JP2851207B2 - Silver halide photographic material - 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 silver halide photographic light-sensitive material having high sensitivity and reduced fog.

[0002]

2. Description of the Related Art In recent years, requirements for silver halide photographic light-sensitive materials have become increasingly severe. In particular, the demands for higher sensitivity and higher image quality have not been known to remain, which has plagued researchers in this field.

[0003] Silver halide emulsions used in silver halide photographic materials are usually subjected to various chemical sensitizations. Typical methods include chalcogen sensitization (sulfur sensitization, selenium sensitization, tellurium sensitization), noble metal sensitization (eg, gold sensitization, platinum sensitization), reduction sensitization, and a combination thereof. Are known.

Among the above sensitization methods, the tellurium sensitization method and the tellurium sensitizer are described, for example, in US Pat.
No. 9, No. 3320069, No. 3772031, No. 3
Nos. 531289 and 3655394; British Patent No. 23
No. 5211, No. 1121496, No. 1295462
No. 1,396,696, and Canadian Patent No. 800958, but a detailed and specific description of tellurium sensitizers can be found in British Patent No. 1295462.
No. 1,396,696 and Canadian Patent No. 800958.

[0005] However, the conventionally known tellurium sensitizer, as exemplified in Canadian Patent No. 800958, for example, differs from sulfur sensitization usually used in the art in that it is used alone. Has high sensitivity and low fog and is excellent in high contrast, but the gold-tellurium sensitizer used in combination with the noble metal sensitizer aiming at higher sensitivity, especially the gold sensitizer, Although the sensitivity is high, there is a drawback that fogging is large, and this improvement has been strongly desired.

Because of these drawbacks, ordinary silver halide light-sensitive materials are generally sensitized by sulfur sensitization, selenium sensitization or a combination thereof.
Tellurium sensitization was not actually used, and there are very few descriptions in the literature compared to these, and among the aforementioned patents, actual experiments are often described only with respect to sulfur sensitization or selenium sensitization .

The present inventor has made various studies in order to solve the drawback of high fog by taking advantage of the high sensitivity of tellurium sensitization.

For example, as a means for reducing fog in selenium sensitization, addition of an unstable sulfur compound described in US Pat. No. 3,297,447, JP-A-59-1805
No. 36, use of a silver halide solvent described in
Use of a monodisperse emulsion described in JP-A-192241
JP-A-185329 proposes chemical sensitization of a monodisperse emulsion in the presence of a nitrogen-containing heterocyclic compound capable of forming a complex with silver.

Although some effects were recognized when these inventions were applied to tellurium sensitization, the effect of suppressing the fog due to tellurium sensitization and the increase in fog generated during storage of the photosensitive material was still insufficient. .

In addition, the spectral sensitization technique is extremely important and indispensable for producing a photosensitive material having high sensitivity and excellent color reproducibility. The spectral sensitizer has a function of absorbing light in a long wavelength range which is not substantially absorbed by the silver halide photographic emulsion and transmitting the light absorption energy to the silver halide.
Therefore, an increase in the amount of light trapped by the spectral sensitizer is advantageous for increasing photographic sensitivity. For this reason, attempts have been made to increase the amount of light trapped by increasing the amount added to the silver halide emulsion. However, if the amount of the spectral sensitizer to be added to the silver halide emulsion exceeds the optimum amount, a large desensitization is brought about. This is generally referred to as dye desensitization, and is a phenomenon in which desensitization occurs in a photosensitive region peculiar to silver halide, which has substantially no light absorption by a sensitizing dye. If the dye desensitization is large, the overall sensitivity will be low although there is a spectral sensitizing effect. In other words, if the dye desensitization decreases,
The sensitivity of the light absorption region by the sensitizing dye (that is, the spectral sensitization) also increases accordingly. Therefore, in spectral sensitization technology, improvement of dye desensitization is a major problem. In general, the dye desensitization is larger for a sensitizing dye having a photosensitive region at a longer wavelength. These are described in C.I. E. FIG. K. Mee, "Theory of the Photographic Process (Thee)
Theory of the Photograph
ic Process) ", pp. 1067-1069 (Macmillan, 1942).

As a method for increasing the sensitivity by reducing the dye desensitization, JP-A-47-28916 and JP-A-49-4673.
No. 8, 54-118236, U.S. Pat.
No. 083 is known. However, in the above-mentioned technology, sensitizing dyes that can be used are limited, and the effects thereof are still unsatisfactory. At present, the most effective means for improving dye desensitization include, for example, Japanese Patent Publication No. 45-2
2189, JP-A-54-18726, JP-A-52-2
No. 4822, JP-A-52-151026 and U.S. Pat. No. 2,945,762 are known in which a bisaminostilbene compound substituted with a pyrimidine derivative or a triazine derivative is used in combination. However, sensitizing dyes in which the above compounds are effective are usually so-called M-ba, which exhibits a gentle sensitizing maximum such as dicarbocyanine, tricarbocyanine, rhodocyanine, and merocyanine.
It is limited to nd-sensitized dyes and dyes having a sensitization maximum in a relatively long wavelength region.

In US Pat. No. 3,695,888, the combination of a specific tricarbocyanine and ascorbic acid can provide sensitization in the infrared region.
No. 84 discloses that the combination of a specific dye with ascorbic acid increases the minus blue sensitivity, and that British Patent 1,06
U.S. Pat. No. 4,809,193 discloses that a specific dye can be used in combination with ascorbic acid to increase sensitivity.
No. 561 describes the combined use of a desensitizing nucleus-containing cyanine dye with a supersensitizer such as ascorbic acid.

However, in the above prior arts, there are few such dyes which still have a satisfactory sensitizing effect of the dye, and those having a high sensitizing effect tend to increase fog.

Attempts have been made to add hydrazines to silver halide photosensitive materials or developers for various purposes.

US Pat. No. 2,419,975;
In JP-A-3-261362 and JP-B-51-15745, hydrazines are used by adding them to a developer.

JP-B-58-9410, 58-9411
In No. 2, acylhydrazines are added to a light-sensitive material in order to obtain a high-contrast silver halide light-sensitive material.

Addition of hydrazines shows a small but sensitizing effect, but increases fog.

JP-A-63-95444, 63-431
In No. 45, the stability of a dye image against heat and light is improved by using a magenta coupler and a specific hydrazine in combination.

JP-A-63-220142, 63-25
Nos. 6951 and 63-229455 prevent photobleaching by using an organic coloring substance and a specific hydrazine in combination.

However, there is no known example of using hydrazines as in the present invention.

[0021]

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

[0022]

As a result of various studies, the present inventor has found that the above object can be achieved by the following means.

(1) In a silver halide photographic material having at least one silver halide emulsion layer on a support, at least one silver halide emulsion contained in the silver halide emulsion layer is increased in tellurium. A silver halide photographic light-sensitive material, characterized in that the silver halide emulsion layer contains at least one compound represented by the following general formula (I).

Formula (I)

[0025]

Embedded image In the formula, R ₁ , R ₂ , R ₃ and R ₄ each represent an alkyl group, an aryl group or a heterocyclic group. Also, R ₁ and R
₂ , R ₃ and R ₄ , R ₁ and R ₃ , and R ₂ and R ₄ may combine with each other to form a ring, but do not form an aromatic ring.

However, among R ₁ , R ₂ , R ₃ and R ₄ , the carbon atom directly bonded to the nitrogen atom of hydrazine is not substituted with an oxo group.

(2) The silver halide photographic material as described in (1), which has been spectrally sensitized with a sensitizing dye.

(3) The halogen according to (1), wherein the compound represented by the general formula (I) is a compound selected from the following general formulas (II), (III) and (IV) Silver halide photographic material.

General formula (II)

[0030]

Embedded image General formula (III)

[0031]

Embedded image General formula (IV)

[0032]

Embedded image In the formula, R ₅ , R ₆ , R ₇ and R ₈ are each an alkyl group,
Represents an aryl group or a heterocyclic group.

Z ₁ represents an alkylene group having 4 or 6 carbon atoms.

Z ₂ represents an alkylene group having 2 carbon atoms.

Z ₃ represents an alkylene group having 1 or 2 carbon atoms.

Z ₄ and Z ₅ represent an alkylene group having 3 carbon atoms.

L ₁ and L ₂ represent a methine group.

However, R ₅ , R ₆ , R ₇ , R ₈ , Z ₁ ,
In Z ₄ and Z _5, the carbon atom directly bonded to the nitrogen atom of hydrazine is not substituted with an oxo group. More preferred are compounds selected from general formulas (II) and (III), and particularly preferred are compounds selected from general formula (II).

[0039] (4) spectrally sensitized by a sensitizing dye (3) the silver halide photographic light-sensitive material as described.

(5) The silver halide photographic light-sensitive material according to any one of (1) to (4), wherein the silver halide emulsion is subjected to sulfur sensitization and tellurium sensitization in combination. material.

(6) The halogen according to any of (1) to (4), wherein the silver halide emulsion has been subjected to sulfur sensitization, selenium sensitization, and tellurium sensitization in combination. Silver halide photographic material.

Hereinafter, the present invention will be described in more detail. First, tellurium sensitization used in the present invention will be described.

As tellurium sensitizers used in the present invention, US Pat. Nos. 1,623,499 and 3,320,
Nos. 069 and 3,772,031, British Patent No. 23
Nos. 5,211, 1,121,496 and 1,29
Nos. 5,462, 1,396,696, Canadian Patent No. 800,958, Japanese Patent Application Nos. 2-333819, 3-
No. 53693, No. 3-131598, No. 4-1297
No. 87, Journal of Chemical Society Chemical Communication (J. Chem. So
c. Chem. Commun. ) 635 (1980),
ibid 1102 (1979), ibid 645
(1979), Journal of Chemical Society Parkin Transaction (J. Chem.
Soc. Perkin Trans. ) 1,191
(1980); S. Pati ed., The Chemistry of Organic Selenium and Tellurium Campounds (The Chemist)
ry of Organic Selenium an
d Tellurium compounds), Vo
It is preferable to use the compounds described in l1 (1986) and Vol2 (1987).

Specific examples of tellurium sensitizers include colloidal tellurium and telluroureas (for example, allyl tellurourea, N, N-dimethyltellurourea, tetramethyltellurourea, N-carboxyethyl-N ', N'-). Dimethyltellurourea, N, N'-dimethylethylenetellurourea,
N, N'-diphenylethylene tellurourea), isotellurocyanates (e.g. allyl isotellurocyanate), telluroketones (e.g. telluroacetophenone), telluroamides (e.g. telluroacetamide,
N, N-dimethyltellurobenzamide), tellurohydrazide (e.g., N, N ', N'-trimethyltellurobenzhydrazide), telluroester (e.g., t-butyl-t)
Hexyl telluride), phosphine tellurides (e.g., tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride, butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride), diacyl (di) tellurides ( For example, bis (diphenylcarbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) telluride, diethylcarbamoyltelluride, bis (ethoxycarbonyl) telluride, (di)
Tellurides, other tellurium compounds (eg, British Patent No. 1,
No. 295,462, negatively charged telluride ion-containing gelatin, potassium telluride, potassium tellurocyanate, sodium telluropentathionate, allyl tellurocyanate).

Of these tellurium compounds, preferred are compounds represented by the following formulas (V), (VI) and (VII).

Formula (V)

[0047]

Embedded image In the formula, R ₁ , R ₂ and R ₃ are an aliphatic group, an aromatic group, a heterocyclic group, OR ₄ , NR ₅ (R ₆ ), SR ₇ , OSiR ₈
(R ₉ ) represents (R ₁₀ ), X or a hydrogen atom. R ₄ and R ₇ represents an aliphatic group, an aromatic group, a heterocyclic group, a hydrogen atom or a cation, R ₅ and R ₆ represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, R ₈ , R ₉ and R ₁₀ represent an aliphatic group, and X represents a halogen atom.

In the general formula (V), R ₁ , R ₂ ,
R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀
The aliphatic group represented by is preferably a group having 1 to 30 carbon atoms, particularly a linear, branched or cyclic alkyl group, alkenyl, alkynyl group or aralkyl group having 1 to 20 carbon atoms. Alkyl group, alkenyl group, alkynyl group,
As the aralkyl group, for example, methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, n
-Decyl, n-hexadecyl, cyclopentyl, cyclohexyl, allyl, 2-butenyl, 3-pentenyl, propargyl, 3-pentynyl, benzyl, phenethyl and the like.

In the general formula (V), R ₁ , R ₂ ,
The aromatic group represented by R ₃ , R ₄ , R ₅ , R ₆ and R ₇ preferably has 6 to 30 carbon atoms, particularly a monocyclic or condensed aryl group having 6 to 20 carbon atoms. And examples thereof include phenyl and naphthyl.

In the general formula (V), R ₁ , R ₂ ,
The heterocyclic group represented by R ₃ , R ₄ , R ₅ , R ₆ and R ₇ is a saturated or unsaturated 3- to 10-membered ring containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom. It is a ring group. These may be monocyclic or may form a condensed ring with another aromatic or heterocyclic ring. The heterocyclic group is preferably a 5- to 6-membered aromatic heterocyclic group, for example, a pyridyl group, a furyl group, a thienyl group,
Thiazolyl, imidazolyl, benzimidazolyl and the like.

In the general formula (V), the cations represented by R ₄ and R ₇ represent an alkali metal and ammonium.

The halogen atom represented by X in the general formula (V) represents, for example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Further, these aliphatic group, aromatic group and heterocyclic group may be substituted. Examples of the substituent include the following.

Representative substituents include, for example, alkyl, aralkyl, alkenyl, alkynyl, aryl, alkoxy, aryloxy, amino,
Acylamino group, ureido group, urethane group, sulfonylamino group, sulfamoyl group, carbamoyl group, sulfonyl group, sulfinyl group, alkyloxycarbonyl group, aryloxycarbonyl group, acyl group, acyloxy group, phosphoric amide group, diacylamino group, Imide group, alkylthio group, arylthio group, halogen atom,
Examples include a cyano group, a sulfo group, a carboxy group, a hydroxy group, a phosphono group, a nitro group, and a heterocyclic group. These groups may be further substituted.

When there are two or more substituents, they may be the same or different.

R ₁ , R ₂ and R ₃ may be bonded to each other to form a ring together with a phosphorus atom, or R ₅ and R ₆ may be bonded to form a nitrogen-containing heterocyclic ring. .

In the general formula (V), R ₁ , R ₂ and R ₃ preferably represent an aliphatic group or an aromatic group, more preferably an alkyl group or an aromatic group.

Formula (VI)

[0059]

Embedded image In the formula, R ₁₁ represents an aliphatic group, an aromatic group, a heterocyclic group or —N
R ₁₃ (R ₁₄ ), and R ₁₂ represents —NR ₁₅ (R ₁₆ ), —N
It represents the _{(R 17) N (R 18} ) R 19 or -OR _20. R ₁₃ ,
R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ and R ₂₀ represent a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group or an acyl group. Where R ₁₁ and R ₁₅ , R ₁₁ and R ₁₇ , R ₁₁ and R ₁₈ , R
₁₁ and R ₂₀ , R ₁₃ and R ₁₅ , R ₁₃ and R ₁₇ , R ₁₃ and R _18, and R ₁₃ and R ₂₀ may combine to form a ring.

In the general formula (VI), R ₁₁ , R ₁₃ ,
The aliphatic group, aromatic group and heterocyclic group represented by R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ and R ₂₀ are represented by the general formula (V)
And is equivalent.

In the general formula (VI), R ₁₃ , R ₁₄ ,
The acyl group represented by R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ and R ₂₀ preferably has 1 to 30 carbon atoms, and particularly has 1 to 20 carbon atoms. Group,
For example, acetyl, benzoyl, formyl, pivaloyl,
Decanoyl and the like.

Where R ₁₁ and R ₁₅ , R ₁₁ and R ₁₇ , R ₁₁ and R
_18, R ₁₁ and R _20, R ₁₃ and R _15, R ₁₃ and R _17, R ₁₃ and R ₁₈
When R ₁₃ and R ₂₀ combine to form a ring, examples thereof include an alkylene group, an arylene group, an aralkylene group and an alkenylene group.

The aliphatic group, aromatic group and heterocyclic group may be substituted with the substituents represented by the formula (V).

In the general formula (VI), R ₁₁ preferably represents an aliphatic group, an aromatic group or —NR ₁₃ (R ₁₄ ), and R ₁₂ represents —
Represents NR ₁₅ (R ₁₆ ). R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ represent an aliphatic group or an aromatic group.

In the general formula (VI), more preferably, R ₁₁ represents an aromatic group or —NR ₁₃ (R ₁₄ ), and R ₁₂ represents —NR ₁₅
(R ₁₆ ). R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ represent an alkyl group or an aromatic group. Here, it is more preferable that R ₁₁ and R ₁₅ and R ₁₃ and R ₁₅ form a ring via an alkylene group, an arylene group, an aralkylene group or an alkenylene group.

[0066] Formula _{(VII) R 21 - (Te} ) in _n -R ₂₂ Formula, R ₂₁ and R ₂₂ may be different even in the same, an aliphatic group, an aromatic group, a heterocyclic group, − (C = Y) −
Representing the R _23. R ₂₃ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, NR ₂₄ (R ₂₅ ), OR ₂₆ or SR ₂₇ ;
Y represents an oxygen atom, a sulfur atom or NR _28. R ₂₄ , R
₂₅ , R ₂₆ , R ₂₇ and R ₂₈ represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, and n represents 1 or 2.

In the general formula (VII), R ₂₁ , R ₂₂ , R ₂₃ ,
The aliphatic group, aromatic group and heterocyclic group represented by R ₂₄ , R ₂₅ , R ₂₆ , R ₂₇ and R ₂₈ have the same meaning as in formula (V).

Further, R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , R
_The aliphatic group, aromatic group and heterocyclic group represented by ₂₆ , R ₂₇ and R ₂₈ may be substituted by the substituents represented by formula (V).

Here, R ₂₁ and R ₂₂ and R ₂₄ and R ₂₅ may combine to form a ring.

In the general formula (VII), preferably, R ₂₁ and R
₂₂ heterocyclic group, or - represents a (C = Y) -R _23. R ₂₃ represents NR ₂₄ (R ₂₅ ) or OR ₂₆ , and Y represents an oxygen atom. R ₂₄ , R ₂₅ and R ₂₆ represent an aliphatic group, an aromatic group or a heterocyclic group.

In formula (VII), R ₂₁ and R ₂₂ more preferably represent-(C = Y) -R ₂₃ . R ₂₃ is NR ₂₄ (R
₂₅ ), and Y represents an oxygen atom. R ₂₄ and R ₂₅ represent an aliphatic group, an aromatic group or a heterocyclic group.

Specific examples of the compounds represented by formulas (V), (VI) and (VII) of the present invention are shown below, but the present invention is not limited thereto.

[0073]

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[0074]

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[0075]

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[0076]

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[0077]

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[0078]

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[0079]

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[0080]

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[0081]

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[0082]

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[0083]

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[0084]

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[0085]

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[0086]

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[0087]

Embedded image The compounds represented by formulas (V), (VI), and (VII) of the present invention can be synthesized according to a known method. For example, Journal of Chemical Society (J. Chem. Soc. (A)) 1969 , 2
927; Journal of Organometallic Chemistry (J. Organomet. Chem.) 4 ,
320 (1965); ibid, 1 , 200 (196
3); ibid, 113 , C35 (1976); Phosphorus Sul.
fur) 15 , 155 (1983); Hemische Berchte (Chem. Ber.) 109 , 2996 (197).
6); Journal of Chemical Society Chemical Communication (J. Chem. Soc.
Chem. Commun. ) 635 (1980), ib
id, 1102 (1979); ibid, 645 (19
79); ibid, 820 (1987);
Of Chemical Society Parkin Transaction (J. Chem. Soc. Perkin Tr)
ans. ) 1 , 2191 (1980); S. Patai ed., The Chemistry of Organo Selenium and Tellurium Campounds (The Chemistry of Organo)
Selenium and Tellurium com
pounds), Volume 2, 216-267 (1987), Tetrahedron L.
et al.) 31 , 3587 (1990), Journal of Chemical Research, Synopses (J.C.
hem. Res. , Synopses) 2 , 56 (19
90), Bretane of the Chemical Society of Japan (Bull. Chem. Soc. J.
apan) 62 , 2117 (1989), ibid, 6
0 , 771 (1987), Journal of Organometallic Chemistry (J. Organometa)
llic Chem. 338 , 9 (1988), ib
id, 306 , C36 (1986), The Chemical Society of Japan 7
Vol., 1475 (1987), Zeitschrift Chemi (Zeitschrift Chemi)
e) 26 , 176 (1986); Chemistry Letters 3 , 475.
(1987), Indian Journal of Chemistry (Indian Journal of Chemistry)
chemistry, Section A) 25A , 57 (1
986), Angevante Hemy (Angewandt)
e Chemie) 97 , 1051 (1985), Spectrochimica acta.
Acta, Part A) 38A, 185 (198
2), Organic Preparation and Prosedia International (Organic Pr.)
evolutions and Procedures
International) 10 , 289 (197)
8), Organometallics (Organometallic)
lics) 1 , 470 (1982).

The tellurium sensitizer used in the present invention is a compound which forms silver telluride which is presumed to be a sensitizing nucleus on the surface of silver halide emulsion grains or inside the grains.

The following test can be performed for the formation rate of silver telluride in a silver halide emulsion.

When a large amount is added (for example, 1 × 10 ⁻³ mol / mol Ag), the formed silver telluride has an absorption in the visible region. Therefore, for the sulfur sensitizer, E.I. Moisar
Is the Journal of Photographic
Science, 14, 181 (1966),
16: 102 (1968). The amount of silver sulfide formed in the silver halide emulsion was determined by measuring the infinite reflectance (in) of the emulsion in the visible region (520 nm).
fine reflectivity) to Kub
The relative rate of silver telluride formation can be easily obtained by the same method as that obtained by using the elka-Munk equation. Since this reaction is apparently close to a first-order reaction, a pseudo-first-order reaction rate constant can also be obtained. For example, an octahedral silver bromide emulsion having an average particle size of 0.5 μm (1 kg
The emulsion contains 0.75 mol of AgBr and 80 g of gelatin) at 50 ° C. while maintaining pH = 6.3 and pAg = 8.3.
And a tellurium compound dissolved in an organic solvent (such as methanol) is added at 1 × 10 ⁻³ mol / mol Ag. Put the emulsion in a 1 cm thick cell with a spectrophotometer with an integrating sphere and reflectivity (R) at 520 nm with reference to the blank emulsion.
Is measured over time. Kubelka reflectivity
Substituting into the expression of -Munk (1-R) ² / 2R, a pseudo first-order reaction rate constant k (min ⁻¹ ) is obtained from a change in the value. Kubel because R = 1 always if silver telluride is not generated
The value of ka-Munk is the same as when there is no tellurium compound, and is 0.
Remains. The apparent first-order reaction rate constant k under exactly the same conditions as this test method is 1 × 10 ⁻⁸ to 1 × 10 ⁰ min.
^-1 is preferred.

In addition, in a smaller amount of addition where the absorption in the visible region is difficult to detect, the generated silver telluride can be separated from the unreacted tellurium sensitizer and quantified. For example, after separation by immersion in a halogen salt aqueous solution or an aqueous solution of a water-soluble mercapto compound, a trace amount of Te is quantitatively analyzed by an atomic absorption method or the like. The reaction rate depends on the silver halide composition of the test emulsion, the temperature to be tested, and the pAg as well as the type of the compound.
It fluctuates greatly within a range of several digits due to pH and pH. The tellurium sensitizer preferably used in the present invention is a compound capable of forming silver telluride in a specific silver halide emulsion having a halogen composition and a crystal habit to be used. Generally speaking, for silver bromide emulsions, a temperature of 40 to 95 ° C. and a pH of
In the range of 3 to 10, or pAg 6 to 11,
A compound capable of forming silver telluride is preferably used in the present invention. In this range, the pseudo-first-order reaction rate constant k according to the above test method is in the range of 1 × 10 ^-7 to 1 × 10 ^-1 min ^-1 . Compounds falling within are preferred as tellurium sensitizers.

The amount of the tellurium sensitizer used in the present invention varies depending on the silver halide grains to be used, the conditions of chemical ripening, and the like, but is generally from 10 ^-8 to 1 ^-8 per mol of silver halide.
It is used in an amount of 10 ⁻² mol, preferably about 10 ^{−7 to} 5 × 10 ⁻³ mol.

The conditions for chemical sensitization in the present invention include:
Although there is no particular limitation, the pAg is 6 to 11, preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 50 to 85 ° C.

In the present invention, it is preferable to use a noble metal sensitizer such as gold, platinum, palladium or iridium in combination. In particular, it is preferable to use a gold sensitizer in combination. Specifically, for example, chloroauric acid, potassium chloroaurate,
Potassium aurithiocyanate, gold sulfide, gold selenide, and 10 ^-7 to 10 ^-2 per mole of silver halide.
About moles can be used.

In the present invention, it is preferable to further use a sulfur sensitizer in combination. Specific examples include known unstable sulfur compounds such as thiosulfates (eg, hypo), thioureas (eg, diphenylthiourea, triethylthiourea, allylthiourea) and rhodanines. About 10 ^-7 to 10 ^-2 mol can be used per mol.

In the present invention, it is preferable to further use a selenium sensitizer in combination.

For example, an unstable selenium sensitizer described in JP-B-44-15748 is preferably used.

Specifically, colloidal selenium, selenoureas (eg, N, N-dimethylselenourea, selenourea, tetramethylselenourea), selenoamides (eg, selenoacetamide, N, N-dimethyl-selenobenzamide) ), Selenoketones (eg, selenoacetone, selenobenzophenone), selenides (eg, triphenylphosphine selenide, diethylselenide), selenophosphates (eg, tri-p-tolylselenophosphate), selenocarbon Examples thereof include compounds such as acids and esters, and isoselenocyanates, and about 10 ^-8 to 10 ^-3 mol can be used per 1 mol of silver halide.

At the time of chemical sensitization, there is no particular limitation on the timing and order of addition of a silver halide solvent, a selenium sensitizer, a sulfur sensitizer and a gold sensitizer. ) Or during the course of chemical ripening, the above compounds can be added at the same time or at different times. In addition, the above compound may be added after being dissolved in water or an organic solvent which can be mixed with water, for example, a single solution or a mixed solution of methanol, ethanol, and acetone.

In the present invention, a reduction sensitizer can be used in combination. Specifically, for example, stannous chloride, aminoiminomethanesulfinic acid, hydrazine derivatives, borane compounds (for example, dimethylamine borane) , Silane compounds and polyamine compounds.

In the present invention, tellurium sensitization is preferably performed in the presence of a silver halide solvent.

Specifically, for example, thiocyanates (eg, potassium thiocyanate), thioether compounds (eg, US Pat. Nos. 3,021,215 and 3,271,157)
No., JP-B-58-30571, JP-A-60-1367
No. 36, especially 3,6-dithia-1,
8-octanediol), tetra-substituted thiourea compounds (for example, Japanese Patent Publication No. 59-11892, U.S. Pat. No. 42218)
No. 63, particularly, tetramethylthiourea), further, a thione compound described in JP-B-60-11341, a mercapto compound described in JP-B-63-29727, and described in JP-A-60-160342. And selenoether compounds described in U.S. Pat. No. 4,781,2013, telluroether compounds described in JP-A-2-118566, and sulfites. In particular, among these, thiocyanates, thioether compounds, tetrasubstituted thiourea compounds and thione compounds can be preferably used. The amount used is about 10 ^-5 to 10 ^-2 mol per mol of silver halide.

Next, the compound (I) used in the present invention,
(II), (III) and (IV) will be described.

The general formula (I) will be described below in detail.

As R ₁ , R ₂ , R ₃ and R ₄ , for example, an unsubstituted alkyl group (for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl,
Octyl, dodecyl, octadecyl, cyclopentyl,
Cyclopropyl, cyclohexyl), substituted alkyl group. When the substituent is V, the substituent represented by V is not particularly limited, and examples thereof include carboxy, sulfo, cyano, and halogen atoms (eg, a fluorine atom, a chlorine atom, a bromine atom,
Iodine atom), hydroxy group, alkoxycarbonyl group (for example, methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl), alkoxy group (for example, methoxy, ethoxy, benzyloxy, phenethyloxy), aryloxy group having 18 or less carbon atoms ( For example, phenoxy, 4-methylphenoxy, α
-Naphthoxy), acyloxy groups (eg, acetyloxy, propionyloxy), acyl groups (eg, acetyl, propionyl, benzoyl, mesyl), carbamoyl groups (eg, carbamoyl, N, N-dimethylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl), Sulfamoyl groups (e.g., sulfamoyl,
N, N-dimethylsulfamoyl, morpholinosulfonyl, piperidinosulfonyl), aryl group (for example, phenyl, 4-chlorophenyl, 4-methylphenyl, α-
Naphthyl), a heterocyclic group (eg, 2-pyridyl, tetrahydrofurfuryl, morpholino, 2-thiopheno), an amino group (eg, amino, dimethylamino, anilino,
Diphenylamino), an alkylthio group (eg, methylthio, ethylthio), an alkylsulfonyl group (eg, methylsulfonyl, propylsulfonyl), an alkylsulfinyl group (eg, methylsulfinyl), a nitro group,
A phosphate group, an acylamino group (eg, acetylamino),
Ammonium group (eg, trimethylammonium, tributylammonium), mercapto group, hydracino group (eg, trimethylhydrazino), ureido group (eg, ureide, N, N-dimethylureido), imide group, unsaturated hydrocarbon group (eg, vinyl, Ethynyl, 1-cyclohexenyl, benzylidine, benzylidene). The number of carbon atoms of the substituent V is preferably 18 or less. V may be further substituted on these substituents.

More specifically, an alkyl group (for example, carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, 2-sulfoethyl,
3-sulfopropyl, 4-sulfobutyl, 3-sulfobutyl, 2-hydroxy-3-sulfopropyl, 2-cyanoethyl, 2-chloroethyl, 2-bromoethyl, 2-
Hydroxyethyl, 3-hydroxypropyl, hydroxymethyl, 2-hydroxyethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-ethoxycarbonylethyl, methoxycarbonylmethyl, 2-methoxyethyl,
2-ethoxyethyl, 2-phenoxyethyl, 2-acetyloxyethyl, 2-propionyloxyethyl, 2
-Acetylethyl, 3-benzoylpropyl, 2-carbamoylethyl, 2-morpholinocarbonylethyl, sulfamoylmethyl, 2- (N, N-dimethylsulfamoyl) ethyl, benzyl, 2-naphthylethyl, 2-
(2-pyridyl) ethyl, allyl, 3-aminopropyl, 3-methylaminopropyl, methylthiomethyl, 2
-Methylsulfonylethyl, methylsulfinylmethyl, 2-acetylaminoethyl, 3-trimethylammoniumethyl, 2-mercaptoethyl, 2-trimethylhydrazinoethyl, methylsulfonylcarbamoylmethyl, (2-methoxy) ethoxymethyl, and the like. ｝, An aryl group (for example, phenyl, α-naphthyl, β
-Naphthyl, for example, phenyl, naphthyl substituted by the substituent V described above, a heterocyclic group (for example, 2-pyridyl,
-Thiazolyl, 2-pyridyl substituted with the substituent V described above) is preferred.

R ₁ and R ₂ , R ₃ and R ₄ , R ₁ and R
₃ and R ₂ and R ₄ may combine with each other to form a ring. However, it does not form an aromatic ring. These rings may be substituted, for example, by the substituent V described above.

However, an oxo group is not substituted on a carbon atom of R ₁ , R ₂ , R ₃ and R ₄ which is directly bonded to a nitrogen atom of hydrazine. For example, R ₁ ,
R ₂ , R ₃ and R ₄ are not an acetyl group, a carboxy group, a benzoyl group, a formyl group, or a malonyl group, a succinyl group, a glutaryl group, or an adipoyl group when two form a ring.

A carbon atom directly bonded to the nitrogen atom of hydrazine among R ₁ , R ₂ , R ₃ and R ₄ is substituted by a thioxo group (for example, thioacetyl, thioaldehyde, thiocarboxy, thiobenzoyl). Not preferred.

More preferably, R ₁ , R ₂ , R ₃ and R ₄ are the above-mentioned unsubstituted alkyl groups, substituted alkyl groups, and R ₁ and R ₂ , R ₃ and R ₄ , R ₁ and R ₃ , and R ₂ and R ₄ are bonded to each other to form a ring other than a carbon atom (eg, an oxygen atom, a sulfur atom, a nitrogen atom)
Is the case where an alkylene group containing no (an alkylene group may be substituted (for example, the substituent V described above)) is formed.

More preferably, as R ₁ , R ₂ , R ₃ and R ₄ , the carbon atom directly bonded to the nitrogen atom of hydrazine is an unsubstituted methylene group or an alkyl group (eg, methyl, ethyl) -substituted methylene group. Is the case. Particularly preferably, an unsubstituted alkyl group (eg, methyl, ethyl, propyl, butyl), a substituted alkyl group {eg, a sulfoalkyl group (eg, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, 3-sulfobutyl), a carboxyalkyl group (Eg, carboxymethyl, 2-carboxyethyl), a hydroxyalkyl group (eg, 2-hydroxyethyl)}, and R ₁ and R ₂ , R ₃ and R ₄ ,
R ₁ and R ₃ and R ₂ and R ₄ are bonded to each other by an alkylene chain to form a 5-membered ring and a 7-membered ring.

The hydrazine compound represented by the general formula (I) may be isolated as a salt at any time in terms of synthesis and storage. In such a case, any compound may be used as long as it can form a salt with hydrazines, but preferred salts include the following.

For example, aryl sulfonates (for example, p
-Toluenesulfonate, p-chlorobenzenesulfonate), aryldisulfonates (eg, 1,3-benzenedisulfonate, 1,5-naphthalenedisulfonate, 2,6-naphthalenedisulfonate), thiocyanate Acid, picrate, carboxylate (eg, oxalate, acetate, benzoate, hydrogen oxalate), halogenate (eg, hydrochloride, hydrofluoride, hydrobromide) , Hydroiodide), sulfate, perchlorate, tetrafluoroborate, sulfite, nitrate, phosphate, carbonate, bicarbonate.

Preferred are hydrogen oxalate, oxalate and hydrooxide.

The general formula (II) will be described below in detail.

R ₅ and R ₆ have the same meanings as R ₁ , R ₂ , R ₃ and R ₄ , and the preferred ranges are also the same.

Particular preference is given to methyl and R ₅ and R ₆
Are bonded to each other to form unsubstituted tetramethylene.

Z ₁ represents an alkylene group having 4 or 6 carbon atoms, preferably an alkylene group having 4 carbon atoms.

However, there is no case where the oxo group is substituted on the carbon atom by directly bonding to the nitrogen atom of hydrazine.

This alkylene group may be unsubstituted or substituted. Examples of the substituent include the above-described substituent V. The carbon atom directly bonded to the nitrogen atom of hydrazine is preferably unsubstituted methylene or an alkyl group (for example, methyl or ethyl) -substituted methylene.

Particularly preferred as Z ₁ is unsubstituted tetramethylene.

The general formula (III) will be described below in detail.

R ₇ and R ₈ have the same meanings as R ₁ , R ₂ , R ₃ and R ₄ , and the preferred range is also the same.

Particularly preferred are a methyl group and R ₇ and R
₈ are bonded to each other to form a trimethylene group.

Z ₂ represents an alkylene group having 2 carbon atoms.

Z ₃ represents an alkylene group having 1 or 2 carbon atoms.

These alkylene groups may be unsubstituted or substituted. Examples of the substituent include the substituent V described above.

As Z ₂ , more preferably, unsubstituted ethylene.

More preferably, Z ₃ is unsubstituted methylene and ethylene.

L ₁ and L ₂ represent methine or substituted methine. Examples of the substituent include the substituent V described above, and preferably an unsubstituted alkyl group (for example, methyl,
t-butyl).

Further preferred is unsubstituted methine.

The general formula (IV) will be described in detail. Z
₄ and Z ₅ represent an alkylene group having 3 carbon atoms.

However, the carbon atom directly bonded to the nitrogen atom of hydrazine is not substituted with an oxo group.

These alkylene groups may be unsubstituted or substituted. Examples of the substituent include the substituent V described above, and the carbon atom directly bonded to the nitrogen atom of hydrazine is preferably an unsubstituted methylene or an alkyl group (for example, methyl or ethyl) -substituted methylene.

Particularly preferred as Z ₄ and Z ₅ are unsubstituted trimethylene and unsubstituted alkyl-substituted trimethylene (for example, 2,2-dimethyltrimethylene).

The compounds represented by formulas (II), (III) and (IV) may be isolated as salts in the same manner as the compounds represented by formula (I). As salt,
The same salts as those represented by the general formula (I) can be mentioned. Preferred are hydrogen oxalate, oxalate and hydrochloride.

Typical examples of the compounds represented by formulas (I), (II), (III) and (IV) are shown below.
It is not limited to this.

Compounds represented by the general formula (I) (The compounds represented by the general formula (I)
Includes compounds represented by (III) and (IV). However, here, as the compound represented by the general formula (I),
Examples excluding the compounds represented by formulas (II), (III) and (IV) will be given.

[0139]

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[0140]

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[0141]

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[0142]

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[0143]

Embedded image Compound represented by general formula (II)

[0144]

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[0145]

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[0146]

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[0147]

Embedded image Compound represented by general formula (III)

[0148]

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[0149]

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[0150]

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[0151]

Embedded image Compound represented by general formula (IV)

[0152]

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[0153]

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[0154]

Embedded image The hydrazines of the present invention can be synthesized by various methods. For example, it can be synthesized by a method of alkylating hydrazine. Examples of the alkylation method include a method of directly alkylating with an alkyl halide and an alkyl sulfonate, a method of reductively alkylating with a carbonyl compound and sodium cyanoborohydride,
Also, a method is known in which the acylated compound is reduced using lithium aluminum hydride. For example, SR Sandler, W. Karo, "Organic Functional Group Preparations (Organi).
c Functional Group Prepara
volume, Chapter 14, Chapter 14, pp. 434-465 (1968), Academic Press (Academ)
ic Press).

The compound represented by the general formula (I) is, for example, EL Clennan
Journal of the American Chemical Society (Journal of The Ame)
rican Chemical Society) 11th
Vol. 2, No. 13, page 5080 (1990), and can be synthesized by referring to them.

Examples of the synthesis of typical compounds are described below. (Synthesis Example 1) Synthesis of Compound (1-1) 70 g of propionaldehyde (1,1 mol) in 500 ml of 1,1-dimethylhydrazine (0.2 mol) and acetonitrile.
2 mol), and 25 g (0.396 mol) of sodium cyanoborohydride is added dropwise with stirring at room temperature. After further stirring for 1 hour, 48.3 g of acetic acid was added under ice cooling.
(0.804 mol) was added dropwise, and the mixture was further stirred at room temperature for 2 hours. Next, 100 ml of concentrated hydrochloric acid was added dropwise under ice-cooling, the solvent was distilled off, and the mixture was distilled under reduced pressure to give compound (1-1) (a colorless liquid,
48-52 ° C./16 mmHg, 3.95 g, yield 14
%). (Synthesis Example 2) Synthesis of compound (1-2) (1-1) 2.5 g (0.027 mol) of oxalic acid / 50 ml of ethyl acetate were added to 3.95 g (0.027 mol) and 50 ml of ethyl acetate. Stir at room temperature. The precipitated crystals were separated by filtration by suction filtration and dried. Compound (1-2) (colorless crystals, mp = 128 to 131 ° C, 5.3 g, yield 83)
%).

Compounds represented by the general formula (II) include, for example, SF Nelsen and the like.
Journal of the American Chemical Society (Journal of The Ameri)
Can Chemical Society) Vol. 98, No. 1
2, No. 5269 (1976), SF Nelsen, GR Weisman, Tetrahedron Letter No. 26,
No. 2321 (1973) and the like, and can be synthesized by referring to them.

Examples of the synthesis of typical compounds are described below. (Synthesis Example 3) Synthesis of Compound (2-3) Synthesis Route

[0159]

Embedded image 20 g (0.163 mol) of compound (A), compound (A)
After heating and refluxing 16.3 g (0.163 mol) and acetic acid 80 ml for 15 hours, 50 ml of water and 100 ml of a 5% aqueous sodium hydroxide solution were added thereto, and chloroform 200 ml was added.
Extract with l. After drying over anhydrous sodium sulfate, the solvent is distilled off under reduced pressure. When 200 ml of ethyl acetate is added to the obtained oil and 200 ml of hexane is further added, crystals are precipitated. After filtration by suction filtration and drying, the compound (C)
(Colorless crystals, 8.65 g, yield 32%) was obtained.

8.9 g of lithium aluminum hydride
(0.235 mol), 100 ml of tetrahydrofuran was cooled to 0 ° C., and 7.9 g (0.04 mol) of (C) was stirred.
7 mol) / 70 ml of tetrahydrofuran solution is slowly added dropwise. At this time, the reaction solution is kept at 5 ° C. or lower. 4 at room temperature
After stirring for an hour, the reaction solution was cooled again to 0 ° C.
1, 15% aqueous sodium hydroxide solution 9 ml, water 27 ml
, And the precipitated colorless crystals are removed by filtration with suction filtration. The filtrate was dried over anhydrous sodium sulfate, and after removing the solvent by distillation under reduced pressure, the compound (2-3) (colorless liquid, 1.44 g, 85-90 ° C./25 mmHg, 17% yield) was obtained by distillation under reduced pressure. Obtained. (Synthesis Example 4) Synthesis of Compound (2-1) To 6 g (0.043 mol) of compound (2-3) and 100 ml of ethyl acetate, a solution of 4.3 g (0.048 mol) of oxalic acid in 120 ml of ethyl acetate was added. And stir. The precipitated crystals were separated by filtration by suction filtration and dried, and then dried. Compound (2-1) (9.3 g of colorless crystals, mp. 129 to 131 ° C, yield: 94%)
I got (Synthesis Example 5) Synthesis of Compound (2-5) Synthesis Route

[0161]

Embedded image Compound (D) 40 g (0.4 mol), Compound (A) 2
5.2 g (0.42 mol) and 20 ml of acetic acid are heated under reflux for 2 hours. 100 ml of water and 100 ml of a 5% aqueous sodium hydroxide solution were added to the reaction solution, and 200 ml of chloroform was added.
Extract with After the chloroform layer is dried over magnesium sulfate, the solvent is distilled off under reduced pressure, and then 50 ml of ethyl acetate and 150 ml of hexane are added and stirred to precipitate crystals. After filtering off with suction filtration, drying is performed to obtain compound (e) (colorless crystals, 26
g, yield 44%).

26.7 g of lithium aluminum hydride
(0.7 mol), 300 ml of tetrahydrofuran at 0 ° C.
The compound (e) 20 g (0.14
Mol) / 100 ml of tetrahydrofuran solution is added dropwise. At this time, the reaction solution is kept at 10 ° C. or lower. 2 hours,
After stirring at room temperature, the mixture was cooled again to 0 ° C., and 27 ml of water, 15%
27 ml of aqueous sodium hydroxide solution and 71 ml of water are added dropwise. At this time, the internal temperature is kept at 25 ° C. or less. The precipitated crystals are removed by filtration by suction filtration, and 200 ml of water and 200 ml of methylene chloride are added to the filtrate, followed by extraction. After the methylene chloride layer was dried over anhydrous sodium sulfate, the solvent was distilled off under normal pressure, and further distilled under normal pressure to obtain the compound (2-5) (liquid,
1.42 g, 75-78 ° C / 760 mmHg, yield 9
%). (Synthesis Example 6) Synthesis of compound (2-4) 0.8 g (0.007 mol) of compound (2-5), 0.63 g (0.007 mol) of oxalic acid in 10 ml of ethyl acetate
/ 10 ml of ethyl acetate is added and stirred. The precipitated crystals were collected by suction filtration and filtered to obtain compound (2-4) (colorless crystals 1.2).
6 g, mp = 104-106 ° C., yield 88%).

The compound represented by the general formula (III) is exemplified by HR Snyder Jr. (HR Sny).
der, JR), J.G. Michel (JG.
Michels), Journal of Organic
Chemistry (Journal of Organic)
Chemistry) 28, 1144 (196
3 years), JE Anderson (JE And
erson), JM Leh
n), Journal of the American Chemistry (Journal of the American Chemistry)
Chemistry) Vol. 89, No. 1, page 81 (196
7 years), Hermann Steter
tter), Peter Woe
rnle) Justus Liebig Analen del Del
Hemy (Justus Liebigs Ammale)
der Chemie) No. 724, p. 150 (1
969), SF Nelsen (SF Nels)
en) and the like, tetrahedro (Tetrahedro)
n), Vol. 42, No. 6, page 1769 (1986) and the like, and can be synthesized by referring to them.

The following are synthesis examples of typical compounds. (Synthesis Example 7) Synthesis of Compound (3-20) Synthesis Route

[0165]

Embedded image 120 g (0.554 mol) of compound (f), 55.5 g (1.11 mol) of compound (g), 30 g (0.554 mol) of sodium methoxide, 150 ml of ethanol
After heating under reflux for 1 hour, ethanol was distilled off under normal pressure, and water 60
0 ml and 450 ml of ether are added and stirred at room temperature. The aqueous layer is separated and brought to pH = 2 with concentrated hydrochloric acid. The precipitated crystals are separated by suction filtration, and the compound (h) (colorless crystals, 2
6 g, yield 30%).

Compound (h) 25 g (0.16 mol),
12.8 g (0.16 mol) of 1,3-cyclohexadiene and 150 ml of methylene chloride were cooled under ice-cooling with 78.8 g (0.178 mol) of lead tetraacetate / 25 methylene chloride.
0 ml solution was added dropwise. After stirring for 6 hours under ice-cooling, the precipitated crystals were removed by filtration, and 0.8 L of water was added to the filtrate for extraction. After the methylene chloride layer was dried over anhydrous sodium sulfate, the solvent was distilled off, and the residue was recrystallized from ligroin to give compound (q) (21 g of colorless crystals, yield 56%).
%).

20.5 g (0.087 mol) of compound (q), 260 ml of ethanol and 2 g of 5% palladium-carbon were subjected to catalytic hydrogen reduction with 16 kg / cm ² of hydrogen gas at room temperature for 12 hours. After removing 5% palladium-carbon by celite filtration, evaporating the solvent and recrystallizing with ligroin, compound (co) (17.4 g of colorless crystals,
(85% yield).

4 g of lithium aluminum hydride (0.1 g)
0.05 mol) and 210 ml of tetrahydrofuran were added dropwise with stirring at room temperature while a solution of 16.5 g (0.07 mol) of compound (co) in 210 ml of tetrahydrofuran was added dropwise.

At this time, the reaction solution was kept at 30 ° C. or lower. After stirring for 3 hours, the reaction solution was cooled to 0 ° C., 4 ml of water,
4 ml of a 15% aqueous sodium hydroxide solution and 12 ml of water were added, the precipitated crystals were removed by filtration by suction filtration, the filtrate was dried over anhydrous sodium sulfate, and the solvent was distilled off. The compound (3-20) (liquid, 125-1) was further distilled under reduced pressure.
28 ° C./4.5 mmHg, 6.4 g, yield 44%). (Synthesis example 8)-Synthesis of compound (3-19) When hydrochloric acid gas is passed through 1.5 g of compound (3-20) and 50 ml of ethyl acetate, crystals are precipitated. The crystals were filtered off by suction filtration and dried, and the compound (3-19) (colorless crystals 1.
17g, mp = 128-130 ° C, yield 66%). (Synthesis Example 9) Synthesis of Compound (3-2) Synthesis Route

[0170]

Embedded image 84.5 g (0.485 mol) of compound (sa) and 100 ml of ether were cooled to 5 ° C. or lower, and 48.1 g (0.728 mol) of compound (cy) cyclopentadiene synthesized by thermal decomposition of dicyclopentadiene with stirring. ) / 60 ml of ether solution was added dropwise. The mixture was further stirred for 1 hour, and the solvent was distilled off under reduced pressure.
04-5 ° C / 0.48 mmHg, 101 g, yield 86
%).

50 g (0.21 mol) of the compound (S), 500 ml of methanol, and 5 g of 5% palladium-carbon were subjected to catalytic hydrogen reduction at room temperature for 12 hours at 14 kg / cm ² of hydrogen gas. The 5% palladium-carbon was removed by celite filtration, the solvent of the filtrate was distilled off under reduced pressure, and the residue was distilled under reduced pressure to obtain a compound (C) (colorless liquid, 135 ° C / 1.5 mmH).
g, 48 g, 95% yield).

7.1 g of lithium aluminum hydride
(0.186 mol), compound (C) in 75 ml of ether
15 g (0.062 mol) / 50 ml of ether were added dropwise. At this time, the temperature of the reaction solution rose to 35 ° C.

Further, the mixture was stirred at room temperature for 2 hours, and 13 ml of water was added.
Was added. The precipitated crystals were removed by filtration by suction filtration, the filtrate was dried over magnesium sulfate, the solvent was distilled off under normal pressure, and the residue was distilled under reduced pressure to give compound (3-2) (colorless liquid, 60 to 50%).
67 ° C./25 mmHg, 2.9 g, 14% yield). (Synthesis Example 10) Synthesis of Compound (3-1) 2.9 g (0.023 mol) of compound (3-2) and 2.25 g (0.025 mol) of oxalic acid in 30 ml of ethyl acetate
/ Ethyl acetate (30 ml) was added, and the precipitated crystals were filtered off by suction filtration and dried. Compound (3-1) (colorless crystals, mp
= 118-120 ° C, 4.2 g, yield 85%). (Synthesis Example 11)-Synthesis of compound (3-27) Lithium aluminum hydride (4.8 g, 0.125 mol) and compound (su) 10 g (0.0
42 mol) / 50 ml of ether was added dropwise. At this time,
The temperature of the reaction rose to 35 ° C.

After stirring at room temperature for 1 hour, water 1
3 ml was added, and the precipitated crystals were removed by suction filtration. The filtrate was dried over magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was distilled under reduced pressure to obtain compound (2-26) (colorless liquid, 8
0-88 ° C / 75 mmHg, 0.9 g, 17% yield). (Synthesis Example 12) Synthesis of compound (3-26) 0.9 g (0.007 mol) of compound (3-26), 0.7 g (0.008 mol) of oxalic acid in 10 ml of ethyl acetate
/ 10 ml of ethyl acetate was added, and the precipitated crystals were filtered off with suction and dried, and dried to give compound (3-25) (colorless crystals, m.p.
p = 106-108 ° C., 1.2 g, yield 76%).

Compounds represented by the general formula (III) include, for example, SF Nelsen and the like.
Journal of the American Chemistry (J
own of the American Ch
Chemical Society), Vol. 96, No. 9, 29
16 (1974), L. Bourre (ELB)
uhl) et al., of the Journal of the American Chemistry (Journal of The Amer)
ican Chemical Society), No. 6
No. 5, p. 29 (1943), and can be synthesized by referring to them.

Examples of the synthesis of typical compounds are described below. (Synthesis Example 13) Synthesis of Compound (4-1) Synthesis Route

[0177]

Embedded image 16 g of the compound (SO), 300 ml of water and 200 g of ice were stirred, and 100 g of the compound (TA) was added dropwise. One hour later, 200 ml of methanol, 100 ml of water and 500 ml of ethyl acetate were added for extraction. After the ethyl acetate layer was dried over magnesium sulfate, the solvent was distilled off under reduced pressure, and water was added to the residue. After filtering the precipitated crystals by suction filtration, and drying,
Compound (H) (colorless crystal, mp = 206-207 ° C., 8
1 g, 94% yield).

Compound (h) 80 g, methanol 200 m
1 liter of sodium methoxide 28% methanol solution 200
Add ml. After heating under reflux for 5 hours, methanol is distilled off under reduced pressure.

200 ml of methanol was added to the residue, the solid was removed by filtration, and the filtrate was concentrated, and then purified by column chromatography using Sephadex LH-20 as a carrier and methanol as an eluent. Recrystallized from water to give compound (T) (colorless crystal, mp = 164 to 16)
7 ° C., 21 g, 36% yield).

7 g of lithium aluminum hydride is added little by little to 17 g of the compound (T) and 200 ml of tetrahydrofuran. After heating under reflux for 6 hours, the reaction solution is poured into ice water, made alkaline with sodium hydroxide, and extracted with 300 ml of ethyl acetate. After drying the ethyl acetate layer over anhydrous sodium sulfate, the solvent is distilled off under reduced pressure, and the residue is purified by column chromatography using alumina as a carrier and ethyl acetate as an eluent. After evaporating the solvent of the target fraction under reduced pressure, the residue is dissolved in 20 ml of ethyl acetate, 10 g of oxalic acid is added, and the mixture is heated and dissolved. After cooling, the precipitated crystals were separated by suction filtration and dried, and the compound (4-
1) (colorless crystals, mp = 203-206 ° C., 4.5 g,
Yield 20%). (Synthesis Example 14) Synthesis of Compound (4-8) Compound (4-1) was dissolved in methanol, and excess NaH was dissolved.
After CO ₃ was added and neutralized, the solid was filtered off, and the solvent of the filtrate was distilled off under reduced pressure to obtain compound (4-8) (colorless liquid).

The compound of the present invention represented by the general formula (I), (II), (III) or (IV) may be added at any time before or after the sensitizing dye, and is preferably in each case per mole of silver halide. 1.times.10.sup.- ^{6 to} 5.times.10.sup.- ¹ mol, more preferably 1.times.10.sup.- ⁵ to 2.times.10.sup.- ² mol, particularly preferably 1.times.10.sup.-1 mol.
It is contained in the silver halide emulsion at a ratio of 0 ^{-4 to} 1.6 × 10 ^-2 mol.

A sensitizing dye and a compound represented by any of formulas (I), (II) and (II)
Ratio (molar ratio) of the compound represented by I) or (IV)
May be any value, but the sensitizing dye / (I), (I
The range of (I), (III) or (IV) = 10/1 to 1/1000 is advantageously used, particularly the range of 1/1 to 1/100 is used advantageously.

In the present invention, a monodispersed silver halide emulsion is preferably used as the silver halide emulsion.

In the present invention, a monodisperse silver halide emulsion means one having a coefficient of variation in particle size distribution of 0.20 or less when the grain group is observed by an electron micrograph. Here, the variation coefficient of the particle size distribution indicates a value obtained by dividing the standard deviation of the particle size distribution by the average particle size.

In the present invention, the monodisperse silver halide emulsion means one having a coefficient of variation of 0.20 or less, preferably 0.18 or less, more preferably 0.15 or less.
It is as follows.

The silver halide emulsion used in the present invention includes silver bromide, silver chloride, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide,
It is silver chloroiodobromide. Other silver salts, such as rodin silver,
Silver sulfide, silver selenide, silver carbonate, silver phosphate, and organic acid silver may be contained as separate grains or as a part of silver halide grains. When rapid development and desilvering (bleaching, fixing and bleach-fixing) steps are desired, silver halide grains having a high silver chloride content are desirable. In order to appropriately suppress development, it is preferable to contain silver iodide.
The preferred silver iodide content depends on the intended light-sensitive material.
For example, the preferred range is 0.1 to 15 mol% for X-ray sensitive materials, and 0.1 to 5 mol% for graphic arts and micro sensitive materials. In the case of a photographic light-sensitive material represented by a color negative, a silver halide containing 1 to 30 mol% of silver iodide is preferred, more preferably 2 to 20 mol%, and particularly preferably 3 to 15 mol%. is there. It is preferable that silver iodobromide grains contain silver chloride in order to reduce lattice strain.

The silver halide emulsion of the present invention preferably has a distribution or structure relating to the halogen composition in the grains. A typical example is, for example,
No. 13162, JP-A-61-215540, JP-A-6-215540
No. 0-222845, JP-A-60-143331, and JP-A-61-75337, which are core-shell type or double structure type particles having a halogen composition in which the inside and the surface of the grains have different halogen compositions. is there. In addition to a simple structure, a triple structure as disclosed in Japanese Patent Application Laid-Open No. 60-222844, or a multilayer structure of more than that, or a different composition on the surface of a core-shell double structure particle Or a thin silver halide having the following formula:

In order to provide a structure inside the particle, not only the above-described wrapping structure but also a particle having a so-called junction structure can be produced. These examples are described in, for example, JP-A-59-133540 and JP-A-58-108526.
No. 199,290A2, Japanese Patent Publication No. 58-2
No. 4772 and JP-A-59-16254. The crystal to be bonded can be formed by bonding to the edge, corner, or surface of the host crystal with a composition different from that of the host crystal. Such a junction crystal can be formed even if the host crystal is uniform in the halogen composition or has a core-shell structure.

In the case of a joint structure, a combination of silver halides is naturally possible, but a silver salt compound having no rock salt structure, such as silver rhodanate or silver carbonate, can also be combined with silver halide to form a joint structure. Further, a non-silver salt compound such as lead oxide may be used as long as the bonding structure is possible.

In the case of silver iodobromide grains having such a structure, it is a preferable embodiment that the core portion has a higher silver iodide content than the shell portion. Conversely, grains having a low silver iodide content in the core portion and a high content in the shell portion are sometimes preferred. Similarly, grains having a junction structure may be grains having a high silver iodide content in the host crystal and relatively low silver iodide content in the junction crystal, or vice versa. Further, the boundary portions having different halogen compositions of the grains having these structures may be clear boundaries or unclear boundaries. In addition, a configuration in which the composition is positively and continuously changed is also a preferable embodiment.

In the case of silver halide grains in which two or more silver halides are present as mixed crystals or with a structure, it is important to control the halogen composition distribution between grains. The method for measuring the halogen composition distribution between grains is described in JP-A-60-254032. Uniform halogen distribution between grains is a desirable property. In particular, a highly uniform emulsion having a coefficient of variation of 20% or less is preferable.
Another preferred form is an emulsion having a correlation between the grain size and the halogen composition. As an example, there is a case where the correlation is such that the iodine content is higher for the larger size particles, while the iodine content is lower for the smaller size particles. Depending on the purpose, an inverse correlation or a correlation with another halogen composition can be selected. For this purpose, it is preferable to mix two or more emulsions having different compositions.

It is important to control the halogen composition near the grain surface. Increase the silver iodide content near the surface,
Alternatively, by increasing the silver chloride content, the adsorptivity of the dye and the developing speed change, so that it can be selected according to the purpose. When changing the halogen composition in the vicinity of the surface, either a structure that wraps the entire grain or a structure that adheres only to a part of the grain can be selected. For example, this is a case where the halogen composition of only one surface of a tetrahedral grain composed of the (100) plane and the (111) plane is changed, or one of the main plane and the side surface of the tabular grain is changed.

The silver halide grains used in the present invention may be, for example, normal crystals containing no twin planes, or edited by the Photographic Society of Japan, basics of the photographic industry, silver salt photography (Corona), P.I. 163, such as a single twin containing one twin plane, a parallel multiple twin containing two or more parallel twin planes, a non-parallel containing two or more non-parallel twin planes It can be selected from multiple twins according to the purpose. An example of mixing particles having different shapes is disclosed in U.S. Pat. No. 4,865,964, but this method can be selected if necessary. In the case of a normal crystal, a cube consisting of (100) planes,
Octahedron consisting of (111) plane, Japanese Patent Publication No. 55-42737
And Japanese Patent Application Laid-Open No. 60-222842 (1).
10) A dodecahedral particle having a plane can be used.
Furthermore, Journal of Imaging Sc
(Vol. 30), p. 247 (h11) plane particles represented by (211), (hh1) plane particles represented by (331), and (2) as reported in 1986.
10) A (hk0) plane particle representing the plane or (32)
The (hk1) plane particles representing the 1) plane also need to be devised in the preparation method, but can be selected and used according to the purpose. (1
A tetrahedral particle in which (00) plane and (111) plane coexist in one particle, a particle in which (100) plane and (110) plane coexist,
Alternatively, a particle in which two surfaces or a large number of surfaces coexist, such as a particle in which the (111) plane and the (110) plane coexist, can be selected and used according to the purpose.

The value obtained by dividing the circle equivalent diameter of the projected area by the grain thickness is called an aspect ratio, and defines the shape of tabular grains. Tabular grains having an aspect ratio of greater than 1 can be used in the present invention. Tabular grains are described, for example, in Cleeve, "Theory and Practice of Photography" (Cleve, Photography).
Theory and Practice (193
0)), p. 131; Gatov, Photographic Science and Engineering (Gutoff, P.
photographic Science and E
14, 248-257 (1970); U.S. Patent Nos. 4,434,226, 4,414,310, 4,433,048, 4,439,520 and UK Patent No. 2,112,1
No. 57 can be prepared. When tabular grains are used, there are advantages such as an increase in covering power and an increase in the efficiency of color sensitization by a sensitizing dye, which is described in detail in U.S. Pat. No. 4,434,226 cited above. . The average aspect ratio of 80% or more of the total projected area of the grains is desirably 1 or more and less than 100. It is more preferably 2 or more and less than 20, particularly preferably 3 or more and 1 or less.
It is less than 0. The shape of the tabular grains can be selected from triangles, hexagons, and circles. US Patent 4,79
A regular hexagon having substantially equal lengths of six sides as described in US Pat. No. 7,354 is a preferred form.

In order to use the tabular grains as the monodispersed silver halide emulsion of the present invention, any method may be employed as long as the resulting composition is monodispersed. For example, U.S. Pat.
It can be obtained by the method described in US Pat.

As the particle size of tabular grains, the circle equivalent diameter of the projected area is often used, but US Pat.
No. 8,106 has an average diameter of 0.6.
Submicron particles are preferred for high image quality. It is preferable to limit the thickness of the tabular grains to 0.5 μm or less, more preferably 0.3 μm or less, in order to increase sharpness. Furthermore, the variation coefficient of the particle thickness is 3
Emulsions having a thickness uniformity of 0% or less are also preferred. Further, particles described in JP-A-63-163451, in which the thickness of the particles and the distance between twin planes are specified, are also preferable.

In the case of tabular grains, dislocation lines can be observed with a transmission electron microscope. It is preferable to select a particle containing no dislocation line, a particle containing several dislocations, or a particle containing many dislocations according to the purpose. In addition, dislocations introduced linearly or distorted dislocations in a specific direction of the crystal orientation of the grain can be selected, dislocations introduced over the entire grain, or introduced only in a specific portion of the grain, For example, it can be selected from dislocations introduced only in the fringe portion of the particle. The introduction of dislocation lines is preferable not only in the case of tabular grains but also in the case of normal grains or irregular grains typified by potato grains. Also in this case, it is a preferable embodiment to limit the particle to a specific portion such as a vertex or a ridge.

The silver halide emulsion used in the present invention may be prepared by subjecting grains to a rounding treatment as disclosed in, for example, European Patent Nos. 96,727B1 and 64,412B1, or West German Patent No. 2,306,447C2. , JP 6
The surface may be modified as disclosed in JP-A-221320.

A structure having a flat particle surface is generally used.
It is sometimes preferable to form the irregularities intentionally. JP-A-58-106532, JP-A-60-221
For example, a method of making a hole in a part of a crystal described in No. 320, for example, a vertex or a center of a plane, or a raffle particle described in US Pat. No. 4,643,966.

The grain size of the emulsion used in the present invention ranges from ultrafine particles having a sphere equivalent diameter of 0.05 μm or less to 1 μm or less.
It can be used by selecting from coarse particles exceeding 0 microns. Preferably, grains of 0.05 to 3 microns can be used as photosensitive silver halide grains.

In order to satisfy the target gradation of the light-sensitive material, two or more kinds of monodisperse silver halide emulsions having different grain sizes are mixed in the same layer in an emulsion layer having substantially the same color sensitivity. Alternatively, it can be applied in another layer. Further, two or more kinds of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion can be used as a mixture or as a mixture.

The photographic emulsion used in the present invention is described, for example, in "Physics and Chemistry of Photography" by Grafkid, published by Paul Montel (P. Glafkids, Chimie et Ph.).
ysique Photographique Pau
l Montel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GF Duffi).
n, Photographic Emulsion C
hemistry (Focal Press, 196)
6)), "Manufacture and Coating of Photographic Emulsion" by Zelikuman et al., Focus Press (VL Zelikman et al.).
al, Making and Coating Ph
autographic Emulsion, Foca
1, Press, 1964). That is, for example, any of an acidic method, a neutral method, and an ammonia method may be used, and as a method for reacting a soluble silver salt and a soluble halide, for example, a one-sided mixing method, a double-mixing method, or a combination thereof may be used. Good. A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained, which is a preferable method for obtaining the emulsion of the present invention.

A method in which silver halide grains previously formed are added to a reaction vessel for preparing an emulsion, or US Pat. Nos. 4,334,012 and 4,301,241.
Nos. 4,150,994 are sometimes preferred. These can be used as seed crystals, and are also effective when supplied as silver halide for growth. In the latter case, it is preferable to add an emulsion having a small grain size, and the addition method can be selected from the method of adding the whole amount at a time, adding in a plurality of times or adding continuously. It is also effective in some cases to add particles of various halogen compositions to modify the surface.

A method for converting most or only a part of the halogen composition of silver halide grains by a halogen conversion method is described, for example, in US Pat. Nos. 3,477,852 and 4,142,900, and EP 273,429. No. 273,430, West German Patent 3,819,241.
And is an effective particle formation method. A solution of a soluble halogen or silver halide grains can be added to convert the silver salt into a sparingly soluble silver salt. It can be selected from methods such as converting at once, converting into a plurality of times, or converting continuously.

Regarding grain growth, in addition to the method of adding a soluble silver salt and a halogen salt at a constant concentration and a constant flow rate, British Patent No. 1,469,480 and US Patent No. 3,650,
As described in U.S. Pat. Nos. 757 and 4,242,445, a particle forming method in which the concentration is changed or the flow rate is changed is also a preferable method. By increasing the concentration or increasing the flow rate, the amount of silver halide to be supplied can be changed by a linear function, a quadratic function, or a more complicated function of the addition time. It is also preferable in some cases to reduce the amount of silver halide supplied as necessary. Further, when adding a plurality of soluble silver salts having different solution compositions or adding a plurality of soluble halide salts having different solution compositions, an addition method of increasing one and decreasing the other is also an effective method. It is.

A mixer for reacting a solution of a soluble silver salt with a soluble halide salt is disclosed in US Pat. No. 2,996,287.
Nos. 3,342,605 and 3,415,650
No. 3,785,777, West German published patent 2,55
6,885 and 2,555,364.

A silver halide solvent is useful for the purpose of accelerating ripening. For example, it is known to have an excess of halogen ions in the reactor to promote ripening. Other ripening agents can also be used. These ripening agents can be incorporated in their entirety in the dispersion medium in the reactor before adding the silver and halide salts,
A halide salt, silver salt or deflocculant can be added and introduced into the reactor. As another variant, the ripening agent can be introduced independently during the halide salt and silver salt addition steps.

Examples of the silver halide solvent include ammonia, thiocyanates (for example, rhodacali and rhodamonium ammonium), and organic thioether compounds (for example, US Pat. Nos. 3,574,628 and 3,021,215;
Nos. 3,057,724, 3,038,805, 4,276,374, 4,297,439, 3,704,130, 4,782,013, JP Compounds described in JP-A-57-104926) and thione compounds (for example, JP-A-53-82408 and JP-A-55-777).
No. 37, tetra-substituted thioureas described in U.S. Pat. No. 4,221,863, compounds described in JP-A-53-144319) and JP-A-57-20253.
Mercapto compounds and amine compounds capable of promoting the growth of silver halide grains described in No. 1 (for example,
No. 4-100717).

Gelatin is advantageously used as a protective colloid used in preparing the emulsion of the present invention and as a binder for other hydrophilic colloid layers, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin with other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives A variety of synthetic hydrophilic polymer substances such as homo- or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Can be used.

Examples of gelatin include lime-processed gelatin, acid-processed gelatin, and Bull. Soc. Sci. Ph
oto. Japan. No. 16. P30 (1966)
Enzyme-treated gelatin as described in may be used,
In addition, a hydrolyzate or enzymatic decomposition product of gelatin can also be used.

The emulsion of the present invention is preferably washed with water for desalting and dispersed in a newly prepared protective colloid. The temperature for water washing can be selected according to the purpose, but is preferably selected in the range of 5 to 50 ° C. The pH at the time of washing can be selected according to the purpose, but is preferably selected from 2 to 10. More preferably, it is in the range of 3 to 8. The pAg at the time of washing can be selected according to the purpose, but is preferably selected from 5 to 10. The method for washing can be selected from noodle washing, dialysis using a semipermeable membrane, centrifugal separation, coagulation sedimentation, and ion exchange. In the case of the coagulation sedimentation method, a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative, and the like can be selected.

When preparing the emulsion of the present invention, for example, during grain formation,
The presence of a metal ion salt during the desalting step, during chemical sensitization, or before coating is preferable depending on the purpose. In the case of doping the grains, it is preferable to add them at the time of grain formation, when modifying the grain surface or when using as a chemical sensitizer, after grain formation and before the end of chemical sensitization. In the case of doping the entire grain, a method of doping only the core portion, only the shell portion, only the epitaxial portion, or only the base grain of the grain can be selected. Specifically, for example, Mg, Ca, Sr, B
a, Al, Sc, Y, LaCr, Mn, Fe, Co, N
i, Cu, Zn, Ga, Ru, Rh, Pd, Re, O
s, Ir, Pt, Au, Cd, Hg, Tl, In, S
n, Pb, and Bi can be used. These metals can be added as long as they can be dissolved at the time of particle formation, such as ammonium salts, acetates, nitrates, sulfates, phosphates, hydroxides, hexacoordinate complex salts, and tetracoordinate complex salts. Examples include CdBr ₂ , CdCl ₂ , Cd (N
O ₃ ) ₂ , Pb (NO ₃ ) ₂ , Pb (CH ₃ CO
O) ₂ , K ₃ [Fe (CN) ₆ ], (NH ₄ ) ₄ [Fe
(CN) ₆ ], K ₃ IrCl ₆ , (NH ₄ ) ₃ RhCl
₆ , K ₄ Ru (CN) ₆ . The ligand of the coordination compound includes halo, aquo, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo,
You can choose from carbonyls. These may be used alone or in combination of two or more metal compounds.

The metal compound is preferably dissolved in water or a suitable solvent such as methanol or acetone and added.
In order to stabilize the solution, a method of adding an aqueous solution of hydrogen halide (eg, HCl, HBr) or an alkali halide (eg, KCl, NaCl, KBr, NaBr) can be used. Further, an acid, an alkali or the like may be added as necessary. The metal compound may be added to the reaction vessel before the formation of the particles or may be added during the formation of the particles.
It can also be added to a water-soluble silver salt (eg, AgNO ₃ ) or an aqueous solution of an alkali halide (eg, NaCl, KBr, KI) and added continuously during the formation of silver halide grains. Further, a solution independent of the water-soluble silver salt and alkali halide may be prepared and added continuously at an appropriate time during grain formation. It is also preferable to combine various addition methods.

A method of adding a chalcogen compound during grain formation as described in US Pat. No. 3,772,031 is sometimes useful.

The silver halide grains of the present invention can be subjected to chemical sensitization in any step of the production process of a silver halide emulsion. It is preferable to combine two or more sensitization methods. Various types of emulsions can be prepared depending on the step of chemical sensitization. There are a type in which a chemical sensitizing nucleus is embedded in the grain, a type in which the chemical sensitizing nucleus is embedded in a position shallow from the grain surface, and a type in which a chemical sensitizing nucleus is formed on the surface.
In the emulsion of the present invention, the location of the chemical sensitization nucleus can be selected according to the purpose. Generally, the case where at least one type of chemical sensitization nucleus is formed near the surface is preferred.

Chemical sensitization can be carried out in the presence of a so-called chemical sensitization aid. Useful chemical sensitization aids include compounds known to suppress fog and increase sensitivity during chemical sensitization, such as azaindene, azapyridazine and azapyrimidine. It should be noted that a chemical sensitization aid modifier can also be allowed to coexist. Examples of such modifiers are described in U.S. Pat. Nos. 2,131,038 and 3,411,
Nos. 914 and 3,554,757, JP-A-58-12
No. 6526 and the above-mentioned "Photographic emulsion chemistry", 1
38-143.

It is preferable to use an oxidizing agent for silver during the production process of the emulsion of the present invention. The oxidizing agent for silver is
A compound that acts on metallic silver to convert it into silver ions. In particular, a compound that converts very fine silver particles by-produced in the process of forming silver halide grains and in the course of chemical sensitization into silver ions is effective. The silver ions generated here may form a silver salt that is hardly soluble in water, such as silver halide, silver sulfide, silver selenide, or a silver salt that is easily soluble in water such as silver nitrate. May be. The oxidizing agent for silver may be inorganic or organic. Examples of the inorganic oxidizing agent include ozone, hydrogen peroxide, and adducts thereof (for example, NaBO ₂ .H ₂ O _2.
3H ₂ O, 2NaCO ₃ .3H ₂ O ₂ , Na ₄ P ₂ O ₇
・ 2H ₂ O ₂ , 2Na ₂ SO ₄・ H ₂ O ₂・ 2H
₂ O), peroxy acid salts (eg, K ₂ S ₂ O ₈ , K ₂ C)
₂ O ₆ , K ₂ P ₂ O ₈ ), peroxy complex compounds (for example, K ₂ [Ti (O ₂ ) C ₂ O ₄ ] · 3H ₂ O, 4K ₂
SO ₄ .Ti (O ₂ ) OH.SO ₄ .2H ₂ O, Na ₃
[VO (O ₂ ) (C ₂ H ₄ ) ₂ .6H ₂ O), permanganate (eg, KMnO ₄ ), chromate (eg,
Oxyacid salts such as K ₂ Cr ₂ O ₇ ), halogen elements such as iodine and bromine, perhalates (eg, potassium periodate), salts of high-valent metals (eg, potassium hexacyanoferric acid) and There are thiosulfonates.

Examples of the organic oxidizing agent include, for example, p
Quinones such as quinones, for example, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogens (eg, N-bromosuccinimide, chloramine T,
Chloramine B) is mentioned by way of example.

Preferred oxidizing agents of the present invention are ozone, hydrogen peroxide and its adducts, halogen elements, inorganic oxidizing agents such as thiosulfonates and organic oxidizing agents such as quinones. It is a preferred embodiment to use the above-described reduction sensitization and an oxidizing agent for silver in combination. In this case, any method of using a oxidizing agent and then performing reduction sensitization, the reverse method, or the method of coexisting both can be used. These methods can be applied in both the grain formation step and the chemical sensitization step.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. . That is, thiazoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole);
Mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadolinthione; azaindenes such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a,
7) Many compounds known as antifoggants or stabilizers, such as tetraazaindenes and pentaazaindenes, can be added. For example, U.S. Pat.
954,474, 3,982,947, Tokubo Sho5
What was described in 2-28660 can be used. One of the preferred compounds is a compound described in Japanese Patent Application No. 62-47225. Antifoggants and stabilizers before particle formation, during particle formation, after particle formation, washing step, during dispersion after water washing, before chemical sensitization, during chemical sensitization, after chemical sensitization,
It can be added at various times before application according to the purpose. In addition to exhibiting the original antifogging and stabilizing effects by adding during emulsion preparation, for example, controlling the crystal habit of the grains, reducing the grain size, reducing the solubility of the grains, controlling the chemical sensitization It can be used for many purposes such as controlling the arrangement of dyes.

The photographic emulsion used in the present invention is preferably spectrally sensitized by a methine dye or the like to exhibit the effects of the present invention. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. These dyes may contain any nucleus commonly used in cyanine dyes as a basic heterocyclic nucleus. Such nuclei include, for example, a pyrroline nucleus,
Oxazoline nucleus, thiozoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus; nucleus in which alicyclic hydrocarbon ring is fused to these nuclei; A nucleus in which hydrogen rings are fused, for example, an indolenine nucleus, a benzindolenin nucleus, an indole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, and a quinoline nucleus. Can be mentioned. These nuclei may be substituted on carbon atoms.

The merocyanine dye or composite merocyanine dye has a ketomethylene structure as a nucleus having a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidin-2,4-dione nucleus, and a thiazolidine-2,4-nucleus.
It may have a 5- to 6-membered heterocyclic nucleus such as a dione nucleus, a rhodanine nucleus, and a thiobarbituric acid nucleus. .

These sensitizing dyes may be used alone or in combination, and a combination of sensitizing dyes is often used particularly for supersensitization. Representative examples are U.S. Pat. Nos. 2,688,545 and 2,972.
7,229, 3,397,060, 3,52
2,052, 3,527,641, 3,61
7,293, 3,628,964 and 3,66
6,480, 3,672,898, 3,67
9,428, 3,703,377, 3,76
9,301, 3,814,609, 3,83
Nos. 7,862, 4,026,707, British Patent Nos. 1,344,281, 1,507,803, JP-B-43-4936, JP-B-53-12,375, JP-A-52 Nos. -110,618 and 52-109,925.

In addition to the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization.

The sensitizing dye may be added to the emulsion at any stage in the preparation of the emulsion which has been known to be useful. Most commonly, it is performed after completion of chemical sensitization and before coating, but US Pat.
As described in JP-A Nos. 628,969 and 4,225,666, spectral sensitization can be carried out simultaneously with chemical sensitization by simultaneous addition with a chemical sensitizer.
It can be carried out prior to chemical sensitization as described in JP-A-113,928, or can be added before the completion of silver halide grain precipitation to initiate spectral sensitization. Furthermore, these sensitizing dyes are added separately as taught in U.S. Pat. No. 4,225,666, i.e., some of these sensitizing dyes are added prior to chemical sensitization, and Can be added after chemical sensitization, and may be at any time during the formation of silver halide grains, including the method disclosed in U.S. Pat. No. 4,183,756. In the present invention, it is preferably added before chemical sensitization.

The sensitizing dye can be used in an amount of from 4 × 10 ⁻⁶ to 8 × 10 ⁻³ mol per mol of silver halide, and a more preferable silver halide grain size is from 0.2 to 10 mol.
In the case of 1.2 μm, about 5 × 10 ⁻⁵ to 2 × 10 ⁻³ mol is more effective.

The above-mentioned various additives are used in the light-sensitive material according to the present technology, but other various additives can be used according to the purpose.

These additives are described in more detail in Research Disclosure Item 17643 (1978).
Item 18716 (January 1979)
Jan.) and Item 307105 (November 1989), and the relevant portions are summarized in the following table.

Additive type RD17643 RD18716 RD307105 1 Chemical sensitizer page 23, page 648, right column, page 966 2 Sensitivity enhancer, page 648, right column 3 Spectral sensitizer, page 23-24, page 648, right column to page 996, right to strong Color sensitizer page 649 right column 998 page right 4 Brightener 24 page 998 page right 5 Antifoggant 24-25 page 649 page right column 998 page right and stabilizer 1000 page right 6 light absorber, 25-26 Page 649 Right column-Page 1003 Left-Filter dye, Page 650 Left column 1003 Right UV absorber 7 Stain inhibitor 25 Page Right column 650 Page Left column-Right column 8 Dye image stabilizer Page 25 9 Hardener 26 Page 651 Left column 1004 page right to 1005 page left 10 Binder 26 page 651 Left column 1003 page right to 1004 page 11 Plasticizer, lubricant 27 page 650 page right column 1006 page left to 1006 page 12 Coating aid 26-27, 650, right column, page 1005, left-surfactant 1006, left 13 Static 27, 650, right column, 1006, right-blocker 1007, left When applying the present invention to a color multilayer light-sensitive material. It is sufficient that at least one layer of a silver halide emulsion agent of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer is provided on the support. There is no particular limitation on the number of layers and the order of the layers. A typical example is a silver halide photographic light-sensitive material having at least one light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. The light-sensitive layer is a unit light-sensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic light-sensitive material, generally, The arrangement is such that a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are arranged in this order from the support side. However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity.

A non-light-sensitive layer such as an intermediate layer of each layer may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer.

In the intermediate layer, for example, JP-A-61-437
No. 48, No. 59-113438, No. 59-11344
The couplers and DIR compounds described in JP-A Nos. 0, 61-20037 and 61-20038 may be contained, and a color-mixing inhibitor as usually used may be contained.

As described in West German Patent No. 1,121,470 or British Patent No. 923,045, a plurality of silver halide emulsion layers constituting each unit photosensitive layer may be composed of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer. A two-layer constitution of an emulsion layer can be preferably used. Usually, it is preferable to arrange them so that the light sensitivity decreases sequentially toward the support, and a non-photosensitive layer may be provided between the respective halogen emulsion layers. Also,
For example, JP-A-57-112751, 62-2003
No. 50, No. 62-206541, No. 62-206543
As described in (1), a low-speed emulsion layer may be provided on the side remote from the support, and a high-speed emulsion layer may be provided on the side near the support.

As specific examples, for example, from the farthest side from the support, a low-sensitivity blue-sensitive layer (BL) / a high-sensitivity blue-sensitive layer (BH) / a high-sensitivity green-sensitive layer (GH) / a low-sensitivity green-sensitive layer Layer (GL) / high-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL), or BH / BL / GL / GH / R
H / RL, or BH / BL / GH / GL / RL /
They can be installed in the order of RH.

As described in JP-B-55-34932, the layers may be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the farthest side from the support. JP-A-56-25738 and JP-A-62-6393.
As described in the specification of JP-A No. 6, the blue light-sensitive layer / GL / RL / GH / RH may be arranged in this order from the farthest side from the support.

As described in JP-B-49-15495, the upper layer is the silver halide emulsion layer having the highest sensitivity, the middle layer is the silver halide emulsion layer having a lower sensitivity, and the lower layer is the silver halide emulsion layer. Further, an arrangement is also possible in which a silver halide emulsion layer having a lower sensitivity is further disposed, and an arrangement is formed of three layers having different sensitivities in which the sensitivities are successively decreased toward the support. Even in the case of three layers having different sensitivities, as described in JP-A-59-202264, a medium-sensitivity emulsion from the side farther from the support in the same color-sensitive layer. Layers / high-speed emulsion layers / low-speed emulsion layers.

In addition, for example, high-speed emulsion layers / low-speed emulsion layers / medium-speed emulsion layers, or low-speed emulsion layers / medium-speed emulsion layers / high-speed emulsion layers may be arranged in this order.

In the case of four or more layers, the arrangement may be changed as described above.

As described above, various layer configurations and arrangements can be selected according to the purpose of each photosensitive material.

In the present invention, it is preferable to use non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is silver halide fine grains that are not exposed during imagewise exposure to obtain a dye image and are not substantially developed in the developing process, and are preferably not fogged in advance. .

The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and / or
Alternatively, it may contain silver iodide. Preferably, it contains 0.5 to 10 mol% of silver iodide.

The fine grain silver halide preferably has an average grain size (average value of the equivalent circle diameter of the projected area) of 0.01 to 0.5 μm, more preferably 0.02 to 2 μm.

The fine silver halide grains can be prepared in the same manner as in the case of ordinary light-sensitive silver halide. In this case, the surface of the silver halide grains does not need to be optically sensitized,
Also, spectral sensitization is not required. However, prior to adding this to the coating solution, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound in advance. Colloidal silver can be preferably contained in the layer containing fine silver halide grains.

The coated silver amount of the light-sensitive material of the present invention was 7.0 g.
/ M ² or less are preferred, 4.5 g / m ² or less is most preferred.

Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat.
It is preferable to add a compound which can be fixed by reacting with formaldehyde, described in JP-A No. 87 or 4,435,503, to the photosensitive material.

The light-sensitive material of the present invention may be added to US Pat.
0,454, 4,788,132, JP-A-62
It is preferable to include a mercapto compound described in JP-A-18539 and JP-A-1-283551.

The light-sensitive material of the present invention may be added to JP-A-1-1060.
No. 52, it is preferable to contain a compound which releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof irrespective of the amount of developed silver produced by the development processing.

The light-sensitive material of the present invention may be added to International Publication WO 88 /
No. 04794, dyes dispersed by the method described in JP-A-1-502912 or EP 317,308A,
U.S. Pat. No. 4,420,555;
The dye described in No. 58 is preferably contained.

Various color couplers can be used in the present invention, and specific examples thereof are described in Research Disclosure No. supra. Nos. 17643, VII-CG and No. 307105, VII-CG.

As the yellow coupler, for example, US Pat. Nos. 3,933,501 and 4,022,620
No. 4,326,024 and 4,401,75
No. 2, No. 4,248,961, Japanese Patent Publication No. 58-107
No. 39, British Patent Nos. 1,425,020 and 1,4
No. 76,760; U.S. Pat. Nos. 3,973,968; 4,314,023; 4,511,649;
Those described in EP 249,473A are preferred.

As the magenta coupler, 5-pyrazolone and pyrazoloazole compounds are preferable. For example, US Pat. Nos. 4,310,619 and 4,351,8
No. 97, EP 73,636, U.S. Pat.
No. 61,432, No. 3,725,067, Research Disclosure No. 24220 (June 1984
), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, JP-A-61-72238, and JP-A-60-72238.
-35730, 55-118034, 60-1
No. 85951, U.S. Pat. Nos. 4,500,630, 4,540,654 and 4,556,630, and WO 88/04795 are particularly preferable.

Examples of the cyan coupler include phenol couplers and naphthol couplers. For example, US Pat. Nos. 4,052,212, 4,146,396, 4,228,233 and 4 , 296, 200,
Nos. 2,369,929 and 2,801,171
No. 2,772,162, No. 2,895,82
No. 6, No. 3,772,002, No. 3,758,3
08, 4,334,011, 4,327,
173, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A and 249,453A,
U.S. Pat. Nos. 3,446,622 and 4,333,9
No. 99, No. 4,775,616, No. 4,451,
Nos. 559, 4,427,767 and 4,69
No. 0,889, No. 4,254,212, No. 4,2
96, 199 and JP-A-61-42658 are preferred.

Typical examples of polymerized dye-forming couplers include, for example, US Pat. Nos. 3,451,820, 4,080,211, 4,367,282, and 4,409, No. 320, No. 4,576,910,
British Patent 2,102,137, European Patent 341,1
No. 88A.

Examples of couplers in which a coloring dye has an appropriate diffusivity include US Pat. No. 4,366,237, British Patent No. 2,125,570, and European Patent No. 96,570.
Those described in West German Patent (Published) No. 3,234,533 are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are available from Research Disclosure N
o. No. 17643, section VII-G; 307105
Section VII-G, U.S. Pat. No. 4,163,670, JP-B-57-39413, U.S. Pat. No. 4,004,929.
No. 4,138,258 and British Patent No. 1,14.
No. 6,368 is preferred. In addition, a coupler described in U.S. Pat. No. 4,774,181 for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling, or reacting with a developing agent described in U.S. Pat. No. 4,777,120. It is also preferable to use a coupler having a dye precursor group capable of forming a dye as a leaving group.

Compounds which release a photographically useful residue upon coupling can also be preferably used in the present invention.
The DIR coupler releasing the development inhibitor is the RD1 described above.
No. 7643, section VII-F and the same No. 307105, VII
-F described in paragraph F or JP-A-57-151
No. 944, No. 57-154234, No. 60-1842
No. 48, 63-37346, 63-37350
Nos. 4,248,962 and 4,782.
No. 012 is preferred.

As a coupler which releases a nucleating agent or a development accelerator in an image-like manner at the time of development, British Patent No. 2,099
7,140,2,131,188, JP-A-59
Preferred are those described in JP-A-157638 and JP-A-59-170840. Also, JP-A-60-107029, JP-A-60-252340, JP-A-1-44940 and JP-A-1-44940.
Also preferred are compounds which release, for example, a fogging agent, a development accelerator, and a silver halide solvent by an oxidation-reduction reaction with an oxidized form of a developing agent described in JP-A-45687.

Other compounds that can be used in the light-sensitive material of the present invention include, for example, US Pat. No. 4,130,
No. 427, for example, US Pat.
No. 283,472, 4,338,393, and 4,310,618, multi-equivalent couplers, for example, JP-A-60-185950 and JP-A-62-24252.
Redox compound-releasing coupler described in item No.
R coupler releasing couplers, DIR coupler releasing redox compounds or DIR redox releasing redox compounds, EP 173,302A, EP 313,30
No. 8A, couplers releasing dyes that recolor after release, such as RD. No. 11449, 24241, bleaching accelerator releasing couplers described in JP-A-61-201247, such as ligand releasing couplers described in U.S. Pat. No. 4,555,477, and leuco dyes described in JP-A-63-75747. Releasing couplers, US Pat. No. 4,7
And couplers which release a fluorescent dye described in JP-A-74,181.

The coupler used in the present invention can be introduced into a light-sensitive material by various known dispersion methods.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in, for example, US Pat. No. 2,322,027.

Specific examples of the high-boiling organic solvent having a boiling point of 175 ° C. or more at normal pressure used in the oil-in-water dispersion method include, for example, phthalic acid esters (for example, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethyl phthalate). Ethylhexyl phthalate, decyl phthalate, bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1
-Diethylpropyl) phthalate), phosphoric acid or phosphonic acid esters (e.g., triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridecyl phosphate, tributoxy) Ethyl phosphate, trichloropropyl phosphate, di-2-ethylhexyl phenyl phosphonate), benzoic acid esters (for example, 2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (for example, N, N- Diethyldodecaneamide, N, N-diethyllauramide, N-tetradecylpyrrolidone), alcohols or phenols (for example, Allyl alcohol, 2,4-di -t
ert-amylphenol), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate), aniline derivatives (for example, N, N-dibutyl) -2-butoxy-5-tert-octylaniline) and hydrocarbons (for example, paraffin, dodecylbenzene, diisopropylnaphthalene). As the auxiliary solvent, for example, the boiling point is about 30 ° C. or more, preferably 50 ° C. or more and about 1 ° C.
Organic solvents of 60 ° C. or lower can be used, and typical examples include, for example, ethyl acetate, butyl acetate, ethyl propionate,
Examples include methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, and dimethylformamide.

Examples of the steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in, for example, US Pat.
No. 99,363, West German Patent Application (OLS) No. 2,54
Nos. 1,274 and 2,541,230.

In the color light-sensitive material of the present invention, for example,
Phenethyl alcohol and JP-A-63-257747,
62-272248 and JP-A-1-80941
No. 1,2-benzisothiazolin-3-one,
adding various preservatives or fungicides such as n-butyl-p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, 2- (4-thiazolyl) benzimidazole; Is preferred.

The present invention can be applied to various color light-sensitive materials. For example, color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers can be mentioned as typical examples.

Suitable supports that can be used in the present invention are described, for example, in RD. No. No. 17643, page 28;
No. 18716, from the right column on page 647 to the left column on page 648; 307105, page 879.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, and 18 μm or less.
m or less, more preferably 16 μm or less.
Further, the film swelling speed T _1/2 is preferably 30 seconds or less, and more preferably 20 seconds or less. The film thickness means a film thickness measured at 25 ° C. and a relative humidity of 55% (2 days), and the film swelling speed T
_1/2 can be measured according to techniques known in the art. For example, A. Green
en) et al., Photographic Science and Engineering (Photogr. Sci. En).
g. ), Vol. 19, No. 2, pp. 124-129 can be measured by using a serometer (swelling meter), and T _1/2 is treated with a color developing solution at 30 ° C. for 3 minutes 15 seconds. 90% of the maximum swelling film thickness reached when
It is defined as the time required to reach 1/2 of the saturated film thickness.

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

In the light-sensitive material of the present invention, a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm is preferably provided on the side opposite to the side having the emulsion layer. In this back layer, for example, the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener,
It is preferable to include a binder, a plasticizer, a lubricant, a coating aid, and a surfactant. The swelling ratio of this back layer is 1
50-500% is preferred.

The color photographic light-sensitive material according to the present invention is prepared according to the RD. No. No. 17643, pages 28 to 29;
No. 18716, page 651, left column to right column; 30
The development can be carried out by a usual method described on pages 880 to 881 of No. 7105.

The color developing solution used for developing the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as the color developing agent, but p-phenylenediamine compounds are preferably used. Typical examples thereof include 3-methyl-4-amino-N, N-diethylaniline and -Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline,
3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-methoxyethylaniline and their sulfates, hydrochlorides or p- Toluenesulfonate is mentioned. Among these, in particular, 3-methyl-4-
Amino-N-ethyl-N-β-hydroxyethylaniline sulfate is preferred. These compounds can be used in combination of two or more depending on the purpose.

The color developing solution may be, for example, a pH buffer such as an alkali metal carbonate, borate or phosphate, a chloride, a bromide, an iodide, a benzimidazole,
It generally contains a development inhibitor or an antifoggant such as a benzothiazole or a mercapto compound. If necessary, various preservatives such as hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazide, triethanolamine, catecholsulfonic acid, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting Agents, aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, various chelating agents represented by phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cycloalkyl Hexane diamine tetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene--
1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N
-Tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof can be mentioned as typical examples.

When the reversal process is performed, color development is usually performed after black and white development. In this black-and-white developer, for example, dihydroxybenzenes such as hydroquinone,
Known black and white developing agents such as 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol can be used alone or in combination.

The pH of these color developing solutions and black-and-white developing solutions
Is generally 9 to 12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per square meter of the photographic material, and 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air.

The contact area between the photographic processing solution and air in the processing tank can be represented by the aperture ratio defined below.

That is, the opening ratio = the contact area (cm ² ) between the processing liquid and the air / the volume of the processing liquid (cm ³ ) The above-mentioned opening ratio is preferably 0.1 or less, more preferably 0.1% or less. 001 to 0.05. As a method of reducing the aperture ratio in this manner, in addition to providing a shield such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033,
A slit developing method described in JP-A-63-216050 can be exemplified. The reduction of the aperture ratio is preferably applied not only to both the color development and black-and-white development steps but also to the following various steps, for example, all the steps such as bleaching, bleach-fixing, fixing, washing and stabilization.
The amount of replenishment can also be reduced by using means for suppressing the accumulation of bromide ions in the developer.

The time of the color development processing is usually set between 2 and 5 minutes, but the processing time can be further reduced by using a high temperature and high pH and using a high concentration of the color developing agent. it can.

The photographic emulsion layer after color development is usually subjected to bleaching. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Further, processing in two successive bleach-fixing baths, fixing before bleach-fixing, or bleaching after bleach-fixing can be arbitrarily performed according to the purpose. As the bleaching agent, for example, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. Typical bleaching agents are, for example, organic complexes of iron (III) such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid. Complex salts with aminopolycarboxylic acids or organic acids such as citric acid, tartaric acid, malic acid can be used. Of these, iron (III) complex salts of aminopolycarboxylic acid such as iron (III) complex salt of ethylenediaminetetraacetate and 1,3-diaminopropanetetraacetate are preferable from the viewpoint of rapid treatment and prevention of environmental pollution. . In addition, iron aminopolycarboxylate (II
I) Complex salts are particularly useful in both bleaching and bleach-fixing solutions. The pH of the bleaching solution or the bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually from 4 to 8, but the processing can be carried out at a lower pH to speed up the processing.

In the bleaching solution, the bleach-fixing solution and the prebath thereof, a bleaching accelerator can be used if necessary.
Specific examples of useful bleaching accelerators include, for example, U.S. Pat. No. 3,893,858 and West German Patent 1,290,812.
No. 2,059,988, JP-A-53-32736.
No. 53-57831, No. 53-37418, No. 53-72623, No. 53-95630, No. 53-
No. 95631, No. 53-104232, No. 53-12
No. 4424, No. 53-141623, No. 53-284
No. 26, Research Disclosure No. 26 1712
No. 9 (July 1978), a compound having a mercapto group or a disulfide group;
No. 9 thiazolidine derivative; Japanese Patent Publication No. 45-850
No. 6, JP-A-52-20832 and JP-A-53-32735.
Thiourea derivatives described in U.S. Patent No. 3,706,561; West German Patent No. 1,127,715;
Iodide salts described in US Pat. No. 16,235; West German Patent No. 96
Polyoxyethylene compounds described in JP-A-6-410 and JP-A-2,748,430; polyamine compounds described in JP-B-45-8836; and other JP-A-49-40,943.
Nos. 49-59,644 and 53-94,927
Nos. 54-35,727 and 55-26,506
No. 58-163,940; bromide ions can be used. Among them, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large accelerating effect, and particularly, compounds described in U.S. Pat. No. 3,893,858, West German Patent 1,290,812, and JP-A-53-95630 are disclosed. The compounds described are preferred. Further, U.S. Pat.
The compounds described in 2,834 are also preferred. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography.

The bleaching solution and the bleach-fixing solution preferably contain an organic acid in order to prevent bleaching stain, in addition to the above compounds. Particularly preferred organic acids are compounds having an acid dissociation constant (pKa) of 2 to 5, specifically, for example, acetic acid and propionic acid.

Examples of the fixing agent used in the fixing solution or the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodides. Is common, and in particular, ammonium thiosulfate can be used most widely. It is also preferable to use a combination of a thiosulfate and a thiocyanate, a thioether-based compound, thiourea, or the like. As a preservative of the fixing solution or the bleach-fixing solution, a sulfite, a bisulfite, a carbonyl bisulfite adduct, or a sulfinic acid compound described in EP-A-294769A is preferable. Further, it is preferable to add various aminopolycarboxylic acids or organic phosphonic acids to the fixing solution or the bleach-fixing solution for the purpose of stabilizing the solution.

In the present invention, a compound having a pKa of 6.0 to 9.0, preferably imidazole, 1-methylimidazole, 1-ethylimidazole, It is preferable to add imidazoles such as methyl imidazole in an amount of 0.1 to 10 mol / l.

The total time of the desilvering step is preferably as short as possible without desilvering failure. Preferred time is 1 minute to 3
Minutes, more preferably 1 to 2 minutes. Further, the processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C.
In a preferable temperature range, the desilvering speed is improved, and generation of stain after processing is effectively prevented.

In the desilvering step, it is preferable that the stirring is strengthened as much as possible. As a specific method of strengthening the stirring, a method described in JP-A-62-183460, in which a jet of a processing solution is made to impinge on the emulsion surface of a photosensitive material, or a method using a rotating means described in JP-A-62-183461, is used. A method of increasing the effect, a method of moving the photosensitive material while bringing the wiper blade provided in the solution into contact with the emulsion surface, and increasing the stirring effect by turbulently flowing the emulsion surface, and circulating the entire processing solution. There is a method of increasing the flow rate. Such stirring improving means include a bleaching solution, a bleach-fixing solution,
It is effective in any of the fixing solutions. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently increases the desilvering speed. Further, the above-mentioned means for improving the stirring is more effective when a bleaching accelerator is used, and can significantly increase the accelerating effect or eliminate the fixing inhibiting effect of the bleaching accelerator.

The automatic developing machine used for the light-sensitive material of the present invention is described in JP-A-60-191257 and JP-A-60-19125.
No. 8, No. 60-191259. JP-A-60-1
As described in JP-A-91257, such a transporting means can significantly reduce the carry-in of the processing liquid from the pre-bath to the post-bath, and is highly effective in preventing the performance of the processing liquid from deteriorating. Such an effect is particularly effective for reducing the processing time in each step and reducing the replenishing amount of the processing solution.

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, the material used such as a coupler), the use, the rinsing water temperature, the number of rinsing tanks (the number of stages), for example, a replenishment method such as countercurrent or forward flow, and various other methods. It can be set in a wide range depending on conditions. Among them, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is described in Journal of the S.
ociety of Motion Picture
and Television Engineers
Vol. 64, p. 248-253 (May, 1955).

According to the multi-stage counter-current method described in the above document,
Although the amount of rinsing water can be greatly reduced, there is a problem in that, for example, bacteria proliferate and generated floating substances adhere to the photosensitive material due to an increase in the residence time of water in the tank. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, a method for reducing calcium ions and magnesium ions described in JP-A-62-28838 can be used very effectively. Also,
JP-A-57-8542, isothiazolone compounds, thiabendazoles, chlorine-based disinfectants such as chlorinated sodium isocyanurate, and other benzotriazoles. (1986) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology"
(1982) The germicidal agent described in "Encyclopedia of Bacterial and Fungicides" (ed. 1986), edited by the Industrial Technology Society of Japan and the Japan Society of Bacterial and Fungicide can also be used.

The pH of the washing water in the processing of the light-sensitive material of the present invention is from 4 to 9, preferably from 5 to 8. The washing temperature and washing time can also be variously set depending on the characteristics of the photosensitive material, the use, etc., but are generally at 15 to 45 ° C. for 20 seconds to 10 minutes,
Preferably, a range of 30 seconds to 5 minutes at 25 to 40 ° C is selected. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned water washing. In such a stabilizing process, JP-A-57-8543 and JP-A-58-8543 are used.
All known methods described in JP-A-14834 and JP-A-60-220345 can be used.

In some cases, a stabilization treatment may be performed after the water washing treatment. For example, a stabilization treatment containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photography, may be used. Baths can be mentioned. Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine and aldehyde sulfite adducts.

A variety of chelating agents and fungicides can be added to this stabilizing bath.

The overflow solution resulting from the washing and / or replenishment of the stabilizing solution can be reused in another step such as a desilvering step.

In the processing using an automatic developing machine or the like, when the above-mentioned processing solutions are concentrated by evaporation, it is preferable to correct the concentration by adding water.

In the silver halide color light-sensitive material of the present invention, a color developing agent may be incorporated for the purpose of simplifying and speeding up the processing. In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, U.S. Pat.
No. 342,597, indoaniline compounds, and No. 3,342,599, Research Disclosure No. 14, 850 and the same No. 15, 159, Schiff base compounds, aldol compounds described in 13,924, metal salt complexes described in U.S. Pat. No. 3,719,492, and urethane-based compounds described in JP-A-53-135628. be able to.

The silver halide color light-sensitive material of the present invention comprises
If necessary, various 1-
Phenyl-3-pyrazolidones may be incorporated. Typical compounds are described in, for example, JP-A-56-64339 and JP-A-57-64339.
Nos. -1444547 and 58-115438.

In the present invention, various processing solutions are used at a temperature of 10 ° C. to 50 ° C.
Used at ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but a higher temperature promotes the processing and shortens the processing time, and a lower temperature achieves an improvement in the image quality and an improvement in the stability of the processing solution. be able to.

Further, the silver halide light-sensitive material of the present invention comprises:
For example, U.S. Pat. No. 4,500,626;
No. 133449, No. 59-218443, No. 61-2
It is also applicable to the photothermographic materials described in Japanese Patent No. 38056 and European Patent 210,660A2.

Hereinafter, the present invention will be described in detail with reference to Examples.

[0297]

【Example】

Example 1 The average iodine content is 8.2 mol%, the iodine content in the core is 20 mol%, the iodine content in the shell surrounding it is 3.5 mol%, the average particle size is 0.6 μm, and the particle size distribution. The emulsion had a slightly rounded monodisperse double-structured octahedral emulsion having a coefficient of variation of 0.18.

After the completion of the particle formation, desalting was carried out by a usual flocculation method. Subsequently, with respect to those to which a sensitizing dye is added, sensitizing dyes D-1 and D-2 are each added to 4.
5 × 10 ^-4 and 1.0 × 10 ^-4 ml / mol Ag were added,
Further, using chloroauric acid, potassium thiocyanate, sulfur sensitizer, selenium sensitizer, and tellurium sensitizer described in Table 1, 1 /
Chemical sensitization was performed at 62 ° C. to optimize the 100 ″ sensitivity. These emulsions were added to the emulsions of the formulas (I), (II), (III) or (IV) at the addition amounts shown in Table 1. The compounds shown were added to obtain Emulsions A to Q.

[0299]

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[0300]

[Table 1] Sample 10 coated with the emulsion thus prepared as follows
Nos. 1-117 were created.

The emulsion layer and the protective layer were coated on the triacetyl cellulose film support provided with the undercoat layer in the following coating amounts. <Emulsion layer> Emulsion Emulsion A to Q shown in Table 1 Silver coating amount 1.1 g / m ² Coupler 1.1 g / m ²

[0302]

Embedded image ・ Tricresyl phosphate 1.3 g / m ²・ Gelatin 2.5 g / m ² <Protective layer> ・ Gelatin 2.2 g / m ²・ Hardener 0.30 g / m ²

[0303]

Embedded image These samples were exposed to sensitometry and subjected to the following color development processing.

The density of the treated sample was measured with a green filter.

The developing process used here was performed under the following conditions.
C. was performed.

[0306] 1. 1. Color development: 2 minutes 45 seconds Bleaching 6 minutes and 30 seconds 3. 3. Rinse ... 3 minutes 15 seconds Fixed arrival: 6 minutes 30 seconds 5. 5. Rinse ... 3 minutes 15 seconds Stability: 3 minutes 15 seconds The composition of the processing solution used in each step is as follows. <Color developer> Sodium nitrilotriacetate 1.4 g Sodium sulfite 4.0 g m Sodium carbonate 30.0 g Potassium bromide 1.4 g Hydroxylamine sulfate 2.4 g 4- (N-ethyl-N-βhydroxyethylamino) -2-Methyl-aniline sulfate 4.5 g 1 L by adding water <Bleaching solution> Ammonium bromide 160.0 g Ammonia water (28%) 25.0 ml Ethylenediamine-tetraacetic acid sodium salt 130 g Glacial acetic acid 14 ml In addition, 1 L <fixing solution> sodium tetrapolyphosphate 2.0 g sodium sulfite 4.0 g ammonium thiosulfate (70%) 175.0 ml sodium bisulfite 4.6 g water was added, and 1 L <stabilizing solution> formalin 8.0 ml water Add 1 L.

The exposure was carried out by using a usual wedge exposure for 1/100 second.

The light source is 480 using a filter.
A color temperature adjusted to 0 ° K was used.

The sensitivity was 0.2% in optical density from fog.
Were compared. The sensitivity is indicated by setting the sensitivity of the sample 101 to 100 for the sample to which no sensitizing dye is added, and setting the sensitivity of the sample 104 to 1 for the sample to which the sensitizing dye is added.
The relative sensitivity was represented as 00.

The results are shown in Table 2 below.

[0311]

[Table 2] From Table 2, the utility of the present invention is clear. That is,
Sample 1 subjected to tellurium sensitization without using a hydrazine compound
02 and 103 have high sensitivity, but have high fog.

The sample 105 of the comparative example to which the hydrazine compound was added without using the tellurium sensitizer certainly had a sensitizing effect, but the sensitivity was considerably lower than that of the tellurium sensitized sample.

On the other hand, the samples 106 and 10 of the present invention
8, 112, and 114 to 117 have high sensitivity, and at the same time, samples 102 and 1 of comparative examples subjected to only tellurium sensitization.
Fog is greatly improved compared to 03.

Samples 102, 106, 108 and 1
Comparison of Sample No. 12 with Samples 104, 107, 109 and 113 shows that the present invention is particularly effective when sensitizing dyes are present.

Further, by comparing Samples 106 and 108, it is understood that it is preferable in the present invention to use both sulfur sensitization and tellurium sensitization. Comparing Samples 107 and 109 shows that the same can be said in the presence of a sensitizing dye.

Further, the samples 108, 112 and 110
It can be seen from the above that the combination of sulfur sensitization, selenium sensitization and tellurium sensitization is more preferable in the present invention. Also, by comparing Samples 109, 113 and 111, it can be seen that the combination of sulfur sensitization, selenium sensitization and tellurium sensitization is more preferable in the present invention even in the presence of a sensitizing dye. Example 2 By the method described in U.S. Pat. No. 4,797,354, parallel twin tabular grains having a narrow grain size distribution and a mainly hexagonal grain shape were prepared. After forming tabular internal nuclei of silver bromide, a first shell of silver iodobromide having a silver iodide content of 11 mol% is grown, followed by a silver iodide content of 13 mol%.
A second shell of silver iodobromide was grown. The silver content of the inner core, first and second shells was 8%, 59% and 33%.
%. The average particle size was 0.85 microns and the coefficient of variation of the particle size was 19%. The aspect ratio obtained by dividing the diameter by the thickness was 9.5. Transmission electron microscope observation confirmed that dislocation lines were mainly present in the fringe portions of the particles.

The same experiment as in Example 1 was conducted using the obtained emulsion, and the usefulness of the present invention was confirmed with this emulsion. Example 3 Iodine structure is uniform, average iodine content is 3.8 mol%,
A silver iodobromide monodispersed cubic emulsion having an average grain size of 0.15 μm and a variation coefficient of the grain size distribution of 0.12 was prepared.
When the same experiment as in Example 1 was performed using the obtained emulsion, the usefulness of the present invention was confirmed also with this emulsion. Example 4 On a subbed cellulose triacetate film support,
Each layer having the composition shown below was applied in multiple layers to prepare a sample 401 as a multilayer color photosensitive material. (Composition of photosensitive layer) The main materials used for each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExY: yellow coupler H: gelatin Curing agent ExS: Sensitizing dye The number corresponding to each component indicates the coating amount in g / m ² , and for silver halide, it indicates the coating amount in terms of silver. However, as for the sensitizing dye, the coating amount is shown in mol unit with respect to 1 mol of silver halide in the same layer. (Sample 401) First Layer (Antihalation Layer) Black Colloidal Silver Silver 0.18 Gelatin 1.40 ExM-1 0.18 ExF-1 2.0 × 10 ^-3 HBS-1 0.20 Second Layer (Intermediate) Layer) Emulsion 4G Silver 0.065 2,5-di-t-pentadecylhydroquinone 0.18 ExC-2 0.020 UV-1 0.060 UV-2 0.080 UV-3 0.10 HBS-10 .10 HBS-2 0.020 gelatin 1.04 Third layer (low-sensitivity red-sensitive emulsion layer) Emulsion 4A silver 0.25 Emulsion 4B silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-7 0.0050 ExC-8 010 Cpd-2 0.025 H S-1 0.10 Gelatin 0.87 Fourth Layer (medium-sensitivity red-sensitive emulsion layer) Emulsion 4D Silver ^{0.70 ExS-1 3.5 × 10 -4} ExS-2 1.6 × 10 -5 ExS-3 5.1 × 10 ^-4 ExC-1 0.13 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.025 ExC-7 0.0010 ExC-8 0.0070 Cpd -0.023 HBS-1 0.10 Gelatin 0.75 Fifth layer (high-sensitivity red-sensitive emulsion layer) Emulsion 4E Silver 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.12 ExC-3 0.045 ExC-6 0.020 ExC-8 0.025 Cpd-2 0.050 HBS-1 0.22 HBS- 2 0.10 Gelatin 1.20 6th layer (middle layer) C d-1 0.10 HBS-1 0.50 Gelatin 1.10 7th layer (low sensitivity green-sensitive emulsion layer) Emulsion 4C silver ^{0.35 ExS-4 3.0 × 10 -5} ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-1 0.010 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73 Eighth Layer (Medium Speed Green Sensitive Emulsion Layer) Emulsion 4D Silver 0.80 ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-6 8.4 × 10 ^-4 ExM-2 0.13 ExM-3 0.030 ExY-1 0.018 HBS-1 0.16 HBS-3 8.0 × 10 ^-3 gelatin 0.90 Ninth layer (high-sensitivity green-sensitive emulsion layer) Emulsion 4E Silver 1.25 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3 0.2 × 10 ^-4 ExC-1 0.010 ExM-1 0.030 ExM-4 0.040 ExM-5 0.019 Cpd-3 0.040 HBS-1 0.25 HBS-2 0.10 Gelatin 1 .44 10th layer (yellow filter layer) Yellow colloidal silver silver 0.030 Cpd-1 0.16 HBS-1 0.60 gelatin 0.60 11th layer (low-sensitivity blue-sensitive emulsion layer) Emulsion 4C silver 0.18 ExS-7 8.6 × 10 ^-4 ExY-1 0.020 ExY-2 0.22 ExY-3 0.50 ExY-4 0.020 HBS-1 0.28 Gelatin 1.10 12th layer (medium sensitivity Blue-sensitive emulsion layer) Emulsion 4D Silver 0.40 ExS-7 7.4 × 10 ^-4 ExC-7 7.0 × 10 ^-3 ExY-2 0.050 ExY-3 0.10 HBS-1 0.050 Gelatin 0.78 thirteenth (High-sensitivity blue-sensitive emulsion layer) Emulsion 4F silver ^{1.00 ExS-7 4.0 × 10 -4} ExY-2 0.10 ExY-3 0.10 HBS-1 0.070 Gelatin 0.86 14th layer ( First protective layer) Emulsion 4G silver 0.20 UV-4 0.11 UV-5 0.17 HBS-1 5.0 × 10 ^-2 gelatin 1.00 Fifteenth layer (second protective layer) H-10 .40 B-1 (1.7 μm in diameter) 5.0 × 10 ^-2 B-2 (1.7 μm in diameter) 0.10 B-3 0.10 S-1 0.20 Gelatin 1.20 Appropriate storage, processing, pressure resistance, fungicide
To improve antibacterial, antistatic and coating properties
1 to W-3, B-4 to B-6, F-1 to F
-17 and iron, lead, gold, platinum, iridium and rhodium salts.

[0318]

[Table 3] In Table 3, (1) Emulsions A to F were subjected to reduction sensitization during the preparation of grains using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938. (2) For preparing tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. (3) In tabular grains and normal crystal grains having a grain structure, dislocation lines as described in JP-A-3-237450 are observed using a high-pressure electron microscope.

[0319]

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[0320]

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[0321]

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[0322]

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[0323]

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[0324]

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[0325]

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[0326]

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[0327]

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[0328]

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[0329]

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[0330]

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[0331]

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[0332]

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[0333]

Embedded image The same experiment as in Example 1 was carried out for the emulsions 4D and 4E, and the effect of the present invention was similarly confirmed in the multilayer color light-sensitive material as in this example.

[0334]

As described above, according to the present invention,
Since the silver halide emulsion layer contains at least one tellurium-sensitized silver halide emulsion and also contains a predetermined hydrazine compound, a silver halide photographic light-sensitive material having high sensitivity and low fog can be obtained. Can be

Continuation of the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) G03C 1/09 G03C 1/34

Claims (6)

(57) [Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on a support,
At least one silver halide emulsion contained in the silver halide emulsion layer is tellurium-sensitized, and the silver halide emulsion layer contains at least one compound represented by the following general formula (I). A silver halide photographic material. General formula (I) In the formula, R ₁ , R ₂ , R ₃ and R ₄ each represent an alkyl group, an aryl group or a heterocyclic group. Also, R ₁ and R
₂ , R ₃ and R ₄ , R ₁ and R ₃ , and R ₂ and R ₄ may combine with each other to form a ring, but do not form an aromatic ring. However, among R ₁ , R ₂ , R ₃ and R ₄ , the oxo group is not substituted on the carbon atom directly bonded to the nitrogen atom of hydrazine. 2. The silver halide photographic material according to claim 1, which has been spectrally sensitized with a sensitizing dye. 3. The halogen according to claim 1, wherein the compound represented by the general formula (I) is a compound selected from the following general formulas (II), (III) and (IV). Silver halide photographic material. General formula (II) General formula (III) General formula (IV) (Wherein R ₅ , R ₆ , R ₇ and R ₈ each represent an alkyl group, an aryl group or a heterocyclic group, Z ₁ is an alkylene group having 4 or 6 carbon atoms, and Z ₂ is an alkylene group having 2 carbon atoms. An alkylene group, Z ₃ represents an alkylene group having 1 or 2 carbon atoms, Z ₄ and Z ₅ represent an alkylene group having 3 carbon atoms, and L ₁ and L ₂ represent a methine group, provided that R ₅ and R _{5 6, R 7, R 8,} Z 1, of Z ₄ and Z _5, never the carbon atom directly bonded to the nitrogen atom of the hydrazine oxo group as a substituent.) 4. The halogenated photographic light-sensitive material according to claim 3, which has been spectrally sensitized with a sensitizing dye. 5. The silver halide photographic light-sensitive material according to claim 1, wherein said silver halide emulsion has been subjected to sulfur sensitization and tellurium sensitization in combination. . 6. The silver halide emulsion according to claim 1, wherein said silver halide emulsion has been subjected to sulfur sensitization, selenium sensitization and tellurium sensitization in combination. Silver photographic photosensitive material.