JPH0980672A - Manufacture of silver halide emulsion, and silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To perform a quick processing, increase the sensitivity, reduce the fogging, and enhance the color residual property by adding a spectral sensitizing pigment before the addition of a chemical sensitizer, and adding an azaindene compound in two installments before and after the addition of the chemical sensitizer. SOLUTION: A spectral sensitizing pigment is added in an amount of 50mg-500mg per mole of silver halide before the addition of a chemical sensitizer, and an azaindene compound is added in two installments before and after the addition of the chemical sensitizer. In this case, the spectral sensitizing pigment is dispersed into solid fine grains, and added. The chemical sensitizer is formed of selenium compound or tellurium compound. Further, the chemical sensitizer is formed of gold compound and selenium compound or tellurium compound. The kind of the spectral sensitizing pigment used therein is not particularly limited, and any photographic spectral sensitizing pigment can be optionally used.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-sensitivity silver halide photographic light-sensitive material having no residual color stain after processing.

[0002]

2. Description of the Related Art In recent years, the processing time has been greatly shortened due to the rapid progress of high temperature in the field of X-ray photographic light-sensitive materials. As a result, demands for improvement in developability, fixability, and dryness of silver halide photographic light-sensitive materials are increasing.

On the other hand, when the treatment is speeded up, a dye residue may occur. Attempts have been made to reduce the amount of the dye in order to improve the residual color, but the sensitivity is remarkably lowered and the fog is increased.

Generally, a tetrazaindene compound is often used for the purpose of suppressing fog. In addition, Japanese Patent Fair 5-1
Often used as a stabilizer to stop chemical sensitization, as described in the 4888 Examples. Japanese Patent Application Laid-Open No. 4-166928 discloses a method of adding a spectral sensitizing dye and an azaindene compound before chemical sensitization to improve the residual color property without deteriorating fog and sensitivity. However, recently, the processing has been further speeded up, and at the same time, the activity of the development processing solution has been increased. Under such circumstances, a silver halide photographic light-sensitive material having less residual color, high sensitivity and low fog has been required.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide light-sensitive material suitable for rapid processing, having high sensitivity, low fog and good residual color.

[0006]

The above object of the present invention is attained by the following constitutions.

1) 50 to 500 mg of the spectral sensitizing dye is added per mol of silver halide before the addition of the chemical sensitizer, and the azaindene compound is added before and after the addition of the chemical sensitizer. A method for producing a silver halide emulsion, which is added in portions.

2) The method for producing a silver halide emulsion as described in 1 above, wherein the spectral sensitizing dye is dispersed and added to solid fine particles.

3) The method for producing a silver halide emulsion as described in 1 or 2 above, wherein the chemical sensitizer is a selenium compound or a tellurium compound.

4) The method for producing a silver halide emulsion as described in 1 or 2 above, wherein the chemical sensitizer is a gold compound and a selenium compound or a tellurium compound.

5) The chemical sensitizer is a gold compound and a selenium compound or a tellurium compound, and the thiocyanate compound is 4.5 × 10 ^-4 mol or more and 1.8 × 10 ^-3 mol / mol of silver halide. 3. The method for producing a silver halide emulsion as described in 1 or 2 above, wherein the content is at most mol.

6) The silver halide according to any one of 1 to 5 above, wherein the spectral sensitizing dye is a compound represented by the following general formula (A) or general formula (B). Emulsion manufacturing method.

[0013]

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In the formula, R ¹ and R ³ each represent a substituted or unsubstituted alkyl group, at least one of R ¹ and R ³ is a group other than an ethyl group, and R ² and R 3 ⁴ represents a lower alkyl group, and at least one of R ² and R ⁴ represents an alkyl group substituted with a hydrophilic group. V ¹ ,
V ² , V ³ and V ⁴ each represent a hydrogen atom or a substitutable group in which the sum of the added Hammett σp values is less than 1.7, and V ¹ , V ² , V ³ and V ⁴ are hydrogen at the same time. It cannot be an atom or a chlorine atom.

X ¹ represents an ion necessary for neutralizing the charge in the molecule, and n represents 1 or 2. However, when an inner salt is formed, n is 1.

[0016]

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In the formula, R ⁵ and R ⁶ each represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, and at least one of R ⁵ and R ⁶ Is a sulfoalkyl group or a carboxyalkyl group.

R ⁷ represents a hydrogen atom, an alkyl group or an aryl group. Z ¹ and Z ² each represent a non-metal atom group necessary for completing a benzene ring or a naphtho ring which may have a substituent. X ² represents an ion necessary for neutralizing the charge in the molecule, and m represents 1 or 2. However, m is 1 when forming an intramolecular salt.

7) The division ratio of the azaindene compound (weight ratio before addition of chemical sensitizer: weight ratio after addition of chemical sensitizer) is 1: 2 to 1: 100, wherein the above 1 to 6 are characterized.
A method for producing a silver halide emulsion according to any one of 1.

8) The addition amount of the azainde compound added before the addition of the chemical sensitizer is 15 mg to 500 mg per mol of silver halide.
8. The method for producing a silver halide emulsion according to any one of items 7 to 7.

9) A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein the silver halide emulsion is the silver halide emulsion according to any one of 1 to 8 above. A silver halide photographic light-sensitive material, which is a silver halide emulsion produced by the production method.

10) The silver halide photographic light-sensitive material as described in 9 above, wherein the amount of the spectral sensitizing dye per one surface of the silver halide photographic light-sensitive material is ² to 7 mg / m ² .

The present invention will be described in detail below. The type of the spectral sensitizing dye used in the present invention is not particularly limited, and any spectral sensitizing dye for photographic use can be used, but a preferable spectral sensitizing dye is represented by the general formula (A). )
Alternatively, it is a compound represented by the general formula (B). In the present invention, the spectral sensitizing dye is 1 μm or less, preferably 0.01 μm or less.
It is preferable to add it to the photosensitive silver halide emulsion after dispersing it in the form of solid fine particles of 1 to 1 μm.

Specific examples of the spectral sensitizing dye represented by the general formula (A) will be given below.

[0025]

[Table 1]

[0026]

[Table 2]

Next, the above general formula (B) used in the present invention.
Specific examples of the spectral sensitizing dye represented by

[0028]

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[0029]

[Chemical 6]

The sensitizing dye represented by the above general formula (A) or (B) used in the present invention is F.I. M. Hamer "H
etherocycle compounds Cy
aninedyes and related com
pounds "(heterocyclic compounds-
Cyanine soybean and related compounds)
IV. V. VI, pp. 89-199 John Wiley
& Sons (New York, London) 1
964, or D.I. M. "Hete" by Sturmer
rocyclic compounds compound speci
al topics in Heterocycle
c chemistry ”(Heterocyclic Compounds-Special Topics in Heterocyclic Chemistry), Chapter VIII, IV. 482-515, John Wiley & Sons (New Yo)
rk, London) 1977 and the like.

It should be noted that each of the above general formulas (A) and (B) merely shows one state of the resonance structure, and even if it is expressed in the limit state where the + charge enters the symmetrical heterocyclic nitrogen atom. It means the same substance.

The addition amount of the spectral sensitizing dye in the present invention is
Type of dye and structure, composition, ripening condition of silver halide,
Depending on the purpose and use, etc., the monolayer coverage of each photosensitive grain in the silver halide emulsion is 40% or more 90
% Or less, preferably 50% to
80% is particularly preferred.

In the present invention, the monolayer coverage is 5
The saturated adsorption amount when the adsorption isotherm is created at 0 ° C. is relatively determined as the amount corresponding to 100% coverage.

The appropriate amount per mol of silver halide varies depending on the total surface area of silver halide grains in the emulsion, but is 6
Less than 00 mg is preferred. Further, it is preferably 450 mg or less.

In the present invention, a method for obtaining a solid dispersion liquid of a spectral sensitizing dye is, for example, JP-A-2-23330.
No. 2, No. 2-23331, No. 2-23332, No. 2-
A method of adding and dispersing an organic solvent and / or a surfactant as described in JP-A-135437 and JP-A-2-135438 may be used, but in the present invention, JP-A-5-927964
As described in No. 4, the solubility at 27 ° C. in an aqueous system substantially free of an organic solvent and / or a surfactant is 2
The most preferable method is to use a spectral sensitizing dye having a concentration of × 10 ^-4 to 4 × 10 ^-2 mol / liter by mechanically dispersing it in solid fine particles of 1 µm or less by adding an amount exceeding the solubility.

The solubility of the spectral sensitizing dye in the present invention in water is preferably 2 × 10 ⁻⁴ to 4 × 10 ⁻² mol / liter, more preferably 1 × 10 ⁻³ to 4 × 10 ⁻² mol / liter. is there.

When the solubility is lower than this range, the dispersion particle size becomes very large and the dispersion becomes non-uniform so that a precipitate of the dispersion may be formed after the dispersion is completed or the dispersion may be added to the silver halide emulsion. Sometimes it interferes with the adsorption process of dyes to silver halide.

On the other hand, when the solubility is higher than the above range, the viscosity of the dispersion is increased more than necessary, air bubbles are entrapped, and the dispersion is hindered. At higher solubility, dispersion becomes impossible. It became clear from the study of the present inventors.

A method for measuring the solubility of the spectral sensitizing dye in water and the particle size of the solid dispersed dye is described in JP-A-5-297496.
Can be used.

The selenium compound of the present invention will be described. As the selenium compound of the present invention, the selenium compounds disclosed in conventionally known patents can be used. That is, the emulsion is usually used by adding an unstable selenium compound and / or a non-unstable selenium compound and stirring the emulsion at a high temperature, preferably at 40 ° C. or higher for a certain period of time. Specific examples of unstable selenium sensitizers include isoselenocyanates (for example, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenamides, selenocarboxylic acids (for example,
2-selenopropionic acid, 2-selenobutyric acid), selenoesters, diacyl selenides (for example, bis (3-chloro-2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides, colloidal metal selenium And so on. The preferred types of labile selenium compounds have been described above, but are not limiting. Speaking to a person skilled in the art as an unstable selenium compound as a sensitizer for a photographic emulsion, the structure of the compound is not so important as long as selenium is unstable,
It is generally understood that the organic portion of the selenium sensitizer molecule carries selenium and plays no role other than allowing it to be present in the emulsion in an unstable form. In the present invention, an unstable selenium compound having such a broad concept is advantageously used. Examples of the non-labile selenium compound include selenous acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenide, diaryl diselenide, dialkyl selenide, dialkyl diselenide, 2-selenazolidinedione, 2-Selenaoxazolidinethione and derivatives thereof. Of these selenium compounds, the following general formulas (1) and (2) are preferable.

[0041]

[Chemical 7]

In the formula, Z ₁ and Z ₂ may be the same or different and each represents an alkyl group (eg, methyl group, ethyl group, t-butyl group, adamantyl group, t-octyl group), alkenyl group (eg, , Vinyl group, propenyl group), aralkyl group (eg, benzyl group, phenethyl group), aryl group (eg, phenyl group, pentafluorophenyl group, 4-chlorophenyl group, 3-nitrophenyl group, 4-octylsulfamoyl) Phenyl group, α-
Naphthyl group), heterocyclic group (for example, pyridyl group, thienyl group), heterocyclic group (for example, pyridyl group, thienyl group,
Furyl group, imidazoltal group), -NR ₁ (R ₂ ), -OR
It represents ₃ or -SR _4. R ₁ , R ₂ , R ₃ and R _{4, which} may be the same or different, each represents an alkyl group, an aralkyl group, an aryl group or a heterocyclic group. Z as an alkyl group, aralkyl group, aryl group or heterocyclic group
An example similar to ₁ is given. However, R ₁ and R ₂ are a hydrogen atom or an acyl group (eg, acetyl group, propanoyl group, benzoyl group, heptafluorobutanoyl group,
Difluoroacetyl group, 4-nitrobenzoyl group, α-
Naphthoyl group, 4-trifluoromethylbenzoyl group)
It may be. In the general formula (1), preferably Z ₁ represents an alkyl group, an aryl group or —NR ₁ (R ₂ ), and Z 1
₂ represents -NR ₅ (R) ₆ . R ₁ , R ₂ , R ₅ and R _{6, which} may be the same or different, each represents a hydrogen atom, an alkyl group, an aryl group or an acyl group. In the general formula (1), more preferably N, N-dialkylselenourea, N, N, N'-trialkyl-N'-acylselenourea, tetraalkylselenourea, N, N-dialkyl-arylselenoamide, N -Alkyl-N-aryl-arylselenoamide.

[0043]

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In the formula, Z ₃ , Z ₄ and Z ₅ may be the same or different, and are an aliphatic group, an aromatic group, a heterocyclic group, --OR ₇ , --NR ₈ (R ₉ ), --SR. ₁₀ , -Se
R _11a , X and a hydrogen atom. R ₇ , R ₁₀ and R _11a represent an aliphatic group, an aromatic group, a heterocyclic group, a hydrogen atom or a cation, and R ₈ and R ₉ represent an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom. , X represents a halogen atom. In the general formula (2), Z ₃ , Z ₄ , Z ₅ , R ₇ , R ₈ , R ₉ ,
The aliphatic group represented by R ₁₀ and R _11a is a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group, aralkyl group (for example, methyl group, ethyl group, n-propyl group, isopropyl group, t- Butyl group, n-butyl group,
n-octyl group, n-decyl group, n-hexadecyl group,
Cyclopentyl group, cyclohexyl group, allyl group, 2-
Butenyl group, 3-pentenyl group, propargyl group, 3-
Pentynyl group, benzyl group, phenethyl group). In the general formula (2), Z ₃ , Z ₄ , Z ₅ , R ₇ , R ₈ , R ₉ ,
The aromatic group represented by R ₁₀ and R _11a is a monocyclic or condensed ring aryl group (eg, phenyl group, pentafluorophenyl group, 4-chlorophenyl group, 3-sulfophenyl group, α-naphthyl group, 4- Represents a methylphenyl group).
In the general formula (2), Z ₃ , Z ₄ , Z ₅ , R ₇ , R ₈ ,
The heterocyclic group represented by R ₉ , R ₁₀ and R _11a is a nitrogen atom,
3 containing at least one of oxygen atom or sulfur atom
A 10-membered saturated or unsaturated heterocyclic group (for example,
Pyridyl group, thienyl group, furyl group, thiazolyl group, imidazolyl group, benzimidazolyl group). In the general formula (2), the cation represented by R ₇ , R ₁₀ and R _11a represents an alkali metal atom or ammonium, and X
The halogen atom represented by represents, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. In the general formula (2),
Preferably Z _3, Z ₄ or Z ₅ represents an aliphatic group, an aromatic group or -OR _7, R ₇ represents an aliphatic group or an aromatic group. In formula (2), more preferably trialkylphosphine selenide, triarylphosphine selenide, trialkylselenophosphate or triarylselenophosphate. Specific examples of the compounds represented by formulas (1) and (2) are shown below, but the invention is not limited thereto.

[0045]

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[0046]

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[0047]

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[0048]

[Chemical 12]

[0049]

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Examples of the tellurium sensitizer used in the present invention include colloidal tellurium and telluroureas (eg, allyl tellurourea, N, N-dimethyl tellurourea, tetramethyl tellurourea, N-carboxyethyl-N ', N). ′
-Dimethyl tellurourea, N, N'-diphenylethylene tellurourea), interrussianates (eg allylisotellurocyanate), telluroketones (eg telluroacetophenone), telluroamides (eg telluroacetamide, N, N-dimethyltelurobenzamide) ),
Tellurohydrazide (eg, N, N ′, N′-trimethyltelulobenzhydrazide), telluroester (eg, t
-Butyl-t-hexyl telluroester), phosphine tellurides (for example, tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride, butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride), diacyl (diacyl) ) Tellurides (eg, bis (diphenylcarbamoyl) ditelluride, bis (N-phenyl-
N-methylcarbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) telluride, diethylcarbamoyl telluride, bis (ethoxycarbonyl) telluride), (di) tellurides, and other tellurium compounds (for example, British Patent No. 1, Negatively charged telluride ion-containing gelatin described in No. 295,462, potassium telluride, potassium tellurocyanate, telluropentathionate sodium salt, allyl tellurocyanate). Of these tellurium compounds, the following general formulas (3), (4) and (5) are preferable.

[0051]

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In the above general formula (3), R ₁₁ , R ₁₂ and R
₁₃ is an aliphatic group, an aromatic group, a heterocyclic group, OR ₁₄ , NR
₁₅ (R ₁₆ ), SR ₁₇ , OSiR ₁₈ (R ₁₉ ) (R ₂₀ ), X
Or represents a hydrogen atom. R ₁₄ and R ₁₇ represent an aliphatic group, an aromatic group, a heterocyclic group, a hydrogen atom or a cation,
₁₅ and R ₁₆ represent an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, R ₁₈ , R ₁₉ and R ₂₀ represent an aliphatic group, and X represents a halogen atom. Next, the general formula (2) will be described in detail. In the general formula (3), R ₁₁ ,
The aliphatic group represented by R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ and R ₂₀ preferably has 1 to 30 carbon atoms.
And particularly a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group or aralkyl group having 1 to 20 carbon atoms. Examples of the alkyl group, alkenyl group, alkynyl group and aralkyl group include methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopentyl, cyclohexyl, allyl and 2-butenyl. , 3-pentenyl, propargyl, 3-pentynyl, benzyl and phenethyl. In the general formula (3), R ₁₁ ,
The aromatic group represented by R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ is preferably an aromatic group having 6 to 30 carbon atoms, particularly a monocyclic or condensed ring having 6 to 20 carbon atoms. Is an aryl group, and examples thereof include phenyl and naphthyl. In the general formula (3), R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆
And the heterocyclic group represented by R ₁₇ is a 3- to 10-membered saturated or unsaturated heterocyclic group containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom. These may be monocyclic or may form a condensed ring with another aromatic or heterocyclic ring. The heterocyclic group is preferably a 5- or 6-membered aromatic heterocyclic group, and examples thereof include pyridyl, furyl, thienyl, thiazolyl, imidazolyl and benzimidazolyl. In the general formula (3), the cation represented by R ₁₄ and R ₁₇ represents an alkali metal or ammonium. The halogen atom represented by X in the general formula (3) is, for example, a fluorine atom, a chlorine atom,
Represents a bromine atom and an iodine atom. Also, this aliphatic group,
The aromatic group and the heterocyclic group may be substituted. The following are mentioned as a substituent. Representative substituents include, for example, alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, aryl groups, alkoxy groups, aryloxy groups, amino groups, acylamino groups, ureido groups,
Urethane group, sulfonylamino group, sulfamoyl group,
Carbamoyl group, sulfonyl group, sulfinyl group, alkyloxycarbonyl group, aryloxycarbonyl group, acyl group, acyloxy group, phosphoramide group, diacylamino group, imide group, alkylthio group, arylthio group, halogen atom, cyano group, sulfo group Group, carboxy group, hydroxy group, phosphono group, nitro group and heterocyclic group. These groups may be further substituted. When there are two or more substituents, they may be the same or different. R ₁₁ , R ₁₂ and R ₁₃ may combine with each other to form a ring together with the phosphorus atom, and R ₁₅ and R ₁₆ may combine with each other to form a nitrogen-containing heterocycle. General formula (3)
Of these, preferably R ₁₁ , R ₁₂ and R ₁₃ represent an aliphatic group or an aromatic group, more preferably an alkyl group or an aromatic group.

[0053]

[Chemical 15]

In the general formula (4), R ₂₁ represents an aliphatic group, an aromatic group, a heterocyclic group or --NR ₂₃ ( ₂₄ ), and R ₂₂ represents --NR ₂₅ (R ₂₆ ) or --N (R). ₂₇₎ N (R ₂₈₎ represents an R ₂₉ or -OR _30. R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ , R ₂₇ ,
R ₂₈ , R ₂₉ and R ₃₀ represent a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group or an acyl group. Where R ₂₁ and R ₂₅ , R ₂₁ and R ₂₇ , R ₂₁ and R ₂₈ , R ₂₁ and R ₃₀ , R ₂₃ and R
₂₅ , R ₂₃ and R ₂₇ , R ₂₃ and R _28, and R ₂₃ and R ₃₀ may combine to form a ring. Next, the general formula (4) will be described in detail. In the general formula (4), R ₂₁ , R ₂₃ ,
The aliphatic group, aromatic group and heterocyclic group represented by R ₂₄ , R ₂₅ , R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ and R ₃₀ have the general formula (1).
Expresses the same meaning as. In the general formula (4), R ₂₃ , R ₂₄ ,
The acyl group represented by R ₂₅ , R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ and R ₃₀ is preferably one having 1 to 30 carbon atoms, and particularly a straight chain or branched acyl group having 1 to 20 carbon atoms. The base,
For example, acetyl, benzoyl, formyl, pivaloyl,
Decanoyl is given. Where R ₂₁ and R ₂₅ , R ₂₁ and R
_27, R ₂₁ and R _28, R ₂₁ and R _30, R ₂₃ and R _25, R ₂₃ and R _27, if R ₂₃ and R ₂₈ and R ₂₃ and R ₃₀ are combined to form a ring, for example an alkylene group , An arylene group, an aralkylene group or an alkenylene group. Also,
The aliphatic group, aromatic group and heterocyclic group have the general formula (3)
It may be substituted with the substituents listed in. General formula (4)
Preferably, R ₂₁ is an aliphatic, aromatic group or —NR ₂₃
(R ₂₄ ) and R ₂₂ represents —NR ₂₅ (R ₂₆ ).
R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ represent an aliphatic group or an aromatic group. In the general formula (4), more preferably R ₂₁ represents an aromatic group or —NR ₂₃ (R ₂₄ ), and R ₂₂ represents —NR ₂₅ (R
₂₆ ). R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ represent an alkyl group or an aromatic group. Where R ₂₁ and R ₂₅ and R ₂₃
More preferably, R ₂₅ and R ₂₅ form a ring via an alkylene group, an arylene group, an aralkylene group or an alkenylene group.

[0055]

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In the above general formula (5), R ₃₁ and R ₃₂ may be the same or different and may be an aliphatic group, an aromatic group, a heterocyclic group, or-(C = Y ')-R _33. Represents R ₃₃ is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, NR
₃₄ (R ₃₅ ), OR ₃₆ or SR 37, and Y ′ represents an oxygen atom, a sulfur atom or NR ₃₈ . R ₃₄ , R ₃₅ ,
R ₃₆ , R ₃₇ and R ₃₈ represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, and n represents 1 or 2. Next, the general formula (5) will be described in detail. In the general formula (5), the aliphatic group, aromatic group or heterocyclic group represented by R ₃₁ , R ₃₂ , R ₃₃ , R ₃₄ , R ₃₅ , R ₃₆ , R ₃₇ and R ₃₈ is represented by the general formula (4). Represents the same meaning as each of. In addition, R ₃₁ , R ₃₂ ,
The aliphatic group, aromatic group and heterocyclic group represented by R ₃₃ , R ₃₄ , R ₃₅ , R ₃₆ , R ₃₇ and R ₃₈ may be substituted with the substituents represented by the general formula (4). . Where R ₃₁ and R ₃₂
And R ₃₄ and R ₃₅ may combine with each other to form a ring. In the general formula (5), preferably R ₃₁ and R ₃₂ represent a heterocyclic group or — (C═Y ′) — R ₃₃ . R ₃₃ is NR ₃₄ (R ₃₅ )
Alternatively, it represents OR ₃₆ , and Y ′ represents an oxygen atom. R ₃₄ , R ₃₅
And R ₃₆ represents an aliphatic group, an aromatic group or a heterocyclic group. In general formula (5), more preferably R ₃₁ and R ₃₂ represent — (C═Y ′) — R ₃₃ . R ₃₃ represents NR ₃₄ (R ₃₅ ), and Y ′ represents an oxygen atom. R ₃₄ and R ₃₅ represent an aliphatic group, an aromatic group or a heterocyclic group.

Specific examples of the compounds represented by formulas (3), (4) and (5) of the present invention are shown below, but the present invention is not limited thereto.

[0058]

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[0059]

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[0060]

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[0061]

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[0062]

[Chemical 21]

[0063]

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[0064]

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[0065]

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The compounds represented by the general formulas (3), (4) and (5) of the present invention can be synthesized according to the already known methods. For example, Journal of Chemical Society (J. Chem. Soc.
(A)) 1969, 2927; Journal of Organometallic Chemistry (J. Organome).
t. Chem. ) 4,320 (1965): ibid,
1,200 (1963); ibid, 113, C35.
(1976); Phosphorus Sulfur (Phos)
phorusSulfur) 15, 155 (198)
3); Hemische Berichte (Chem. Ber) 10
9, 2996 (1976); Journal of Chemical Society Chemical Communication (J. Chem. Soc. Chem. Commun.).
635 (1980); ibid, 1102 (197).
9); ibid, 645 (1979); ibid, 82
0 (1987); Journal of Chemical Society Perkin Transactions (J. Chem.
Soc. Perkin. Trans. ) 1,191
(1980); S. Patai, The
Chemistry of Organo Selenium and
Tellurium and Tellurium Campaigns (Th
e Chemistry of Organo Sel
enium and Tellurium Compound
ds) Volume 2 216-267 (1987) Tetrahedron Letters
s) 31, 3587 (1990), Journal of.
Chemical Research, Synopses (J. Chem. R
es. , Synopses) 2, 56 (1990), Bulletin of the Chemical Society of Japan (Bull. Chem. Soc., Japan).
62, 2117 (1989), ibid, 60, 771.
(1987), Journal of Organometallic Chemistry (J. Organometallic).
Chem. ) 338, 9 (1988), ibid, 30
6, C36 (1986), The Chemical Society of Japan, Volume 7, 1475.
(1987), Zeitschrift Chemie 26,17.
9 (1986), Chemistry Letters (Chemi
story Letters) 3,475 (1987),
Indian Journal of Chemistry (In
dian Journol of Chemistr
y, Section A) 25A, 57 (1986),
Angewandte Chemie
Mie, 97, 1051 (1985), Spectrochimica Acta (Spectrochimica Act)
a, Part A) 38A, 185 (1982), Organic Preparation and Prosedia International (Organic Preparat)
ions and Procedures Inter
national) 10,289 (1978), Organometallics (Organometallics)
It can be synthesized by the method described in 1,470 (1982).

The amount of the selenium sensitizer or tellurium sensitizer used in the present invention varies depending on the silver halide grains used, the chemical ripening conditions and the like, but it is generally 10 ^-8 to 10 per mol of silver halide. ^-2 mol, preferably 10 ^-7
About 5 × 10 ⁻³ mol is used.

The conditions for the chemical sensitization in the present invention are:
Although not particularly limited, pAg is 6 to 11, preferably 7 to 10, and temperature is 40 to 95 ° C, preferably 45 to 85.

In the present invention, it is preferable to use a noble metal sensitizer such as gold, palladium, platinum or iridium together. It is particularly preferable to use a gold sensitizer, and specific examples thereof include chloroauric acid, potassium chloroauric acid, chloroauric acid thiocyanate and the like.

In the present invention, it is also preferable to use a sulfur sensitizer together. As a preferable sulfur sensitizer, various sulfur compounds such as thiosulfates, thioureas, rhodanins and polysulfide compounds can be used in addition to the sulfur compounds contained in gelatin. In the present invention, a reduction sensitizer may also be used in combination.

The azaindene compound of the present invention includes various compounds, and tetrazaindene represented by the following general formula (T) is particularly preferable.

[0072]

Embedded image

In the formula, R ¹¹ represents a hydrogen atom, a carboxylic acid group and its ester group, a mercapto group, an alkyl group (including those having a substituent), an aryl group (including those having a substituent), a hetero group. Ring group (including those having a substituent), alkylthio group (including those having a substituent),
Represents an alicyclic group (including a group having a substituent), R ¹² represents a hydrogen atom, a halogen atom, a carboxylic acid group and an ester group thereof, an alkyl group (including a group having a substituent), an aryl group (substituted) A group having a group), a heterocyclic group (including a group having a substituent), an alicyclic group (including a group having a substituent), R ¹³ is a hydrogen atom, a hydroxyl group or a carboxylic acid group. And its ester groups, amino groups (including those having a substituent), alkyl groups (including those having a substituent), aryl groups (including those having a substituent), heterocyclic groups (having a substituent) And R ¹² and R ¹³ may combine with each other to form a heterocycle or a carbocycle. Specific examples of tetrazaindene represented by formula (T) are shown below.

[0074]

[Chemical formula 26]

[0075]

Embedded image

[0076]

Embedded image

The azaindene compound is added dividedly before the addition of the chemical sensitizer and after the addition of the chemical sensitizer. The division ratio (before addition of the chemical sensitizer: weight after addition of the chemical sensitizer) It is preferable that the ratio) is 1: 2 to 1: 100. The addition amount of the azaindene compound added before the addition of the chemical sensitizer is 15 per mol of silver halide.
It is preferably mg to 500 mg, and further 15 mg to
300 mg is more preferred. The amount of the azaindene compound added after the addition of the chemical sensitizer is 300 mg to 2500 mg per mol of silver halide. Also,
The addition timing is 5 minutes or more before the addition of the chemical sensitizer, 10 minutes or more after the addition of the chemical sensitizer, and more preferably 30 minutes or more.
Immediately before application.

In the present invention, it is preferable to use a thiocyanate compound such as sodium thiocyanate, potassium thiocyanate, ammonium thiocyanate, etc. in combination as the silver halide solvent. The amount of the thiocyanic acid compound added is 4.5 × 10 ⁻⁴ mol or more and 1.8 × 10 ⁻³ mol or less per mol of silver halide.

The silver halide grains in the silver halide emulsion layer according to the present invention are normal crystal grains, ie, cubic grains, octahedron grains, 14 grains.
All isotropically grown such as a faced body, polyhedral crystal type such as a sphere, or twin crystals having a plane defect, or a mixed type or a compound type thereof. However, tabular silver halide grains are preferably used.

The emulsion used in the silver halide photographic light-sensitive material of the present invention can be produced by a known method. For example, Research Disclosure (RD) No. 17643
(December 1978) 1. Emulsion preparation method on page 22 to 23 "Emulsion Preparation and
Types ”or the same (RD) No.
18716 (November, 1979), it can be prepared with reference to the method described on page 648.

The emulsion used in the silver halide photographic light-sensitive material of the present invention is, for example, T.I. H. By James, "T
he Theory of the Photogra
phy Process "4th edition Macmilla
n, published by Company (1977), pp. 38-104,
G. F. "Photographic Emulsion Chemistry" by Dauffin, "Photo
optic Emulsion Chemist
published by ry "Focal Press (1966),
P. "The Physics and Chemistry of Photography" by Glafkids, "Ch
imie et Physique Photogra
phique "Paul Montel (196
7 years). L. Zelikman et al., "Making and Coating of Photographic Emulsions".
Photographic Emulsion "Fo
It is prepared by the method described in Cal Press (1964) and the like.

That is, under the solution conditions such as the acidic method, the ammonia method, the neutral method, etc., the forward mixing method, the reverse mixing method, the double jet method, the controlled double jet method and the like, the conversion method, the core / shell method, etc. And the like, and a combination method thereof.

A preferred embodiment of the emulsion used in the silver halide photographic light-sensitive material of the present invention is a monodisperse emulsion in which silver iodide is localized inside the grains.

The monodisperse emulsion referred to here means that when the average grain diameter is measured from a photomicrograph of silver halide grains or the like,
At least 95% of the grains by number or weight are silver halide grains within ± 30%, preferably ± 20%, of the average grain diameter. The monodispersity referred to here is defined in JP-A-60-162244, and the coefficient of variation with respect to particle diameter is 20% or less.

The crystal structure of silver halide may have a silver halide composition in which the inside and the outside are different. That is, the core and the core have at least one different silver halide composition.
It has a core / shell structure composed of shells of layers or more. The silver iodide content of the high iodine portion is 5 to 40 mol%,
Particularly preferably, it is 5 to 30 mol%.

As a method for obtaining the above-mentioned monodisperse emulsion, for example, a method of using a seed crystal and supplying silver ions and halide ions as growth nuclei to grow the seed crystal is particularly preferable.

The silver halide photographic light-sensitive material of the present invention comprises
Tabular grains having an aspect ratio (ratio of grain size / grain thickness) of 3 or more are preferably used.

The average grain size of the tabular silver halide grains is 0.
3 to 3.0 μm is preferable, and 0.1 to 1.5 μm is particularly preferable.

In the present invention, the average aspect ratio of the tabular silver halide emulsion (referred to as average aspect ratio) is 3 or more, preferably 3 to 20, and particularly preferably 3 to 10.

In the present invention, the average thickness of the silver halide emulsion is preferably 1.0 μm or less, particularly preferably 0.
It is 5 μm or less, and more preferably 0.3 μm or less.

In the present invention, the diameter of a tabular silver halide grain is defined as the diameter of a circle having an area equal to the projected area of the grain from the observation of an electron micrograph of the silver halide grain.

In the present invention, the thickness of a silver halide grain is defined as the minimum distance between two parallel planes constituting a tabular silver halide grain.

The thickness of tabular silver halide grains can be determined by observing the electron micrograph of a silver halide grain shaded with an electron microscope photograph or the slice of a sample obtained by coating a silver halide emulsion on a support and drying it. You can At least 100 samples are measured to obtain the average aspect ratio.

In the silver halide emulsion of the present invention, the proportion of tabular silver halide grains in all silver halide grains is 50% or more, preferably 60% or more, particularly preferably 70% or more.

The tabular silver halide emulsion according to the present invention is preferably monodisperse, which means that the coefficient of variation of grain size (grain size / average grain size × 100) is 25.
% Or less, preferably 20% or less, particularly preferably 15% or less.

The silver halide emulsion according to the present invention may have any halogen composition such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc. Silver iodide or silver chlorobromide is preferable, and in the case of silver iodobromide, the average silver iodide content is 0.1.
Is preferably 3.0 mol% to 3.0 mol%, and in the case of silver chloride, the silver chloride content is 5 mol% or more and 95 mol% or less, preferably 10 mol% or more and 60 mol% or less.

The silver iodide content of each emulsion grain can be measured by analyzing the composition of each silver halide grain by using, for example, an X-ray microanalyzer. As the coefficient of variation of the silver iodide content of each grain, the standard deviation of the silver iodide content when measuring the silver iodide content of at least 100 emulsion grains was divided by the average silver iodide content. 1 for the value
It is a value obtained by multiplying by 00.

In the present invention, two twin planes parallel to each other are used.
As a method for producing twinned particles having one or more particles, pBr is 3.
It can be obtained by adding a silver nitrate aqueous solution to a gelatin aqueous solution kept at 0 or less, or simultaneously adding a silver nitrate aqueous solution and a halide aqueous solution to generate twinned seed grains, and then growing them by the double jet method. The size of silver halide grains can be controlled by the temperature at the time of grain formation and the addition rate of silver salt and halide aqueous solution.

The emulsion may be subjected to a water washing method such as a Nudel water washing method or a flocculation sedimentation method in order to remove soluble salts (desalting treatment step). As a preferred water washing method, for example, a method using an aromatic hydrocarbon aldehyde resin containing a sulfo group described in JP-B-35-16086, or a coagulated polymer agent described in JP-A-2-7037, exemplified by G-
3, a method using G-8 or the like is a particularly preferred desalting method.

The temperature of the chemical ripening of the silver halide emulsion according to the present invention can be arbitrarily determined, but within the range of 20 to 90 ° C.
It is preferably 30 to 80 ° C., and more preferably 35 to
It is 70 ° C.

The silver halide photographic light-sensitive material of the present invention has at least one light-sensitive layer described above on a support and may optionally have an undercoat layer, an antihalation layer, an intermediate layer and a protective layer. Good.

The support which can be used in the silver halide photographic light-sensitive material of the present invention is, for example, a polyethylene terephthalate film or the like, and an undercoat layer is formed on the surface of these supports to improve the adhesion of the coating layer. Set up,
You may give corona discharge, ultraviolet irradiation, etc.

[0103]

EXAMPLES Examples of the present invention will be described below. However, as a matter of course, the present invention is not limited to the examples described below.

Example 1 (Preparation of seed emulsion-1) Seed emulsion-1 was prepared by the following method.

[A ₁ ] Ocein gelatin 24.2 g Distilled water 9657 ml Polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% methanol aqueous solution) 6.78 ml Potassium bromide 10.8 g 10% nitric acid 114 ml [B ₁ ] 2.5N AgNO ₃ aqueous solution 2825 ml [C ₁ ] potassium bromide 837 g potassium iodide 5.86 g Finish with water to 2825 ml [D ₁ ] 1.75 N KBr aqueous solution Silver potential control amount at 42 ° C. JP-B-58-58288, Same as 58-5828
Using a mixing stirrer described in the specification of No. 9, 464.3 ml of each of the solution B ₁ and the solution C ₁ was added to the solution A ₁ by a simultaneous mixing method over 1.5 minutes to form nuclei. .

After stopping the addition of solution B ₁ and solution C ₁ ,
Over a period of 40 minutes of time to raise the temperature of the solution A ₁ to 50 ° C., after adjusting the pH to 5.0 with 3% KOH, the solution again B ₁ and solution C ₁ simultaneous mixing method, each 55 0.4 ml /
Min was added at a flow rate of 42 minutes. 50 from 42 ℃
The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during the temperature increase to ℃ and re-simultaneous mixing with the solutions B ₁ and C ₁ was +8 mV and +16 mV, respectively, using the solution D _1. Controlled to be.

After the addition was completed, the pH was adjusted to 6 with 3% KOH, and desalting and washing with water were immediately performed. In this seed emulsion, 90% or more of the total projected area of the silver halide grains is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0, and the average thickness of the hexagonal tabular grains is 0.045 μm. It was confirmed by an electron microscope that the average particle size (circular diameter conversion) was 0.42 μm. The variation coefficient of the thickness was 42%, and the variation coefficient of the distance between twin planes was 45%.

Preparation of tabular silver bromide emulsion A tabular pure silver bromide emulsion was prepared using seed emulsion-1 and the following three solutions.

[A ₂ ] Ocein gelatin 34.03 g Polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% aqueous methanol solution) 2.25 ml Seed emulsion-1 1.218 mol equivalent Water to make up 3669 ml [B ₂ ] Potassium bromide 1747 g Finish with water to 3669 ml [C ₂ ] Silver nitrate 2493 g Finish with water to 4193 ml Solution A ₂ was stirred vigorously while keeping it at 50 ° C., and the total amount of solution B ₂ and solution C ₂ was added thereto. It was added by the double-sided mixing method over 100 minutes. During this time, the pH was kept at 9.0 with the KOH solution, and the pAg was kept at 8.6 throughout. Here, the addition rates of the solution B ₂ and the solution C ₂ were changed functionally with respect to time so as to match the critical growth rate. That is, they were added at an appropriate addition rate so that no small particles were generated except for the seed particles that were growing, and that they did not become multicomponent due to Ostwald ripening.

After the completion of addition, the emulsion was cooled to 40 ° C., and 1800 ml of an aqueous solution of 13.8% (weight) of modified gelatin modified with phenylcarbamoyl groups (substitution rate 90%) was added as an aggregating polymer agent. Stir for 3 minutes. Thereafter, a 56% (by weight) aqueous solution of acetic acid is added to adjust the pH of the emulsion.
Was adjusted to 4.6 and stirred for 3 minutes, allowed to stand for 20 minutes, and the supernatant was drained by decantation.
1.25 l was added, and after stirring and standing, the supernatant was drained.

Then, an aqueous gelatin solution and sodium carbonate 1
A 0% (by weight) aqueous solution was added to adjust the pH to 5.80, and the mixture was stirred at 50 ° C. for 30 minutes and redispersed. After redispersion, pH was adjusted to 5.80 and pAg was adjusted to 8.06 at 40 ° C.

Observation of the obtained silver halide emulsion with an electron microscope revealed that the average grain size was 0.84 μm, the average thickness was 0.16 μm, the average aspect ratio was about 5.3, and the grain size distribution was 20%. It was a tabular silver halide grain. The amount of gelatin at the end of physical ripening was 15.9 g per mol of silver halide.

After the emulsion prepared above was heated to 55 ° C., the sample No. Except for No. 23, the spectral sensitizing dye dispersions D-1 and D-2 described below were added in the amounts shown in Table 3, and the azaindene compound described in Table 3 was added. No. For No. 23, D-2 was added in the amount shown in Table 3 immediately before the end of chemical sensitization (immediately before cooling).
After 10 minutes, 3.5 mg of chloroauric acid, 10 mg of sodium thiosulfate, and the thiocyanic acid compound were added in the amounts shown in Table 3. After 40 minutes, 0.3 mol of silver iodide fine particles was added, after 10 minutes, the selenium compound shown in Table 3 was added, after 40 minutes, the azaindene compound shown in Table 3 was added, and after 5 minutes, trimethylolpropane. After 13 g and 30 g of gelatin were added, rapid cooling was carried out to gelate the emulsion to complete the chemical sensitization.

Dispersion of Spectral Sensitizing Dye (D-1): 14.8 g of Exemplified spectral sensitizing dye B-2 and 0.2 g of A-55 were taken, and methanol was added and dissolved at 27 ° C. to perform spectral sensitization. A solution of the dye in methanol was obtained.

(D-2): 9.87 g of Exemplified spectral sensitizing dye B-2 and 0.13 g of A-55 were taken, and 490 g of water preliminarily adjusted to 27 ° C. was added thereto, followed by a high speed stirrer ( A dispersion liquid of the spectral sensitizing dye was obtained by stirring with a dissolver) at 3,500 rpm for 30 to 120 minutes. The average particle size of the disperse dye was 0.7 μm.

By the addition of the silver iodide grains described above, the average iodine content of the outermost surface of the silver halide grains in the silver halide emulsion was about 11 mol%.

Next, the emulsion thus sensitized was heated and redissolved, and then the additives described below were added to prepare an emulsion coating solution. At the same time, a coating solution for the protective layer was prepared. The coating amount was 1.4 / m ² on one side and the amount with gelatin was 2.0 g / m ² , using two slide hopper type coaters to coat both sides of the support simultaneously and dry. , A sample was obtained.

The support has a thickness of 175 μm and a density of 0.
Dilution 17 was carried out so that the concentration of a copolymer composed of three monomers of 50 wt% of glycidyl methacrylate, 10 wt% of methyl methacrylate, and 40 wt% of butyl methacrylate was 10 wt% on both sides of a polyethylene terephthalate film base for radiography which was colored blue. The following filter dye and gelatin were dispersed in the aqueous copolymer dispersion thus obtained and applied as a subbing liquid. The coating weight at this time was 15 mg / m ^{2 for the} dye and 0.15 for the gelatin.
mg / m ² .

[0119]

[Chemical 29]

The additives added to the emulsion are as follows.
The amount of addition is shown in an amount per mole of silver halide.

1,1-Dimethylol-1-bromo-1-nitromethane 70 mg Polyvinylpyrrolidone (molecular weight 10,000) 1.0 g Styrene-maleic anhydride copolymer 2.5 g Nitrophenyl-triphenylphosphonium chloride 50 mg C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 1.0 g 1-phenyl-5-mercaptotetrazole 8.5 mg

[0122]

Embedded image

Protective Layer Solution Next, the following was prepared as a protective layer coating solution. Additives are shown in amounts per liter of coating solution.

Lime-treated inert gelatin 68 g Acid-treated gelatin 2.0 g Sodium-i-amyl-n-decylsulfosuccinate 1.0 g Polymethylmethacrylate (matting agent having an area average particle size of 3.5 μm) 1.1 g Silicon dioxide particles (A matting agent having an area average particle diameter of 1.2 μm) 0.5 g (CH ₂ = CHSO ₂ CH ₂ ) ₂ (hardening agent) 500 mg C ₄ F ₉ SO ₃ K 2.0 mg C ₁₂ H ₂₅ CONH (CH ₂ CH ₂ O) ₅ H 2.0 g

[0125]

[Chemical 31]

Photographic properties (sensitivity) of the obtained samples were evaluated. The evaluation method is as follows. First, the sample is two intensifying screens KO.
-250 (manufactured by Konica Corporation), a tube voltage of 80 kVP, a tube current of 100 mA, and a 0.05 through a penetrameter.
The second tube was exposed to X-rays for exposure.

The development processing was carried out by modifying the automatic developing machine SRX-502 (manufactured by Konica Corp.) to a line speed of 1.8 times and using a developing solution and a fixing solution having the following formulations.

Developer formulation Part-A (for 12 liter finish) potassium hydroxide 450 g potassium sulfite (50% solution) 2280 g diethylenetetraamine pentaacetic acid 120 g sodium hydrogen carbonate 132 g 5-methylbenzotriazole 1.2 g 1-phenyl- 5-mercaptotetrazole 0.2 g 1,4-dihydroxybenzene 340 g Add water to make 5000 ml Part-B (for finishing 12 liters) Glacial acetic acid 170 g Triethylene glycol 185 g 1-phenyl-3-pyrazolidone 22 g 5-nitroindazole 0 4 g Starter solution formulation (for 1 liter finish) Glacial acetic acid 120 g Potassium bromide 225 g Add water to finish to 1000 ml Fixer formulation Part-A (for 18 liter finish) Anne thiosulfate Monium (70 wt / vol%) 6000 g Sodium sulfite 110 g Sodium acetate trihydrate 450 g Sodium citrate 50 g Gluconic acid 70 g 1- (N, N-Dimethylamino) -ethyl-5-mercaptotetrazole U 18 g Part-B Aluminum sulfate 800 g Preparation of developer The developer is prepared by adding Part-A and Pa to about 5 liters of water.
rt-B was added at the same time, and water was added while dissolving with stirring.
After finishing to 1 liter, the pH was adjusted to 10.40 with glacial acetic acid to obtain a developer.

20 ml of the starter solution was added to 1 liter of the developer, and the pH was adjusted to 10.40 to prepare a working solution.

Preparation of fixer The fixer was prepared by adding Part-A and Par to about 5 liters of water.
t-B was added at the same time, and water was added while stirring and dissolving to give 18
Liters, p with sulfuric acid and sodium hydroxide
H was adjusted to 4.4, and this was used as a fixing solution working solution and a fixing solution replenisher.

The processing temperature is development 35 ° C., fixing 33 ° C., water washing 20 ° C., drying 50 ° C., processing time is Dry.
The time to dry (that is, the time from when the leading end of the photosensitive material starts to be immersed in the developing solution to when the leading end comes out of the drying zone through the processing step) is 25 seconds.

The replenishment amounts of the developing solution and the fixing solution were respectively 10 ml per four-cut film, and after processing 3,000 four-cut films of SR-ESG (manufactured by Konica Corporation), the samples of Examples were processed. Then, the fog and the sensitivity were measured. The sensitivity is expressed by the reciprocal of the amount of exposure energy required to give a density of fog +1.0. It was shown as a relative value with the sensitivity of 1 being 100.

<Evaluation of Color Remaining> The sample was developed in the same manner as above without exposing it to light, and the color remaining was visually evaluated according to the following criteria. The larger the value is, the less the residual color contamination is and the more excellent it is.

5: Almost no residual color contamination 4: Less residual color contamination, good 3: Some residual color contamination, but acceptable level for practical use 2: Some residual color contamination, no practical use 1: Sufficient residual color contamination No Level The results obtained are shown in the table below.

[0135]

[Table 3]

As is apparent from the table, according to the present invention, it is possible to obtain a high-sensitivity and low-fog silver halide photographic light-sensitive material having no residual color stain on the processed film.

[0137]

According to the present invention, it is suitable for rapid processing,
A silver halide light-sensitive material having high sensitivity, low fog and good residual color, and a method for producing the silver halide emulsion can be provided.

Claims (10)

[Claims] 1. A spectral sensitizing dye is added before the addition of the chemical sensitizer in an amount of 50 mg to 500 mg per mol of silver halide, and an azaindene compound is added before the addition of the chemical sensitizer and after the addition of the chemical sensitizer. A method for producing a silver halide emulsion, which is added in portions. 2. The method for producing a silver halide emulsion according to claim 1, wherein the spectral sensitizing dye is dispersed in solid fine particles and added. 3. The method for producing a silver halide emulsion according to claim 1, wherein the chemical sensitizer is a selenium compound or a tellurium compound. 4. The method for producing a silver halide emulsion according to claim 1, wherein the chemical sensitizer is a gold compound and a selenium compound or a tellurium compound. 5. The chemical sensitizer is a gold compound and a selenium compound or a tellurium compound, and the thiocyanate compound is 4.5 × 10 ⁻⁴ mol or more and 1.8 × 10 ⁻³ per mol of silver halide. 3. The method for producing a silver halide emulsion according to claim 1, wherein the silver halide content is not more than mol. 6. The spectral sensitizing dye is represented by the following general formula (A):
Alternatively, it is a compound represented by the general formula (B), and the method for producing a silver halide emulsion according to any one of claims 1 to 5. Embedded image In the formula, R ¹ and R ³ each represent a substituted or unsubstituted alkyl group, at least one of R ¹ and R ³ is a group other than an ethyl group, and R ² and R ⁴ are lower groups. It represents an alkyl group, and at least one of R ² and R ⁴ represents an alkyl group substituted with a hydrophilic group. V ¹ , V ² , V ³ and V
⁴ represents a hydrogen atom or a substitutable group in which the sum of added Hammett σp values is smaller than 1.7,
V ¹ , V ² , V ³ and V ⁴ cannot be hydrogen atoms or chloro atoms at the same time. X ¹ represents an ion necessary for neutralizing the charge in the molecule, and n represents 1 or 2. However, when an inner salt is formed, n is 1. Embedded image In the formula, R ⁵ and R ⁶ each represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group, and at least one of R ⁵ and R ⁶ is sulfoalkyl. A group or a carboxyalkyl group. R ⁷ represents a hydrogen atom, an alkyl group or an aryl group.
Z ¹ and Z ² each represent a non-metal atom group necessary for completing a benzene ring or a naphtho ring which may have a substituent. X ² represents an ion necessary for neutralizing the charge in the molecule, and m represents 1 or 2. However, m is 1 when forming an intramolecular salt. 7. The division ratio of the azaindene compound (before addition of chemical sensitizer: weight ratio after addition of chemical sensitizer) is 1: 2 to 2.
It is 1: 100, The manufacturing method of the silver halide emulsion of any one of Claims 1-6 characterized by the above-mentioned. 8. The addition amount of the azaindene compound added before the addition of the chemical sensitizer is 15 mg to 500 mg per mol of silver halide.
8. The method for producing a silver halide emulsion according to any one of items 7 to 7. 9. A silver halide photographic material having at least one silver halide emulsion layer on a support,
A silver halide photographic light-sensitive material characterized in that the silver halide emulsion is a silver halide emulsion produced by the method for producing a silver halide emulsion according to any one of claims 1 to 8. 10. The silver halide photographic light-sensitive material according to claim 9, wherein the amount of the spectral sensitizing dye per one side of the silver halide photographic light-sensitive material is ² to 7 mg / m ² .