0.10 UV-3 0.10 UV- 4 0.20 Solv-3 4.0 x 10 ^-2 P-2 9.0 x 10 ^-2

14th layer (second protective layer) Gelatin 0.90 B-1 (diameter 1.5 μm) 0.10 B-2 (diameter 1.5 μm) 0.10 B-3 2.0 × 10 ^-2 H-1 0.40

Furthermore, storability, processability, pressure resistance, anti-mold and
The following Cpd-3, Cpd-5, Cpd-6, and Cpd- are used to improve antibacterial / antistatic properties and applicability.
7, Cpd-8, P-1, W-1, W-2, W-3 were added. In addition to the above, n-butyl-p-hydroxybenzoate was added. Furthermore, B-4, F-1, F-
4, F-5, F-6, F-7, F-8, F-9, F-1
0, F-11, and iron salt, lead salt, gold salt, platinum salt, iridium salt, and rhodium salt. Next, the chemical structural formulas or chemical names of the compounds used in the present invention are shown below.

[0129]

[Chemical 32]

[0130]

[Chemical 33]

[0131]

[Chemical 34]

[0132]

[Chemical 35]

[0133]

[Chemical 36]

[0134]

[Chemical 37]

[0135]

[Chemical 38]

[0136]

[Chemical Formula 39]

[0137]

[Chemical 40]

[0138]

[Chemical 41]

[0139]

[Chemical 42]

[0140]

[Chemical 43]

[0141]

[Chemical 44]

[0142]

[Chemical formula 45]

Preparation of Samples 302 to 312 Samples 302 to 310 were prepared by the same preparation procedure except that ExS-10 was replaced with the combination of sensitizing dyes shown in Table 4.

[0144]

[Table 9]

Samples 301 to 310 were exposed to a white wedge at 50 CMS for 1/100 second, and after the following treatment, sensitometry was performed. As a result, it was revealed that the present invention has high green sensitivity and excellent storability as in Example 2.

(Processing method) Process processing time processing temperature replenishment amount tank capacity color development 3 minutes 15 seconds 37.8 ° C 25 ml 10 liters bleaching 45 seconds 38 ° C 5 ml 4 liters bleach-fixing (1) 45 seconds 38 ° C-4 liters Bleach-fixing (2) 45 seconds 38 ° C 30 ml 4 liters Washing with water (1) 20 seconds 38 ° C-2 liters Washing with water (2) 20 seconds 38 ° C 30 mls 2 liters Stability 20 seconds 38 ° C 20 mls 2 liters Drying 1 minute 55 ℃ * Replenishment amount is 35mm width 1m per length. Each step of bleach-fixing and washing is from (2) to (1).
And the overflow of the bleaching solution was all introduced into the bleach-fixing (2). In the above processing, the amount of the bleach-fixing solution brought into the washing step was 2 ml per 1 m length of the light-sensitive material having a width of 35 m / m.

The composition of the processing liquid is shown below. (Color developer) Mother liquor (g) Replenisher (g)     Diethylenetriamine pentaacetic acid 5.0 6.0     Sodium sulfite 4.0 5.0     Potassium carbonate 30.0 37.0     Potassium bromide 1.3 0.5     Potassium iodide 1.2 mg −     Hydroxylamine sulfate 2.0 3.6     4- [N-ethyl-N-β-hydroxyethyl       Emino] -2-methylaniline sulfate 4.7 6.2     1.0 liter with water added 1.0 liter     pH 10.00 10.15

[0148] (Bleach) Mother liquor (g) Replenisher (g)     1,3-Diaminopropanetetraacetic acid ferric ammo       N-monohydrate 144.0 206.0     1,3-Diaminopropanetetraacetic acid 2.8 4.0     Ammonium bromide 84.0 120.0     Ammonium nitrate 17.5 25.0     Ammonia water (27%) 10.0 1.8     Acetic acid (98%) 51.1 73.0     1.0 liter with water added 1.0 liter     pH 4.3 3.4

[0149] (Bleach-fixer) Mother liquor (g) Replenisher (g)     Ethylenediaminetetraacetic acid ferric ammonium chloride       Water salt 50.0 −     Ethylenediaminetetraacetic acid disodium salt 5.0 25.0     Ammonium sulfite 12.0 20.0     Ammonium thiosulfate aqueous solution (700 g / liter)                                    290.0 ml 320.0 ml     Ammonia water (27%) 6.0 ml 15.0 ml     1.0 liter with water added 1.0 liter     pH 6.8 8.0

(Washing liquid) Mother liquor and replenisher common tap water were mixed with H type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas Co.) and OH type anion exchange resin (Amberlite IR-400). Water was passed through the packed mixed-bed column to adjust the concentration of calcium and magnesium ions to 3 mg / liter or less, and subsequently, 20 mg / liter of sodium isocyanurate dichloride and 150 mg / liter of sodium sulfate were added. The pH of this liquid was in the range of 6.5 to 7.5.

(Stabilizer) Common to mother liquor and replenisher (Unit: g) Formalin (37%) 1.2 ml Surfactant [C ₁₀ H ₂₁ -O- (CH ₂ CH ₂ O) ₁₀ -H] 0.4 Ethylene glycol 1.0 Water Add 1.0 liter pH 5.0-7.0

Example 4 Preparation of Sample 401 A color photographic light-sensitive material was prepared by coating the following first to twelfth layers in multilayer on a paper support laminated on both sides with polyethylene. 15% by weight on the coated side of the first layer of polyethylene
Of anatase type titanium oxide as a white pigment and a trace amount of ultramarine as a bluish dye. (Photosensitive layer composition) The components and the coating amounts shown in g / m ² are shown below. For silver halide, the coating amount in terms of silver is shown. 1st layer (gelatin layer) Gelatin ... 1.30 2nd layer (antihalation layer) Black colloidal silver ... 0.10 Gelatin ... 0.70 3rd layer (low sensitivity red sensitive layer) Red increase Silver chloroiodobromide spectrally sensitized with a dye (ExS-3) (1 mol% silver chloride, 4 mol% silver iodide, average grain size 0.3 µ, grain size distribution 10%, cube, core Iodine type core / shell) 0.06 Silver iodobromide spectrally sensitized with a red sensitizing dye (ExS-3) (silver iodide 4 mol%, average grain size 0.5 μ, grain size distribution 15%) , Cube) 0.10 Gelatin 1.00 Cyan coupler (ExC-1) 0.14 Cyan coupler (ExC-2) 0.07 Anti-fading agent (Cpd-2, 0.14 Coupler dispersion medium (Cpd-6) .... 0. 3 Coupler solvent (Solv-1, 2, 3 equivalents) …… 0.06 Development accelerator (Cpd-13) …… 0.05 Fourth layer (high sensitivity red sensitive layer) Red sensitizing dye (ExS Silver iodobromide spectrally sensitized in (3) (6 mol% silver iodide, average grain size 0.8 μ, grain size distribution 20%, flat plate (aspect ratio = 8, core iodine)) .... 0.15 Gelatin ...... 1.00 Cyan coupler (ExC-1) ...... 0.20 Cyan coupler (ExC-2) ...... 0.10 Anti-fading agent (Cpd-2, 3, 4 equivalents) ………… 0.15 Coupler dispersion medium (Cpd-6) ………… 0.03 Coupler solvent (Solv-1, 2, 3 equivalents) …… 0.10 Fifth layer (intermediate layer) Magenta colloidal silver …… …… 0.02 Gelatin ………… 1.00 Anti-fading agent (Cpd-7, 16) ……. 8 Anti-fading agent solvent (Solv-4, 5) ... 0.16 Polymer latex (Cpd-8) ... 0.10 Sixth layer (low-sensitivity green-sensitive layer) Green sensitizing dye (ExS-1, Silver chloroiodobromide spectrally sensitized in 2) (1 mol% silver chloride, 2.5 mol% silver iodide, average grain size 0.28 μ, grain size distribution 8%, cubic, core iodide core shell ) ... 0.04 Silver iodobromide spectrally sensitized with a green sensitizing dye (ExS-1, 2) (2.5 mol% silver iodide, average particle size 0.48 µ, particle size distribution 12) %, Cube) 0.06 Gelatin 0.80 Magenta coupler (ExM-1, 2 equivalents) 0.10 Anti-fading agent (Cpd-9) 0.10 Stin prevention Agent (Cpd-10, 11 equivalents) ………… 0.01 Stin inhibitor (Cpd-5) …… 0.001 Anti-stin agent (Cpd-12) ... 0.01 Coupler dispersion medium (Cpd-6) ... 0.05 Coupler solvent (Solv-4, 6) ... 0.15 7th layer ( High-sensitivity green-sensitive layer) Silver iodobromide spectrally sensitized with a green sensitizing dye (ExS-1, 2) (3.5 mol% silver iodide, average grain size 1.0 µ, grain size distribution 21%, Flat plate (aspect ratio = 9, uniform iodine type) ... 0.10 Gelatin ... 0.80 Magenta coupler (ExM-1, 2 equivalents) 0.10 Anti-fading agent (Cpd-9) ) ... 0.10 Anti-staining agent (Cpd-10, 11, 22 equivalents) ... 0.01 Anti-staining agent (Cpd-5) ... 0.001 Anti-staining agent (Cpd-12) ... …… 0.01 Coupler dispersion medium (Cpd-6) ……… 0.05 Solvent (Solv-4, 6) 0.15 Eighth layer (yellow filter layer) Yellow colloidal silver 0.20 Gelatin 1.00 Anti-fading agent (Cpd-7) 0.06 Anti-fading solvent (Solv-4, 5) ...... 0.15 Polymer latex (Cpd-8) ...... 0.10 9th layer (low sensitivity blue sensitive layer) Blue sensitizing dye (ExS- 4,5) spectrally sensitized with silver chloroiodobromide (silver chloride 2 mol%, silver iodide 2.5 mol%, average grain size 0.38μ, grain size distribution 8%, cubic, core iodine Type core shell)) ... 0.07 Silver iodobromide spectrally sensitized with a blue sensitizing dye (ExS-4, 5) (2.5 mol% silver iodide, average grain size 0.55 μ, grain size) Distribution 11%, cube) ………… 0.10 Gelatin ………… 0.50 Yellow cover Ra (ExY-1, 2 equivalents) 0.20 Anti-staining agent (Cpd-5) 0.001 Anti-fading agent (Cpd-14) 0.10 Coupler dispersion medium (Cpd-) 6) ...... 0.05 Coupler solvent (Solv-2) 0.05 Tenth layer (high-sensitivity blue-sensitive layer) Silver iodobromide spectrally sensitized with a blue sensitizing dye (ExS-4, 5) ( Silver iodide 2.5 mol%, average particle size 1.4 μ, particle size distribution 21%, flat plate (aspect ratio = 14)) 0.25 gelatin 1.00 yellow coupler (ExY-1, ExY-1, 0.40 Anti-staining agent (Cpd-5) 0.002 Anti-fading agent (Cpd-14) 0.10 Coupler dispersion medium (Cpd-6) 0 .15 Coupler solvent (Splv-2) ... 0.10 11th layer ( Outer line absorption layer) Gelatin 1.50 UV absorber (Cpd-1, 2, 4, 15 equivalents) 1.00 Anti-fading agent (Cpd-7, 16) 0.06 Dispersion Medium (Cpd-6) ... 0.10 UV absorber solvent (Solv-1, 2) ... 0.15 Anti-irradiation dye (Cpd-17, 18) ... 0.02 Anti-irradiation dye (Cpd-19, 20) ..... 0.02 12th layer (protective layer) Fine grained silver chlorobromide (97 mol% of silver chloride, average size 0.2 µ) ... 0.07 Modified Poval ...... 0 .02 Gelatin ... 1.50 Gelatin hardening agent (H-1, 2 equivalents) 0.17 Further, in each layer, alkanol XC (D
upont) and sodium alkylbenzenesulfonate as succinate and Magefac as coating aids.
F-120 (manufactured by Dainippon Ink and Chemicals, Inc.) was used. For the layer containing silver halide or colloidal silver, a stabilizer (Cpd-
21, 22, 23) was used. The compounds used in the examples are shown below.

[0153]

[Chemical formula 46]

[0154]

[Chemical 47]

[0155]

[Chemical 48]

[0156]

[Chemical 49]

[0157]

[Chemical 50]

[0158]

[Chemical 51]

[0159]

[Chemical 52]

[0160]

[Chemical 53]

[0161]

[Chemical 54]

[0162]

[Chemical 55]

The sensitizing dye ExS-1 of Sample 401 was replaced with the same combination of sensitizing dyes as in Example 3 and white wedge exposure was carried out, and then the following processing was carried out and the same evaluation as in Examples 2 and 3 was carried out. As a result, it was found that the same effect as in Examples 2 and 3 was obtained. <Processing Step> First development (black and white development) 38 ° C. 75 seconds Water washing 38 ° C. 90 seconds Reverse exposure 100 lux or more 60 seconds or more Color development 38 ° C. 135 seconds Water washing 38 ° C. 45 seconds Bleach fixing 38 ° C. 120 seconds Water washing 38 ℃ 135 seconds Dry 60 ℃ 1 minute <Processing solution composition> (First developer) Nitrilo-N, N, N-trimethylenephosphonic acid penta sodium salt 0.6 g Diethylenetriamine pentaacetic acid pentasodium salt 4.0 g Potassium sulfite 30.0 g Potassium thiocyanate 1.2 g Potassium carbonate 35.0 g Hydroquinone monosulfonate / potassium salt 25.0 g Diethylene glycol 15.0 ml 1-Phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 2.0 g Odor Potassium iodide 0.5 g Potassium iodide 5.0 mg Water was added to 1 liter (pH 9.7). ) (Color developer) Benzyl alcohol 15.0 ml Diethylene glycol 12.0 ml 3,6-Dithia-1,8-octanediol 0.2 g Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 0.5 g Diethylenetriamine pentaacetic acid pentasodium salt 2.0 g Sodium sulfite 2.0 g Potassium carbonate 25.0 g Hydroxylamine sulfate 3.0 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-amino Aniline sulfate 5.0 g Potassium bromide 0.5 g Potassium iodide 1.0 mg Water was added to 1 liter (pH 10.40) (bleach-fixing solution) 2-mercapto-1,3,4-triazole 1.0 g Ethylenediamine tetra Acetic acid / Disodium / Dihydrate 5.0 g Ethylenediaminetetraacetic acid / Fe (III) / A Moniumu monohydrate 80.0g sodium 15.0g Sodium thiosulfate sulfite (700 g / l solution) added 160.0ml glacial acetic acid 5.0ml water 1 liter (PH6.50)

[0164]

As described in detail above, according to the present invention, it is possible to obtain the effects of enhancing the green sensitivity and suppressing the deterioration of the sensitivity of the photographic light-sensitive material during storage.

Continuation of the front page (56) Reference JP-A-62-128941 (JP, A) JP-A-4-138450 (JP, A) JP-A-4-21842 (JP, A) JP-A-6-230500 (JP , A) JP-A-6-230501 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03C 1/18 CA (STN)

Claims (6)

(57) [Claims] 1. A compound containing a compound represented by the following general formula (I):
Silver halide containing at least one kind
Photographic material. General formula (I) [Chemical 1] R in the general formula (I)₁₁And R₁₂Are each alkyl
Represents a group. R₁₃Is a hydrogen atom, an alkyl group or an aryl group
Represents V₁, V₂, V₃, V_Four, V_Five, V₆, V₇, V₈, V ₉, V_Ten,
V₁₁And W₀₁Each represents a hydrogen atom or a substituent, V
₇And V₁₁At least one of them is a substituent. X₁
Represents a charge-balancing counterion and m neutralizes the charge in the molecule.
It is a number greater than or equal to 0 that is required to make it. 2. A silver halide photographic light-sensitive material containing at least one compound represented by the following general formula (II). General formula (II) In the general formula (II), R ₂₁ and R ₂₂ each represent an alkyl group. R ₂₃ represents a hydrogen atom, an alkyl group or an aryl group. X ₂ represents a charge balancing counter ion, and n is a number of 0 or more necessary for neutralizing the charge in the molecule.
V _4A , V _5A , V _6A and W ₀₂ each represent a hydrogen atom or a substituent, and W ₂₁ represents a substituent having 2 or more carbon atoms. 3. A compound represented by the following general formula (III)
Silver halide containing at least one kind
Photographic material. General formula (III) [Chemical 3] R in the general formula (III)₁₁And R₁₂Are each alkyl
Represents a group. R₁₃Is a hydrogen atom, an alkyl group or an aryl group
Represents V₁, V₂, V₃, V_Four, V_Five, V₆, V₇, V₈, V ₉, V_Ten,
V₁₁, V₁₂, V₁₃, V₁₄, V₁₅And V₁₆Are each hydrogen
Represents an atom or a substituent, V₇And V₁₁At least of
One is a substituent, V₁₂And V₁₆At least one of
One is a substituent. X₁Represents a charge-balancing counterion, m
Is a number of 0 or more required to neutralize the charge in the molecule.
It 4. A silver halide photographic light-sensitive material containing at least one compound represented by the following general formula (IV). General formula (IV): In the general formula (IV), R ₂₁ and R ₂₂ each represent an alkyl group. R ₂₃ represents a hydrogen atom, an alkyl group or an aryl group. X ₂ represents a charge balancing counter ion, and n is a number of 0 or more necessary for neutralizing the charge in the molecule. W ₂₁
And W ₂₂ each represent a substituent, and at least one of W ₂₁ and W ₂₂ represents a substituent having 2 or more carbon atoms. 5. A compound represented by the general formula (III) according to claim 3. 6. A compound represented by the general formula (IV) according to claim 4.