JP3270172B2 - Chemical sensitization of silver halide emulsion - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for chemically sensitizing a silver halide emulsion. More specifically, the present invention particularly relates to a chemical sensitization method using a selenium sensitizer and / or a tellurium sensitizer capable of obtaining a silver halide emulsion having improved fog and sensitivity.

[0002]

2. Description of the Related Art A silver halide emulsion used in a silver halide photographic light-sensitive material is usually subjected to chemical sensitization using various chemical substances in order to obtain a desired sensitivity, gradation and the like. As typical examples thereof, sulfur sensitization, selenium sensitization, tellurium sensitization, sensitization of noble metals such as gold, reduction sensitization, and various sensitization methods using a combination thereof are known.

In recent years, there has been a strong demand for high sensitivity, excellent graininess and high sharpness in silver halide photographic light-sensitive materials, as well as rapid processing in which development progress has been accelerated. Has been done. Of the above, sulfur sensitization, selenium sensitization, and tellurium sensitization are collectively referred to as chalcogen sensitization. Among them, sulfur sensitization is the most basic sensitization method, and significant efforts and improvements have already been made. It has been.

On the other hand, selenium sensitization is disclosed in US Pat. Nos. 1,574,944, 1,602,592, 1,623,499, 3,297,446, and 32.
97447, 3320069, 34081
No. 96, No. 3408197, No. 3442453
No. 3,420,670, No. 3,591,385, French Patent No. 2,693,038, No. 2,093,209
No., JP-B-52-34491 and JP-B-52-34492
Nos. 53-295, 57-22090, JP-A-59-180536, 59-185330, and 5
Nos. 9-181337, 59-187338, 59
No. 192241, No. 60-150046, No. 60-
JP-A-151637 and JP-A-61-246738;
No. 4221, No. 3-148648, No. 3-11183
No. 8, 3-116132, 3-237450,
No. 4-16838, No. 4-25832, No. 4-14
Nos. 0738 and 4-140739, European Patent No. 506
009A1 and also GB 255,846, 861984, and H.C. E. FIG. Spencer et al., J
own of Photographic Sc
ence magazine, vol. 31, pp. 158-169 (198
6 years), and it was known that the sensitization effect was larger than the above-mentioned sulfur sensitization generally performed in the art.

As for the tellurium sensitization, US Pat.
No. 623499, No. 3320069, No. 3772
No. 031, No. 3531289, No. 3655394
No. 4,704,349 and British Patent No. 235211.
No. 1,112,496, No. 1,295,462, No. 1,396,696, No. 2,160,993, and Canadian Patent No. 800958. In recent years, remarkable progress has been made.
No. 271341, No. 4-330430, Japanese Patent Application No. 3-1
No. 83486, No. 3-183487, No. 3-1834
No. 91, 3-221268, 3-221270
As disclosed in JP-A Nos. 4-129787 and 4-185004, the sensitizing effect is larger than that of sulfur sensitization, the development proceeds faster, the reciprocity characteristics are good, and the color sensitization sensitivity is higher. It has been found that it has many advantages such as high pressure effect and good pressure effect.

[0006] Although both selenium sensitization and tellurium sensitization have the above-mentioned advantages such as higher arrival sensitivity than sulfur sensitization generally used in the art, gold sensitization is aimed at higher sensitivity. There are drawbacks, such as fogging and softening easily, including when sensitization is combined, and fog during storage over time and a large decrease in sensitivity. Improvement of these has been strongly desired.

In order to improve these, for example, a method of adding a chemical sensitizer in the form of a solution dissolved in water or an organic solvent to an emulsion to perform chemical sensitization has been adopted. JP-A-4-140738 and JP-A-4-1407.
Japanese Patent No. 39 proposes a method of dispersing a selenium sensitizer in gelatin or a high-molecular polymer and adding this to an emulsion to perform chemical sensitization, but this method is still insufficient. In addition,
Japanese Patent Application Laid-Open No. 4-342249 discloses that a silver halide emulsion is chemically sensitized by previously adding silver halide fine particles having silver sulfide, gold silver sulfide and gold sulfide formed thereon. However, this publication does not disclose any specific description or specific examples (methods), and further does not disclose selenium sensitization or tellurium sensitization.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a chemical sensitization method using a selenium sensitizer and / or a tellurium sensitizer which can produce a silver halide emulsion with less fog and high sensitivity. It is to be. Another object of the present invention is to provide a chemical sensitization method using a selenium sensitizer and / or a tellurium sensitizer, which can provide a silver halide emulsion with little deterioration in photographic performance during storage over time. .

[0009]

The present invention is characterized in that silver halide fine grains which have been subjected to selenium sensitization and / or tellurium sensitization in advance are added to a silver halide emulsion of a host and chemically sensitized. Chemical sensitization of silver halide emulsions.

The present invention preferably has the following aspects. (1) The silver halide fine grains are further subjected to gold sensitization. (2) The silver halide fine grains are further subjected to sulfur sensitization. (3) A selenium sensitizer and / or tellurium sensitizer is used, and 50% or more of the selenium sensitizer and / or tellurium sensitizer reacts with silver halide fine particles. (4) The silver halide fine particles dissolve during the chemical sensitization of the silver halide emulsion of the host. (5) The size of the silver halide fine grains and the grain diameter are 0.
It is in the range of 01 μm to 0.3 μm. (6) The halogen composition of the silver halide fine particles is silver chloride,
Silver chlorobromide, silver bromide or silver iodobromide. (7) Chemical sensitization of silver halide as a host is performed by further adding a chemical sensitizer to silver halide fine particles. (8) Chemical sensitization of the host silver halide is carried out in the presence of a silver halide solvent (particularly thiocyanate).

DETAILED DESCRIPTION OF THE INVENTION In the chemical sensitization method of the present invention, a selenium sensitizer and / or a tellurium sensitizer are added to fine silver halide grains, and the selenium sensitizer and / or the tellurium sensitizer are added. And silver halide to cause a chemical sensitization reaction, whereby the silver halide fine particles are selenium sensitized and / or
Alternatively, after the tellurium sensitization, the selenium sensitized and / or tellurium sensitized silver halide fine grains are mixed with a host silver halide emulsion (finally selenium sensitized and / or tellurium sensitized to obtain a desired sensitivity). Silver halide emulsion), and chemically sensitizes the silver halide emulsion. In the present invention, selenium sensitization and / or
Alternatively, the tellurium-sensitized silver halide fine particles may include at least 30% (preferably 50% or more, more preferably 65% or more) of the added selenium sensitizer and / or tellurium sensitizer. It means that it reacts with silver halide fine particles to form silver (or gold, or a mixture thereof) chalcogenide.

The size of the silver halide fine particles used in the above method is 0.01 μm to 0.3 μm.
A range of m is preferred. More preferably, 0.01
The range is from μm to 0.2 μm. The halogen composition of the silver halide fine grains may be any of silver chloride, silver bromide, silver iodide or a mixed crystal thereof. Particularly, silver chloride, silver chlorobromide, silver bromide or silver iodobromide is preferred. It is preferred that these silver halide fine particles dissolve during chemical sensitization of the silver halide emulsion of the host.

[0013] The following are used in the above-mentioned chemical sensitization method.
The selenium sensitizer and the tellurium sensitizer will be described. First,
The selenium sensitizer will be described. As the selenium sensitizer used in the present invention, selenium compounds (unstable selenium compounds and non-unstable selenium compounds) disclosed in conventionally known patents can be used. Unstable selenium compounds used in the present invention include Japanese Patent Publication No. 43-13 / 1973.
No. 489, JP-A-44-15748, JP-A-4-25832, JP-A-4-109240, or compounds described in Japanese Patent Application Nos. 3-82929 and 3-53693 are preferred. Specific examples of unstable selenium sensitizers include, for example, isoselenocyanates (aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenoamides, and selenocarboxylic acids (for example, 2 -Selenopropionic acid, 2-selenobutyric acid), selenoesters, diacylselenides (for example, bis (3-chloro-2,6-
Dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides, colloidal metal selenium, and the like. Non-labile selenium compounds used in the present invention include JP-B-46-4553 and JP-B-52-553.
The compounds described in JP-A-34491 and JP-A-52-34492 are preferred. As the non-labile selenium compound, for example, selenous acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenide, diaryl diselenide, dialkyl selenide,
Dialkyl diselenide, 2-selenazolidinedione, 2
-Selenooxazolidinethione and derivatives thereof.

In the present invention, an unstable selenium compound can be preferably used rather than a non-unstable selenium compound. Among the selenium compounds, a selenium compound represented by the following formula (I) or (II) is preferable.

[0015]

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[In the formula (I), Z ¹¹ and Z ¹² are each independently an alkyl group, an alkenyl group, an aryl group, an aralkyl group, a heterocyclic group, -NR ¹¹ (R ¹² ), -OR ¹³ or -SR ¹⁴ (R ¹¹ and R ¹² are each independently a hydrogen atom,
Represents an alkyl group, an aralkyl group, an aryl group, an acyl group or a heterocyclic group, wherein R ¹³ and R ¹⁴ independently of one another,
Represents an alkyl group, an aralkyl group, an aryl group or a heterocyclic group. ). ]

[0017]

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[In the formula (II), Z ²¹ , Z ²² and Z ²³ each independently represent an aliphatic group, an aromatic group, a heterocyclic group, —O
R ²¹ , —NR ²² (R ²³ ), —SR ²⁴ , —SeR ²⁵ , a halogen atom or a hydrogen atom (R ²¹ , R ²⁴ and R
²⁵ represents an aliphatic group, an aromatic group, a heterocyclic group, a hydrogen atom or a cation independently of each other, and R ²² and R ²³ each independently represent an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom. Express. ) Or any of Z ²¹ , Z ²² and Z ²³ as a linking group to form a dimer. ]

First, the selenium compound represented by the above formula (I) will be described in detail. Examples of the alkyl group represented by Z ¹¹ and Z ¹² include methyl, ethyl, te
Mention may be made of rt-butyl, adamantyl groups and tert-octyl. Examples of the alkenyl groups represented by Z ¹¹ and Z ¹² include vinyl and propenyl. Examples of the aralkyl groups represented by Z ¹¹ and Z ¹² include benzyl and phenethyl. Examples of the aryl group represented by Z ¹¹ and Z ¹² include phenyl, pentafluorophenyl, 4-chlorophenyl, 3-nitrophenyl,
-Octylsulfamoylphenyl and α-naphthyl. Examples of the heterocyclic group represented by Z ¹¹ and Z ¹² include pyridyl, thienyl, furyl and imidazolyl. An alkyl group represented by the above R ¹¹ , R ¹² , R ¹³ and R ¹⁴ ;
An aralkyl group, an aryl group or a heterocyclic group is a group represented by the aforementioned Z ¹¹
Has the same meaning as an alkyl group, an aralkyl group, an aryl group or a heterocyclic group. Examples of the acyl group represented by R ¹¹ and R ¹² include acetyl, propanoyl,
Mention may be made of benzoyl, heptafluorobutanoyl, difluoroacetyl, 4-nitrobenzoyl, α-naphthoyl and 4-trifluoromethylbenzoyl.

In the above formula (I), Z ¹¹ represents an alkyl group, an aryl group or —NR ¹¹ (R ¹² ) (R ¹¹ and R
¹² represents a hydrogen atom, an alkyl group, an aryl group or an acyl group. ) Is preferable. The Z ¹² are -N
It is preferably R ¹¹ (R ¹² ) (R ¹¹ and R ¹² represent a hydrogen atom, an alkyl group, an aryl group or an acyl group). Examples of the selenium compound represented by the above formula (I) include N, N-dialkylselenourea, N, N, N ′
-Trialkyl-N'-acylselenoureas, tetraalkylselenoureas, N, N-dialkyl-arylselenoamides, N-alkyl-N-aryl-arylselenoamides are preferred.

Specific examples of the selenium compound represented by the formula (I) are shown below.

[0022]

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[0023]

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[0024]

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Next, the selenium compound represented by the above formula (II) will be described in detail. The above Z ²¹ , Z ²² and Z
Examples of the aliphatic groups represented by ²³ and R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ include linear, branched or cyclic alkyl, alkenyl, alkynyl and aralkyl groups. Can be. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, n-octyl, n-
Decyl, n-hexadecyl, cyclopentyl and cyclohexyl can be mentioned. Examples of the alkenyl group include, for example, allyl, 2-butenyl and 3-pentenyl. Examples of the alkynyl group include propargyl and 3-pentynyl. As the aralkyl group, for example,
Benzyl and phenethyl can be mentioned. The above Z ²¹ , Z ²² and Z ²³ , and R ²¹ , R ²² , R ²³ and R ²⁴
And examples of the aromatic group represented by R ²⁵ include a monocyclic or condensed-ring aryl group (eg, phenyl, pentafluorophenyl, 4-chlorophenyl, 3-sulfophenyl, α-naphthyl, 4-methylphenyl). Can be mentioned. The above Z ²¹ , Z ²² and Z ²³ , and R ²¹ , R
^The heterocyclic group represented by ²² , R ²³ , R ²⁴ and R ²⁵ is a 3- to 10-membered saturated or unsaturated heterocyclic group containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom. And examples of such a heterocyclic group include pyridyl, thienyl, furyl, thiazonyl, imidazolyl and benzimidazolyl. Examples of the halogen atom represented by Z ²¹ , Z ²² and Z ²³ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. In the selenium compound represented by the formula (II), any of Z ²¹ , Z ²² and Z ²³ may be a linking group to form a dimer. As a linking group,
Methylene groups can be mentioned. The cation represented by R ²¹ , R ²⁴ and R ²⁵ represents an alkali metal atom or ammonium.

In the above formula (II), Z ²¹ , Z ²² and Z ²³ are preferably an aliphatic group, an aromatic group or —OR ²¹ (R ²¹ represents an aliphatic group or an aromatic group). As the selenium compound represented by the above formula (II), a trialkylphosphine selenide, a triarylphosphine selenide, a trialkylselenophosphate, or a triarylselenophosphate is preferable.

Specific examples of the selenium compound represented by the formula (II) are shown below.

[0028]

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[0029]

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[0030]

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The selenium compounds represented by the above formulas (I) and (II) may be used alone or in combination of two or more. An unstable selenium compound and a non-unstable selenium compound can be used in combination.

Next, the tellurium compound will be described. Regarding tellurium sensitization, US Pat. No. 16,223,499,
Nos. 3320069, 3772031, British Patent No. 235111, No. 1121496, and No. 12
No. 95462, No. 1396696, Canadian Patent No. 8
00958, JP-A-4-204640, 4-27
No. 1341, No. 4-3333034, Japanese Patent Application No. 4-129
No. 787, No. 4-185004, Journal of
Chemical Society Chemical Communication (J. Chem. Soc. Chem. Commu)
n. ) 635 (1980), ibid 1102 (19)
79), ibid 645 (1979), Journal
Of Chemical Society Parkin Transaction (J. Chem. Soc. PerkinTra)
ns. ) 1, 191 (1980); Patai (S.
Patai) ed., The Chemistry of Organic Selenium and Tellurium Campounds (The Chemistry of Organic)
Selenium and Tellurium c
mpounds), Vol. 1 (1986), Vo
l. 2 (1987) and the like.

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′-diphenylethylene tellurourea), isotellurocyanates (eg, allyl isotellurocyanate),
Telluroketones (eg, telluroacetone, telluroacetophenone), telluroamides (eg, telluroacetamide, N, N′-dimethyltellurobenzamide), tellurohydrazide (eg, N ′, N′-trimethyltellurobenzhydrazide), telluroester ( For example, t-
Butyl-t-hexyl telluride), phosphine tellurides (for example, tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride, butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride), diacyl (diacyl) ) Tellurides (for example, bis (diphenylcarbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) telluride, diethylcarbamoyltelluride, bis (ethoxycarbonyl) telluride )), (Di) tellurides, and other tellurium compounds (eg, negatively charged telluride ion-containing gelatin described in British Patent No. 1295462, potassium telluride, potassium tellurocyaner) , Tellurocarbonyl penta isethionate, sodium salt, allyl tellurocyanate), and the like.

Among these tellurium compounds, compounds represented by the following formulas (III), (IV) or (V) are preferred.

[0035]

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[In the formula (III), R ³¹ , R ³² and R ³³ are each independently an aliphatic group, an aromatic group, a heterocyclic group, —O
^{R 34, -NR 35 (R 36} ), - SR 37, -OSiR 38 (R
³⁹⁾ R ^40, represent each a halogen atom or a hydrogen atom (said R ³⁴ and R ³⁷ are an aliphatic group, an aromatic group, a heterocyclic group, a hydrogen atom or a cation, R ³⁵ and R
³⁶ represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, respectively, and R ³⁸ , R ³⁹ and R ⁴⁰ each represent an aliphatic group. ]

[0037]

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[In the formula (IV), R⁴¹Is an aliphatic group, aromatic
Group, heterocyclic group or -NR⁴³(R⁴⁴) And R
⁴²Is -NR⁴⁵(R⁴⁶), -N (R⁴⁷) NR⁴⁸(R⁴⁹)
Or -OR³⁰(The above R⁴³, R⁴⁴, R⁴⁵,
R⁴⁶, R⁴⁷, R⁴⁸, R⁴⁹Or R⁵⁰Is the hydrogen source
Represents an aliphatic group, an aliphatic group, an aromatic group or an acyl group), provided that
Then R ⁴¹And R⁴⁵, R⁴¹And R⁴⁷, R⁴¹And R⁴⁸, R⁴¹When
R⁵⁰, R⁴³And R⁴⁵, R⁴³And R⁴⁷, R⁴³And R⁴⁸, And R
⁴³And R⁵⁰May be bonded to each other to form a ring
No. ]

[0039]

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[In the formula (V), R ⁵¹ and R ⁵² are each independently an aliphatic group, an aromatic group, a heterocyclic group or-(C ＝ R
⁵⁹⁾ represents a -R ^53, R ⁵³ is a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic ^{group, -NR 54 (R 55),} - represents OR ⁵⁶ or -SR ^57, R ⁵⁹ is oxygen An atom, a sulfur atom or —NR ⁵⁸ (the above R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ and R ⁵⁸ each represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group); Or 2 is represented. ]

The tellurium compounds represented by the above formulas (III), (IV) or (V) will be described below in order.
First, the tellurium compound represented by the above formula (III) will be described in detail. R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ ,
As the aliphatic group represented by R ³⁷ , R ³⁸ , R ³⁹ and R ⁴⁰ , an aliphatic group having 1 to 30 carbon atoms is preferable, and in particular, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms (for example, , Methyl, ethyl, n-propyl, isopropyl, t
-Butyl, n-octyl, n-decyl, n-hexadecyl, cyclopetyl, cyclohexyl), alkenyl groups (e.g. allyl, 2-butenyl, 3-pentenyl),
Alkynyl groups (eg, propargyl, 3-pentynyl) and aralkyl groups (eg, benzyl, phenethyl) are preferred.

The above R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶
And the aromatic group represented by R ^37,. 6 to carbon atoms
An aromatic group of 30 is preferable, and a monocyclic or condensed aryl group having 6 to 20 carbon atoms (for example, a phenyl group or a naphthyl group) is particularly preferable.

The above R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶
And the heterocyclic group represented by R ³⁷ includes a nitrogen atom,
Containing at least one of an oxygen atom and a sulfur atom 3
It is a 10-membered saturated or unsaturated heterocyclic 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 ring, and examples thereof include a pyridyl group, a furyl group, a thienyl group, a thiazolyl group, an imidazolyl group, and a benzimidazolyl group.

The cation represented by R ³⁴ and R ³⁷ represents an alkali metal or ammonium. R ³¹ ,
The halogen atom represented by R ³² and R ³³ is, for example,
Represents a fluorine atom, chlorine atom, bromine atom or iodine atom.

The above aliphatic group, aromatic group and heterocyclic group may be substituted. Representative substituents include the following. Alkyl group, aralkyl group, alkenyl group, alkynyl group, aryl group, alkoxy group, aryloxy group, amino group, 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, cyano group, sulfo group, carboxy group, hydroxyl group, phosphono group Group, nitro group, and heterocyclic group. These groups may be further substituted. When there are two or more substituents, they may be the same or different.

R ³¹ , R ³² and R ³³ may be bonded to each other to form a ring together with a phosphorus atom, and R ³⁵ and R ³⁶
May combine to form a nitrogen-containing heterocyclic ring.

The above R ³¹ , R ³² and R ³³ are each preferably an aliphatic group (particularly an alkyl group) or an aromatic group.

Specific examples of the compound represented by the above formula (III) are shown below, but it should not be construed that the invention is limited thereto.

[0049]

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[0050]

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Next, the tellurium compound represented by the formula (IV) will be described in detail. The above R ⁴¹ , R ⁴³ , R ⁴⁴ , R ⁴⁵ ,
As the aliphatic group, aromatic group and heterocyclic group represented by R ⁴⁶ , R ⁴⁷ , R ⁴⁸ , R ⁴⁹ and R ⁵⁰ , the aliphatic group, aromatic group represented by the above formula (III), And a heterocyclic group.

The above R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁷ ,
The acyl groups represented by R ⁴⁸ , R ⁴⁹ and R ⁵⁰ include
Those having 1 to 30 carbon atoms are preferred, and particularly those having 1 to 20 carbon atoms.
(E.g., acetyl, benzoyl, formyl, pivaloyl, decanoyl, etc.) are preferred.

The above R ⁴¹ and R ⁴⁵ , R ⁴¹ and R ⁴⁷ , R ⁴¹ and R ⁴⁸ , R ⁴¹ and R ⁵⁰ , R ⁴³ and R ⁴⁵ , R ⁴³ and R ⁴⁷ , R ⁴³ and R ^47
48 , and R ⁴³ and R ⁵⁰ are each linked to each other to form a ring, for example, an alkylene group,
Examples include an arylene group, an aralkylene group, and an alkenylene group. The aliphatic group, aromatic group and heterocyclic group may be substituted with the substituents described in the above formula (III).

R ⁴¹ is an aliphatic group, an aromatic group or-
NR ⁴³ (R ⁴⁴ ) is preferred, and more preferably an aromatic group or —NR ⁴³ (R ⁴⁴ ). The R ⁴² are, -NR ⁴⁵
(R ⁴⁶ ) is preferred, and R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ are preferably an aliphatic group (more preferably an alkyl group) or an aromatic group. It is preferred that R ⁴¹ and R ⁴⁵ and R ⁴³ and R ⁴⁵ form a ring via an alkylene group, an arylene group, an aralkylene group or an alkenylene group.

Specific examples of the compound represented by the above formula (IV) are shown below, but it should not be construed that the invention is limited thereto.

[0056]

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[0057]

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Next, the tellurium compound represented by the formula (V) will be described in detail. R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ ,
As the aliphatic group, aromatic group and heterocyclic group represented by R ⁵⁵ , R ⁵⁶ , R ⁵⁷ and R ⁵⁸ , the above-mentioned formula (II)
It has the same meaning as the aliphatic group, aromatic group and heterocyclic group represented by I). The aliphatic group, aromatic group and heterocyclic group may be substituted with the substituents described in the above formula (III). R ⁵¹ and R ⁵² , and R ⁵³ and R ⁵⁴ may be bonded to each other to form a ring.

R ⁵¹ and R ⁵² are each preferably a heterocyclic group or — (C ＝ R ⁵⁹ ) —R ^53, more preferably — (C ＝ R ⁵⁹ ) —R ⁵³ . R ⁵³ is —NR
⁵⁴ (R ⁵⁵ ) or —OR ⁵⁶ is preferred, and more preferably
—NR ⁵⁴ (R ⁵⁵ ). R ⁵⁹ is preferably an oxygen atom. R ⁵⁴ , R ⁵⁵ and R ⁵⁶ each represent an aliphatic group,
An aromatic group or a heterocyclic group is preferred. More preferably, R
^{The case where 54} and R ⁵⁵ are each an aliphatic group, an aromatic group or a heterocyclic group.

Specific examples of the compound represented by the above formula (V) are shown below, but it should not be construed that the invention is limited thereto.

[0061]

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[0062]

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[0063]

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[0064]

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The tellurium compounds represented by the above formulas (III) to (V) may be used alone or in combination of two or more. The tellurium sensitizer used in the present invention is a compound that forms silver telluride which is presumed to be a sensitizing nucleus on the surface of silver halide grains or inside the grains. The following test can be performed for the formation rate of silver telluride in a silver halide emulsion. Add a large amount (for example, 1 × 10
^-3 mol / mol Ag), the formed silver telluride has absorption in the visible region. Therefore, for the sulfur sensitizer, E.I. M
oisar is the Journal of Photogra
Phys Science, 14, 181 (196)
6) and Vol. 16, p. 102 (1968). The amount of silver sulfide formed in the silver halide emulsion was determined from the relative infinite reflectance of the emulsion in the visible region (520 nm) by a method similar to that obtained by using the Kubelka-Munk equation. The rate of silver telluride formation can be easily determined. Since this reaction is apparently close to a first-order reaction, a pseudo-first-order reaction rate constant can also be obtained. For example, a silver bromide octahedral emulsion having an average grain size of 0.5 μm (0.75 mol of AgBr and 80 mg of gelatin in a 1 kg emulsion)
g) is maintained 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.
The emulsion is placed in a 1 cm thick cell having an integrating sphere and having a spectrophotometer, and the reflectance (R) at 520 nm is measured over time with reference to the blank emulsion. Kube reflectivity
The pseudo-first-order reaction rate constant k (/ min) is obtained from the change of the value by substituting into the equation (1-R) ² / 2R of lka-Munk. If silver telluride is not generated, Ku is always R = 1.
The value of belka-munk remains the same as without the tellurium compound and remains at 0. The apparent first-order reaction rate constant k under the same conditions as in this test method is 1 × 10 ⁻⁸ to 1 × 10 ^0.
/ Min compound is preferred.

In a smaller amount of addition where the absorption in the visible region is difficult to detect, the silver telluride formed 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, the pA
It fluctuates greatly within a range of several digits depending on g and pH. The tellurium sensitizer preferably used in the present invention is a compound capable of forming silver telluride with respect to a specific silver halide emulsion having a halogen composition and a crystal habit to be used. Generally speaking, for a silver bromide emulsion, a temperature of 40 to 90 ° C.,
A compound capable of forming silver telluride at any one of pH 3 to 10 or pAg 6 to 11 is preferably used in the present invention. Compounds falling within the range of 1 × 10 ^-7 to 1 × 10 ^-1 / min are more preferred as tellurium sensitizers.

In preparing silver halide fine grains which have been subjected to selenium sensitization and / or tellurium sensitization in advance, the above selenium sensitizer and / or tellurium sensitizer may be used, and these may be mixed with water or water. It can be carried out by dissolving in an organic solvent (alcohols, esters, amides, etc.), adding to a silver halide fine grain emulsion, and aging under predetermined conditions. The amount of the selenium sensitizer and / or tellurium sensitizer used is
Although it varies depending on the silver halide grains of the host to be used and the conditions of chemical ripening, it is generally 10 ^-8 to 10 ^-2 mol, preferably 10 ^{-7 to} 5 ×, per mol of the silver halide of the host.
It is about 10 ^-3 mol. As described above, the sensitizing conditions for the silver halide fine grains are such that at least 30% or more of the added selenium sensitizer and / or tellurium sensitizer react with the silver halide fine grains. Preferably, specifically, pAg is in the range of 6 to 11, preferably in the range of 7 to 10. Temperature is 40-95 ° C
, Preferably in the range of 45 to 85 ° C. The aging time in this state is in the range of 5 minutes to 180 minutes, preferably in the range of 5 minutes to 120 minutes.

In preparing the silver halide fine particles as described above, it is preferable to further use a noble metal sensitizer such as gold, platinum, palladium or iridium. In particular, it is preferable to use a gold sensitizer. Specific examples include chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, and gold selenide. The amount of the gold sensitizer used is 10 ⁻⁷ to 1 mol per mol of silver halide.
It is about 10 ^-2 mol.

Further, in preparing the silver halide fine particles as described above, it is preferable to further use a sulfur sensitizer in combination. Specifically, thiosulfates (eg, hypo), thioureas (eg, diphenylthiourea, triethylthiourea, allylthiourea, etc.), rhodanines (eg, rhodanine, N-ethylrhodanine, 5-pendylidene) Rhodanine, 5-benzylidene-N-ethyl-rhodanine), thioamides (e.g., thioacetamide, N-phenylthioacetamide), and furthermore, thiohydantoins, 4-oxo-oxazoline-2-thiones, and dipoly. Known unstable sulfur compounds such as sulfides, cysteine mercapto compounds, polythionates, elemental sulfur and the like can be mentioned. The amount of the sulfur sensitizer used is about 10 ^-7 to 10 ^-2 mol per mol of silver halide.

In preparing the silver halide fine grains as described above, the sensitization conditions when gold sensitization and sulfur sensitization are used together are the same as those when selenium sensitization and / or tellurium sensitization are performed. is there.

The selenium- and / or tellurium-sensitized silver halide fine particles prepared as described above are then added to a host silver halide emulsion to obtain
The host silver halide emulsion is chemically sensitized. In this case, the chemical sensitization can be performed under the same conditions as the above-described conditions for selenium sensitization and / or tellurium sensitization of silver halide fine particles. When chemically sensitizing the silver halide emulsion of the host using silver halide fine particles which have been chemically sensitized in advance, the above-mentioned sulfur sensitizer, selenium sensitizer, tellurium sensitizer, gold sensitizer, It is preferable to add a sensitizer or an appropriate combination of these. The host silver halide emulsion will be described later.

In the present invention, a reduction sensitizer may be used in combination, and specifically, stannous chloride,
Aminoiminomethanesulfinic acid, hydrazine derivatives,
Examples include borane compounds (eg, dimethylamine borane), silane compounds, and polyamine compounds.

In the present invention, the chemical sensitization of the fine particles or the silver halide of the host is preferably carried out in the presence of a silver halide solvent. Specifically, thiocyanates (eg, potassium thiocyanate), thioether compounds (eg, US Pat. Nos. 3,012,215 and 3,271)
No. 157, JP-B-58-30571, JP-A-60-1
36736, especially 3,6-dithia-
1,8-octanediol, etc.), tetra-substituted thiourea compounds (for example, JP-B-59-11892, U.S. Pat.
Compounds described in JP-B-21863, particularly tetramethylthiourea), further, thione compounds described in JP-B-60-1134, mercapto compounds described in JP-B-63-29727, and JP-A-60-163242 Examples include a mesoionic compound, a selenoether compound described in U.S. Pat. No. 4,781,2013, a terether compound described in JP-A-2-118566, and a sulfite. In particular, among these, thiocyanates, thioether compounds, tetrasubstituted thiourea compounds and thione compounds can be preferably used. The amount used is 1 mol per mol of silver halide.
It is about 0 ^-5 to 10 ^-2 mol.

Next, a silver halide photographic light-sensitive material (sometimes simply referred to as a light-sensitive material) using a host silver halide emulsion prepared using the silver halide fine particles of the present invention will be described. The silver halide photographic material has a host silver halide emulsion layer on a support. The silver halide emulsion of the host used in the present invention is preferably silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide or silver chloride. The silver halide grains of the host used in the present invention have a regular (r) like cubic or octahedral shape.
Those having an amorphous crystal form, those having an irregular crystal form such as sphere, plate, or the like, or those having a composite form of these crystal forms. Although a mixture of particles of various crystal forms can be used, it is preferable to use a regular crystal form.

The silver halide grains of the host used in the present invention may have different phases in the inside and the surface layer or may consist of a uniform phase. Particles having two or more multi-structures having different iodine compositions between the inside of the particle and the surface layer (particularly, the iodine content inside is larger) are also preferred. Further, grains which mainly form a latent image on the surface thereof (for example, a negative emulsion) may be used, and grains which are mainly formed inside the grains (for example, an internal latent image type emulsion, a directly fogged emulsion which has been previously fogged) ). Preferably, the particles are such that the latent image is mainly formed on the surface. Further, particles containing dislocation lines are preferable.

The host silver halide emulsion used in the present invention has a thickness of 0.5 μm or less, preferably 0.1 μm or less.
Tabular grain emulsions having a size of 3 μm or less, preferably having a diameter of 0.6 μm or more, and having an average aspect ratio of 3 or more occupying 50% or more of the total projected area are also preferred. Further, tabular emulsions having good monodispersity described in JP-A-2-838 are particularly preferred.

The silver halide emulsion of the host used in the present invention has a statistical variation coefficient (a value obtained by dividing the standard deviation S by the diameter d in the distribution expressed by the diameter when the projected area is approximated by a circle). Monodisperse emulsions in which d) is at most 20% are particularly preferred. Further, two or more emulsions may be mixed.

The photographic emulsion used in the present invention is, for example, Chimie Physique Photography by P. Glafkids.
er Physique Photographeq
ue) (Paul Montell, 1967), by GF Duffin, Photographic Emulsion Chemistry (Photog)
raphic Emulsion Chemistr
y) (Focal Press, 1966), Making and Coating Photographic, by VL Zelikman et al.
Emulsion (Making and Coating
Photographic Emulsion (Focal Press, 1964).

In forming the silver halide grains,
As a silver halide solvent for controlling the growth of grains, for example, ammonia, rodancali, rodanammon, thioether compounds (for example, US Pat. No. 3,271)
No. 157, No. 3574628, No. 3704130
Nos. 4,297,439 and 4,276,374),
Thione compounds (for example, JP-A-53-144319, JP-A-53-82408, and JP-A-55-77737) and amine compounds (for example, JP-A-54-100717) can be used.

Cadmium salts, zinc salts,
A thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, and the like may coexist. As a binder or protective colloid which can be used in the emulsion layer or the intermediate layer of the photographic material, gelatin is advantageously used, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and 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; polyvinyl alcohol , Polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone,
Various synthetic hydrophilic polymer substances such as a single or copolymer of polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, and polyvinylpyrazole can be used.

Examples of the gelatin include general-purpose lime-processed gelatin, acid gelatin, and the journal of the Japan Science Photographic Society (Bul
l. Soc. Photo. Japan), No. 16,3
Enzyme-treated gelatin as described on page 0 (1966) may be used, or a hydrolyzate of gelatin may be used.

The photographic light-sensitive material may contain an inorganic or organic hardener in any hydrophilic colloid layer constituting the photographic light-sensitive layer or the back layer. For example, chromium salt,
Aldehyde salts (for example, formaldehyde, glyoxal, glutaraldehyde) and N-methylol-based compounds (for example, dimethylol urea) are specifically mentioned. Active halogen compounds (for example, 2,4-dichloro-6
-Hydroxy-1,3,5-triazine and its sodium salt) and active vinyl compounds (e.g., 1,3-bisvinylsulfonyl-2-propanol, 1,2-bis (vinylsulfonylacetamido) ethane, bis (vinylsulfonylmethyl) ) A vinyl polymer having an ether or bitylsulfonyl group in the side chain) is preferable because it rapidly cures a hydrophilic colloid such as gelatin and gives stable photographic properties. N-carbamoylpyridinium salts (eg, (1-morpholinocarbonyl-3-pyridinio) methanesulfonate) and haloamidinium salts (eg, 1- (1-chloro-1-pyridinomethylene) pyrrolidinium-2-naphthalenesulfonate) also cure. Excellent early.

The silver halide photographic emulsion of the host used in the present invention is preferably spectrally sensitized with a methine dye or the like. 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. Any of the nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, the pyrroline nucleus is an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus,
A selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, etc .; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, that is, an indolenine nucleus, a benz Indolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, and the like can be applied. These nuclei may have a substituent on a carbon atom.

In the merocyanine dye or the complex merocyanine dye, nuclei having a ketomethylene structure such as pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thiooxazolidin-2,4-dione nucleus, thiazolidine-2,
A 5- to 6-membered heterocyclic nucleus of a 4-dione nucleus, a rhodanine nucleus, and a thiobarbituric acid nucleus can be applied.

These sensitizing dyes may be used alone or in combination, and a combination of sensitizing dyes is often used particularly for supersensitization. Along with 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. For example, a substituted aminostilbenzene compound having a nitrogen-containing heterocyclic nucleus group (for example, US Pat. Nos. 2,933,390 and 36)
No. 35721), formaldehyde condensates of aromatic organic acids (for example, those described in US Pat. No. 3,743,510), cadmium salts, azaindene compounds and the like. U.S. Pat. Nos. 3,615,613 and 361
The combinations described in JP-A-5641, JP-A-3617295 and JP-A-3635721 are particularly useful.

The silver halide photographic emulsion of a host or a fine grain used in the present invention may be used for various purposes, for example, to prevent fogging during the production process of a photographic material, storage or photographic processing, or to stabilize photographic performance. Can be contained. That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, and aminotriazole , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-
Mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrithione; azaindenes; for example, triazaindenes, tetraazaindenes (especially 4-
Hydroxy-6-methyl (1,3,3a, 7) tetraazaindene), pentaazaindenes; known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid and benzenesulfonamide Many compounds can be added.

The photographic light-sensitive material contains one or more surfactants for various purposes such as coating aids, antistatic properties, improvement of slipperiness, emulsification / dispersion, prevention of adhesion and improvement of photographic properties (eg, development acceleration, high contrast, sensitization). May be included.

The photographic light-sensitive material is used as a filter dye.
Alternatively, a water-soluble dye may be contained in the hydrophilic colloid layer for the purpose of preventing irradiation or halation and other various purposes. As such dyes, oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, anthraquinone dyes, and azo dyes are preferably used.In addition, cyanine dyes, azomethine dyes, triarylmethane dyes, and phthalocyanine dyes are also useful. . The oil-soluble dye may be emulsified by an oil-in-water dispersion method and added to the hydrophilic colloid layer.

The photographic light-sensitive material has at least two
It can be constructed as a multilayer multicolor photographic material having two different spectral sensitivities. The multilayer natural color photographic material usually has at least one red-sensitive emulsion layer, one green-sensitive emulsion layer and one blue-sensitive emulsion layer on a support. The arrangement order of these layers can be arbitrarily selected as needed. The preferred layer arrangement is from the support side in the order of red sensitivity, green sensitivity and blue sensitivity, blue sensitivity, green sensitivity and red sensitivity or blue sensitivity, red sensitivity and green sensitivity. In addition, any emulsion layer having the same color sensitivity may be composed of two or more emulsion layers having different sensitivities to improve the reaching sensitivity, or a three-layer constitution may be used to further improve the graininess.
Further, a non-photosensitive layer may be present between two or more emulsion layers having the same color sensitivity. An emulsion layer having a different color sensitivity may be inserted between emulsion layers having the same color sensitivity. A reflective layer of fine grain silver halide or the like may be provided below the high-sensitivity layer, particularly the high-sensitivity blue-sensitive layer, to improve the sensitivity.

It is common to include a cyan-forming coupler in the red-sensitive emulsion layer, a magenta-forming coupler in the green-sensitive emulsion layer, and a yellow-forming coupler in the blue-sensitive emulsion layer. Can also. For example, a combination of infrared-sensitive layers may be used for pseudo color photography or semiconductor laser exposure.

Various color couplers can be used, and specific examples thereof are described in Research Disclosure (RD) No. 17643, 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, Japanese Patent Publication No. 58-10739, British Patent No. 1,42
Nos. 5,020 and 1,476,760 are preferred.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based 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, U.S. Pat. No. 4,500,603
No. 4,540,654 are preferred.

Examples of the cyan coupler include phenol type and naphthol type couplers. For example, US Pat. Nos. 4,052,212, 4,146,396, 4,228,233, and 4th. , 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,
No. 173, West German Patent Publication No. 3,329,729, European Patent No. 121,365A, U.S. Pat. No. 3,446,6.
No. 22, No. 4,333,999, No. 4,451,
No. 559, No. 4,427,767, European Patent No. 16
Those described in 1,626A are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are described in, for example, Research Disclosure No. 17643, section VII-G, U.S. Pat.
No. 3,670, JP-B-57-39413, U.S. Pat. Nos. 4,004,929 and 4,138,258 and British Patent 1,146,368 are preferred.

Examples of couplers in which a coloring dye has an appropriate diffusibility include, for example, US Pat. No. 4,366,237, British Patent No. 2,125,570, and European Patent No. 96,57.
No. 0 and West German Patent (Publication) No. 3,234,533 are preferred.

Typical examples of polymerized dye-forming couplers are described in US Pat. Nos. 3,451,820 and 4,084.
Nos. 0,211 and 4,367,282, and British Patent No. 2,102,173.

Couplers 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 same as described above for R
D17643, Patents described in Section VII-F,
Nos. 7-151944, 57-154234, 6
No. 0-184248 and U.S. Pat. No. 4,248,962 are preferred.

Examples of couplers which release a nucleating agent or a development accelerator imagewise during development include, for example, British Patent No.
Nos. 097,140 and 2,131,188, and JP-A-59-157638 and JP-A-59-170840 are preferred.

Other couplers that can be used in photographic materials include, for example, US Pat. No. 4,130,4.
No. 27, U.S. Pat. No. 4,283,
No. 472, No. 4,338,393, No. 4,31
No. 0,618, a multi-equivalent coupler described in JP-A-60-1
No. 85950, DI described in JP-A-62-24252.
R redox compounds or DIR coupler releasing couplers, couplers which release dyes which recolor after release as described in EP 173302A; D. No. 1144
9, 24241, and bleaching accelerator releasing couplers described in JP-A-61-201247; U.S. Pat.
No. 77, and the like.

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 US Pat. No. 2,322,027 and the like.

Specific examples of the high-boiling organic solvent having a boiling point at normal pressure of 175 ° C. or higher used in the oil-in-water dispersion method include phthalic acid esters (for example, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate). , Decyl phthalate, bis (2,4-di-t-aminophenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate), phosphoric acid or Esters of phosphonic acid (for example, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridecyl phosphate, tributoxyethyl phosphate and trichloropropyl phosphate DOO, di-2-ethylhexyl phenyl phosphate), benzoic acid esters (e.g., 2-
Ethylhexyl benzoate, dodecyl benzoate,
2-ethylhexyl-p-hydroxybenzoate),
Amides (for example, N, N-diethyldodecaneamide,
N, N-diethyllaurylamide, N-tetradecylpyrrolidone), alcohols or phenols (eg, isostearyl alcohol, 2,4-di-tert)
-Amylphenol), aliphatic carboxylic acid esters (for example, bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate),
Examples include aniline derivatives (for example, N, N-dibutyl-2-butoxy-5-tert-octylaniline) and hydrocarbons (for example, paraffin, dodecylbenzene, diisopropylnaphthalene). The auxiliary solvent has a boiling point of 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C.
Organic solvents having a temperature of not more than ℃ can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, and dimethylformamide.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,3.
No. 63, West German Patent Application (OLS) No. 2,541,274
And No. 2,541,230.

In the photographic light-sensitive material, the photographic emulsion layer and other layers are coated on a flexible support such as a plastic film, paper, cloth or the like or a rigid support such as glass, pottery or metal which is usually used for the photographic light-sensitive material. Is done. Useful as a flexible support are films made of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, etc., baryta layer or α-olefin polymer. (Eg polyethyne,
Paper or the like coated or laminated with polypropylene, ethylene / butene copolymer). The support may be colored using a dye or a pigment. It may be black for the purpose of shading. The surface of these supports is generally subjected to a subbing treatment in order to improve adhesion with a photographic emulsion layer or the like. The surface of the support may be subjected to glow discharge, corona discharge, ultraviolet irradiation, flame treatment or the like before or after the undercoating treatment.

For coating the photographic emulsion layer and other hydrophilic colloid layers, various known coating methods such as dip coating method, roller coating method, curtain coating method and extrusion coating method can be used. U.S. Pat.
No. 681,294, No. 2,761,791, No. 3,526,528 and No. 3,508,947, the multilayer may be applied simultaneously.

The present invention can be applied to various color and black-and-white photographic materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers, color diffusion transfer type photosensitive materials and heat development type color photosensitive materials. . Research Disclosure No. 171
23 (July 1978), or by utilizing a three-color coupler mixture or as described in U.S. Pat.
The present invention can be applied to black-and-white photographic materials such as those for X-rays by utilizing the black color couplers described in U.S. Pat. No. 461 and British Patent No. 2,102,136. Stencil film such as squirrel film or scanner film,
The present invention is also applied to X-ray film for direct medical treatment, indirect medical treatment, or industrial use, negative black-and-white film for photography, black-and-white photographic paper, COM or ordinary microfilm, silver salt diffusion transfer type photosensitive material and printout type photosensitive material. it can.

When the present invention is applied to the color diffusion transfer photographic method, a peeling (peel apartment) type or a special
Nos. 6-16356 and 48-33697, JP-A-50
Integrated type as described in US Pat. No. -13040 and British Patent 1,330,524;
A structure of a film unit that does not require peeling as described in JP-A-57-119345 can be employed.

In any of the above formats, the use of a polymer acid layer protected by a neutralization timing layer is advantageous in widening the allowable range of processing temperatures. When used in color diffusion transfer photography, it may be used by adding to any layer in the light-sensitive material, or
It may be used as a developer component by being enclosed in a processing solution container.

Various exposure means can be used in the photographic light-sensitive material. Any light source that emits radiation corresponding to the sensitivity wavelength of the photosensitive material can be used as the illumination light source or the writing light source. Flash light sources such as natural light (sunlight), incandescent lamps, halogen-filled lamps, mercury lamps, fluorescent lamps, and strobe or metal-burning flash bulbs are common.

Gas, dye solution or semiconductor lasers, light emitting diodes, and plasma light sources that emit light in the wavelength range from ultraviolet to infrared can also be used as the recording light source. Also, a phosphor screen (such as a CRT) emitted from a phosphor excited by an electron beam or the like, a liquid crystal (LCD) or lanthanum-doped lead zirconate titanate (PLZ)
Exposure means in which a linear or planar light source is combined with a micro shutter array using T) or the like can also be used. If necessary, the spectral distribution used for exposure can be adjusted with a color filter.

The light-emitting developer used in the development of the photographic light-sensitive material is preferably an alkaline aqueous solution mainly containing an aromatic primary amine color developing agent. Aminophenol compounds are also useful as the color developing agent, but P-phenylenediamine compounds are preferably used, and a typical example thereof is 3-methyl-4-amino-N, N
-Diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl- 4-Amino-N-ethyl-N-β-methoxyethylaniline and sulfates, hydrochlorides or p-toluenesulfonates thereof. These diamines are generally more stable in a salt than in a free state, and are preferably used.

The color developing solution includes a pH buffer such as an alkali metal carbonate, borate or phosphate, bromide,
It generally contains development inhibitors or antifoggants such as iodides, benzimidazoles, benzothiazoles or mercapto compounds. Also, if necessary,
Preservatives such as hydroxyamine or sulfite, organic solvents such as triethanolamine, diethylene glycol, benzyl alcohol, polyethylene glycol,
Quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competing couplers, nucleating agents such as sodium boron hydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity-imparting agents, amino Polycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid,
Various chelating agents represented by phosphonocarboxylic acid and antioxidants described in West German Patent Application (OLS) No. 2,622,950 may be added to the color developer.

In the development process of the reversal color photosensitive material, color development is usually performed after black and white development. The black-and-white developer includes dihydroxybenzenes such as hydroquinone,
Known black-and-white developers such as 3-pyrazolidones such as -phenyl-3-pyrazolidone or N-methyl-p-aminophenols can be used alone or in combination.

The photographic emulsion layer after color development is usually subjected to bleaching. The bleaching process may be performed simultaneously with the 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. Examples of the bleaching agent include compounds of polyvalent metals such as iron (III), cobalt (III), chromium (IV), and copper (II), peracids, quinones, and nitrone compounds. Representative bleaches include ferricyanide; dichromate; organic complexes of iron (III) or cobalt (III), such as ethylenediaminetetraacetic acid, diethyleneaminepentaacetic acid, nitrilotriacetic acid,
Use of aminopolycarboxylic acids such as 1,3-diamino-2-propanoltetraacetic acid or complex salts of organic acids such as citric acid, tartaric acid and malic acid; manganate; persulfate; manganate; Can be. Of these, iron (III) ethylenediaminetetraacetate,
Diethylenetriaminepentaacetate iron (III) salt and persulfate are preferred from the viewpoint of rapid processing and environmental pollution. Further, the iron (III) complex salt of ethylenediaminetetraacetate is particularly useful in an independent bleaching solution or a single-bath bleach-fixing solution.

In the bleaching solution, the bleach-fixing solution and the prebath thereof, a bleaching accelerator can be used if necessary.
Specific examples of useful bleach accelerators are described in the following specification. U.S. Patent 3,893,858, West German Patent 1,290,812
No. 2,059,988, JP-A-53-32736, JP-A-53-57831
Nos. 37418, 53-65732, 53-72623, 53-9
No. 5630, No. 53-95631, No. 53-104232, No. 53-124424
No. 53-141623, 53-28426, Research Disclosure No. 17129 (July 1978), etc., having a mercapto group or a disulfide group;
Thiazolidine derivatives as described in JP-A-50-140129; JP-B-45-8506; JP-A-52-20832;
Thiourea derivatives described in U.S. Pat. No. 3,706,561;
Iodides described in West German Patent No. 1,127,715, JP-A-58-16235; Polyethylene oxides described in West German Patents 966,410 and 2,748,430; Polyamine compounds described in JP-B-45-8836; No.49-42434, 49-596
The compounds described in Nos. 44, 53-94927, 54-35727, 55-26506 and 58-163940 and iodine and bromide ions can also be used. Among them, compounds having a mercapto group or a disulfide group are preferred in view of a large accelerating effect, and in particular, U.S. Pat. No. 3,893,858 and West German Patent 1,290,8
No. 12, JP-A-53-95630 are preferred. Further, the compounds described in U.S. Pat. No. 4,552,834 are also preferred.
These bleaching accelerators may be added to the light-sensitive material. When bleach-fixing a color photographic material for photography, these bleaching accelerators are particularly effective.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide, and thiosulfates are generally used. As a preservative for the bleach-fixing solution or the fixing solution, a sulfite, a bisulfite or a carbonyl bisulfite adduct is preferable.

After the bleach-fixing process or the fixing process, a washing process and a stabilizing process are usually performed. In the washing step and the stabilizing step, various known compounds may be added for the purpose of preventing precipitation and saving water. For example, in order to prevent precipitation, water hardeners such as inorganic phosphoric acid, aminopolycarboxylic acid, organic aminopolyphosphonic acid, and organic phosphoric acid, fungicides for preventing the generation of various bacteria, algae and fungi, and antibacterial agents are used. Agents, metal salts such as magnesium salts, aluminum salts and bismuth salts, surfactants for preventing drying load and unevenness, and various hardeners can be added as necessary. Or West, Photographic Science and Engineering (LE West, Phot. Sci. Eng.), No. 6,
Vol., Pages 344 to 359 (1965) and the like. Particularly, the addition of a chelating agent or an anti-binder is effective.

In the water washing step, two or more tanks are subjected to countercurrent water washing.
It is common to save water. Further, instead of the water washing step, a multi-stage countercurrent stabilization step as described in JP-A-57-8543 may be carried out. In the case of this step, 2 to 9 countercurrent baths are required. Various compounds other than the above-mentioned additives are added to the stabilizing bath for the purpose of stabilizing an image. For example, various buffers (for example, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, etc.) for adjusting the membrane pH (for example, pH 3 to 9) Aldehydes such as monocarboxylic acid, dicarboxylic acid and polycarboxylic acid) and formalin can be mentioned as typical examples. In addition, if necessary, chelating agents (eg, inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, organic phosphonic acid, aminophosphonic acid, phosphonocarboxylic acid), bactericides (eg, benzoisothiazolinone, isothiazolone, 4- Various additives such as thiazoline benzimidazole, halogenated phenol, sulfanilamide, benzotriazole), surfactants, optical brighteners, hardeners, etc. may be used, and two or more kinds of the same or different target compounds may be used. You may use together.

It is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, ammonium thiosulfate and the like as a membrane pH adjuster after the treatment.

Further, in the color photographic light-sensitive material for photography, the usual step after fixing (washing-stabilization) can be replaced by the above-mentioned stabilizing step and washing step (water saving processing). At this time, when the amount of the magenta coupler is 2 equivalents, formalin in the stabilizing bath may be removed.

The washing and stabilizing processing time of the present invention varies depending on the type of the light-sensitive material and the processing conditions, but is usually 20 seconds to 10 minutes, preferably 20 seconds to 5 minutes.

The silver halide color light-sensitive material may contain a color developing agent 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.
Indoaniline compounds described in No. 597, 3,342,599
No., Research Disclosure No. 14850 and No. 15
JP-A-56-6235, including Schiff base-type compounds described in JP-A-159, aldol compounds described in JP-A-13924, metal salt complexes described in U.S. Patent No. 3,719,492, and urethane-based compounds described in JP-A-53-135628. No., 56-16133, 56-5
9232, 56-67842, 56-83734, 56-83735,
56-83736, 56-89735, 56-81837, 56-544
No. 30, No. 56-106241, No. 56-107236, No. 57-97531 and No. 57-83565.

The silver halide color light-sensitive material may contain various 1-phenyl-3-pyrazolidones as necessary for the purpose of accelerating color development. Typical compounds are described in JP-A-56-64339, JP-A-57-144547 and JP-A-57-211.
No. 147, No. 58-50532, No. 58-50536, No. 58-50533,
Nos. 58-50534, 58-50535 and 58-115438.

Various processing solutions are used at 10 ° C. to 50 ° C. Temperatures of 33 ° C. to 38 ° C. are standard,
A higher temperature promotes the processing to shorten the processing time, while a lower temperature improves the image quality and the stability of the processing solution. Further, in order to save silver of the light-sensitive material, a process using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or U.S. Pat. No. 3,674,499 may be performed.

A heater, a temperature sensor, a liquid level sensor, a circulating pump, a filter, a floating pig, a squeegee, etc. may be provided in the various treatment baths, if necessary.

In the continuous processing, a certain finish can be obtained by using the replenisher of each processing solution to prevent the fluctuation of the liquid composition. The replenishment amount can be reduced to half or less of the standard replenishment amount for cost reduction and the like.

When the photographic light-sensitive material is color paper, it can be very commonly used, and when it is a photographic color photographic material, it can be subjected to bleach-fixing if necessary.

[0129]

EXAMPLES The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to only these examples.

[Example 1] (Preparation of silver halide fine grain emulsion sensitized with selenium or / and tellurium) AgCl _0.75 Br _0.25 fine grain emulsion (particle diameter 0.12 μm, pH 6.5, pAg 7.6, gelatin 8)
% Sensitizers shown in Table 1 below, and ripened at 56 ° C. for 15 minutes to prepare chemically sensitized silver halide fine grain emulsions Em-101 to Em-110. . Selenium sensitizers and tellurium sensitizers represented by I-1 to V-24 are given by the following formulas.

[0131]

[Table 1] Table 1 ──────────────────────────────────── Fine particle chalcogen sensitizer Chloroauric acid Emulsion (addition amount: mol / mol Ag) (addition amount: mol / mol Ag)ナ ト リ ウ ム Em-101 Sodium thiosulfate 3.2 × 10 ^-3 6.4 × 10 ^-3 Em-102 I-1 (Se) Same as above Em-103 I-6 (Se) Same as above Em-104 I-12 (Se) Same as Em-105 II-1 (Se) Same as Em-106 II-21 (Se) 2.4 × 10 ^-3 Same as Em-107 III-12 (Te) 6.4 × 10 ^-3: Em-108 IV-1 (Te) 6.4 × 10 ^-3: Em-109 V-1 (Te): 1.6 × 10 ^-3: Em-110 V-24 (Te): 1.6 × 10 ^-3 same ─────────────────────────────── ────

[0132]

Embedded image

(Preparation of Host Silver Halide Emulsion Em-A) A silver nitrate aqueous solution (18 g of AgNO ₃₎ was stirred at a temperature of 75 ° C. in 1 liter of an aqueous solution containing 0.35 g of potassium bromide and 40 g of gelatin and having a pH of 5.0. ) And an aqueous potassium bromide solution (KBr 12.7 g) were added simultaneously over 20 minutes. Next, an aqueous solution of silver nitrate (156 g of AgNO ₃ ) and a mixed aqueous solution of potassium iodide and potassium bromide (6.1 g +
196 g / l) was added simultaneously over 20 minutes by a flow rate accelerating method that makes the final rate of the addition flow rate 5.4 times, while keeping the silver potential at -25 mV with respect to the saturated calomel electrode. After completion of particle formation, desalting and washing with ordinary flocculation method are performed, and gelatin and water are added to adjust the pH to 6.
The pAg was adjusted to 8.3 and 8.3. The obtained silver bromide emulsion (Em-A) was a monodispersed octahedral emulsion having a silver iodide content of about 2 mol%, a grain diameter of 0.49 μm, and a coefficient of variation of the grain diameter of 9.5%. Was.

(Preparation of Emulsion According to the Present Invention) The emulsion Em-A prepared above was divided into small portions and the temperature was raised to 60 ° C. next,
As shown in Table 2, corresponding Em-101 to 110 (previously chemically sensitized fine grain emulsion) were added per mole Ag of emulsion Em-A (0.5% of Em-A in silver amount). In addition, sodium thiosulfate (1.6 × 10 ⁻⁵ mol / mol Ag) and potassium thiocyanate (1 × 10 ⁻³ mol / mol Ag) are added, and the mixture is aged for 60 minutes, according to the present invention. Various emulsions were prepared.

(Preparation of Comparative Emulsion) The emulsion Em-A prepared above was divided into small portions and the temperature was raised to 60 ° C. Then, the same chemical sensitizer as used for the sensitization of the fine grain emulsion was dissolved in water or a methanol solution so as to have the same addition amount, added to the emulsion Em-A, chemically sensitized, and used for comparison. Was prepared.

(Preparation of Photographic Material (Sample)) Anhydro-5-chloro-5'-phenyl-9-ethyl-3,3'-di (3-sulfopropyl) benzoxa was added to each emulsion obtained above. Carbocyanine hydroxide sodium salt (sensitizing dye), phenoxyethanol, gelatin,
4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, potassium poly-styrenesulfonate, and sodium dodecylbenzenesulfonate are added to prepare a coating solution for forming a photosensitive layer, and the undercoat layer is formed. Gelatin, polymethyl methacrylate particles, and 2,4-dichloro-
Co-extrusion was applied together with a coating solution for forming a protective layer containing 6-hydroxy-s-triazine sodium salt to prepare Samples 1 to 20 corresponding to each.

[Evaluation as Photographic Photosensitive Material] Each of the samples obtained above was evaluated for photographic properties (fog, relative spectral sensitivity) as follows. (1) To the sample obtained above, exposure for sensitometry (1/100 second) was given through an optical wedge using an SC-50 filter (manufactured by Fuji Photo Film Co., Ltd.). Then, it developed with Kodak prescription D-19 developer at 20 degreeC for 10 minutes. Stop, fix, wash, dry, and
The concentration was measured to obtain the results shown in Table 2. The relative spectral sensitivity is represented by a relative value of a reciprocal of an exposure amount necessary to obtain an optical density of (fog value + maximum density) / 2.

[0138]

Table 2 ──────────────────────────────────── Sample Fine particles used for emulsion preparation or Sensitizer Relative spectral number (addition amount: mol / mol Ag) Fog sensitivity ───────────────────────────────── １ 1 (comparison) Sodium thiosulfate (S) + chloroauric acid (Au) 0.10 100 2 (comparison) Em-101 (S: 1.6 × 10 ^{−5 /} Au: 3.2 × 10 ⁻⁵ ) 08 118 ────────────────────────────────────3 (comparison) I-1 (Se) + chloride Auric acid (Au) 0.19 169 4 (the present invention) Em-102 (Se: 1.6 × 10 ^{-5 /} Au: 3.2 × 10 ^-5 ) 0.14 238 ──────────── ５5 (comparison) I-6 (Se) + chloroauric acid (Au) 0.17 1 6 6 (present invention) Em-103 (Se: 1.6 × 10 -5 /Au:3.2×10 -5) 0.13 240 ──────────────────── ７7 (comparative) I-12 (Se) + chloroauric acid (Au) 0.17 176 8 (invention) Em-104 (Se: 1.6 × 10 ^-5 /Au:3.2×10 ^-5 ) 0.13 242 ────────────────────────────────── ９ 9 (comparative) II-1 (Se) + chloroauric acid (Au) 0.14 182 10 (invention) Em-105 (Se: 1.6 × 10 ⁻⁵ /Au:3.2×10 ⁻⁵ ) 13 240 11 (comparison) II-21 (Se) + chloride Auric acid (Au) 0.14 188 12 (Invention) Em-106 (Se: 1.2 × 10 ⁻⁵ /Au:3.2×10 ⁻⁵ ) 0.12 244 ° ───────────────────── ─── 13 (comparative) III-12 (Te) + chloroauric acid (Au) 0.31 204 14 (invention) Em-107 (Te: 3.2 × 10 ⁻⁵ /Au:3.2×10 ⁻⁵ ) 0 .21 308 ──────────────────────────────────── 15 (comparison) IV-1 (Te) + Chloroauric acid (Au) 0.36 208 16 (invention) Em-108 (Te: 3.2 × 10 ^{-5 /} Au: 3.2 × 10 ^-5 ) 0.21 312 ─────────── ───────────────────────── 17 (comparison) V-1 (Te) + chloroauric acid (Au) 0.26 224 18 (the present invention) ) Em-109 (Te: 8 × 10 ^-6 /Au:3.2×10 ^-5 ) 0.20 322───────────────────────── ───────────19 (comparison) V-24 (Te) + chloroauric acid (Au) 0.24 220 20 (Invention) Em-110 (Te: 8 × 10 ^-6 / Au ^{: 3.2 × 10 -5) 0.20 320} ───────── ──────────────────────────

As is evident from the results shown in Table 2 above, a sensitization method according to the present invention, in which sensitization was previously performed using selenium or / and tellurium-sensitized silver halide fine grains, was introduced. By using a silver halide emulsion (an even-numbered sample excluding Sample 2), a photographic light-sensitive material having less fog and high spectral sensitivity can be obtained.

(2) 1, 2, 11, 1
Using each of the samples 2, 19 and 20, the photographic properties after storage were evaluated. Each sample was stored under high temperature and high humidity of 45 ° C. and relative humidity of 80% RH for 3 days, and a sample stored in a refrigerator (about 5 ° C. for 3 days) for comparison was subjected to the same treatment as described above. This was used to evaluate the photographic properties. Table 3 shows the results.

[0141]

Table 3 Table 3 の Refrigerator used for emulsion preparation Storage Storage under high temperature and high humidity Sample Fine particles or sensitizer Relative Relative number (addition amount: mol / mol Ag) Fog sensitivity Fog sensitivity ────────────────────── ────────────── 1 (comparison) sodium thiosulfate (S) 0.10 100 0.16 76 + chloroauric acid (Au) 2 (comparison) Em-101 0.08 118 0.14 98 (S: 1.6 × 10 ^-5 /Au:3.2×10 ^-5 ) ───────────────────────────── ─────── 11 (comparison) II-21 (Se) 0.14 188 0.39 132 + chloroauric acid (Au) 12 (invention) Em-106 0.12 244 0.32 217 (Se ^{: 1.2 × 10 -5 /Au:3.2×10 -5)} ───────── ────────────────────────── 19 (comparison) V-24 (Te) 0.24 220 0.31 187 + chloroauric acid (Au ) 20 (invention) Em-110 0.20 320 0.24 302 (Te: 8 × 10 ⁻⁶ /Au:3.2×10 ⁻⁵ ) ────────────────────

As is evident from the results shown in Table 3 above, a sensitization method according to the present invention, in which sensitization was previously performed using selenium or / and tellurium-sensitized silver halide fine grains, was introduced. Silver halide emulsion (Samples 12 and 2)
By using 0), a photographic light-sensitive material having less fog and high spectral sensitivity even when stored under high temperature and high humidity can be obtained.

Example 2 AgBr _0.995 I _0.005 fine grain emulsion (particle size 0.08 μm, pH 6.5, pAg8.
0, containing 8% of gelatin), sensitized at 56 ° C. for 20 minutes, and chemically sensitized silver halide fine grain emulsions Em-201 to Em-
I made 206. Selenium sensitizers and tellurium sensitizers represented by I-7 to V to 32 are given by the following formulas.

[0144]

[Table 4] ──────────────────────────────────── Fine particle chalcogen sensitizer Chloroauric acid Emulsion (addition amount: mol / mol Ag) (addition amount: mol / mol Ag)ナ ト リ ウ ム Em-201 Sodium thiosulfate 1.2 × 10 ^-3 2.0 × 10 ^-3 Em-202 I-7 (Se) 1.0 × 10 ^-3 Same as Em-203 II-21 (Se ) 8.0 × 10 ^-4 Em-204 III-10 (Te) 1.0 × 10 ^-3 Em-205 V-32 (Te) 6.0 × 10 ^-4 Em-206 II-21 ( Se) 4.0 × 10 ⁻⁴ 1.6 × 10 ⁻³ + V−32 (Te) 4.0 × 10 ⁻⁴ } ───────────────

[0145]

Embedded image

(Preparation of Host Silver Halide Emulsion Em-B) 10 g of potassium bromide, 0.4 g of potassium iodide and 15 g of inert gelatin having an average molecular weight of 15,000 were distilled water.
While thoroughly stirring the aqueous solution dissolved in 7 liters, a 14% aqueous solution of potassium bromide and a 20% aqueous solution of silver nitrate were added thereto at a constant flow rate for 15 seconds at 55 ° C. and pBr 1.0 by the double jet method ( This addition consumed 5.5% of the total silver.) Gelatin aqueous solution (1
After stirring at 55 ° C., a 20% aqueous silver nitrate solution was added at a constant flow rate until pBr reached 1.4 (this addition consumed 5.0% of the total silver). . Furthermore, a 20% potassium iodobromide solution (KB
_{r 1-X I X:.} X = 0.04) and was added over 43 minutes with a 33% aqueous solution of silver nitrate double jet (consumed 25% of the total silver amount in this added) Here,
After adding an aqueous solution containing 4.5 g of potassium iodide,
14.5m of 0.001 / wt% K ₃ IrCl ₆ aqueous solution
and a mixed aqueous solution of 18% potassium bromide and 3% potassium iodide and a 33% aqueous silver nitrate solution were added by a double jet method over 39 minutes (this addition consumed 64.5% of the total silver amount). did). The amount of silver nitrate used in this emulsion was 425 g. Next, desalting was carried out by a usual flocculation method. After desalting, gelatin and water were added to adjust the pAg to 8.2 and the pH to 5.8 at 40 ° C. Thus, tabular grains having an aspect ratio of 5 or more have a total projected area of 5
Tabular grains having an aspect ratio of 2 or more occupy 90% of the total projected area;
0), a tabular silver iodobromide emulsion (Em-B) having a coefficient of variation of 18% and an equivalent sphere diameter of 0.6 μm was prepared. According to observation with a 200 kV transmission electron microscope at liquid N ₂ temperature, 1
Grains having more than 50 dislocation lines per grain accounted for 60%.

(Preparation of Emulsion According to the Present Invention) The emulsion Em-B prepared above was divided into small portions and the temperature was raised to 60 ° C. next,
As shown in Table 2, the corresponding Em-201 to 206 (previously chemically sensitized fine grain emulsion) was added per mole Ag of the emulsion Em-B (1.0% of Em-B in silver amount). In addition, sodium thiosulfate (1.8 × 10 ⁻⁵ mol / mol Ag) and potassium thiocyanate (2 × 10 ⁻³ mol / mol Ag) are added, and the mixture is aged for 45 minutes, according to the present invention. Various emulsions were prepared.

(Preparation of Comparative Emulsion) The emulsion Em-B prepared above was divided into small portions and the temperature was raised to 60 ° C. Then, the same chemical sensitizer as used for the sensitization of the fine grain emulsion was dissolved in water or a methanol solution so as to have the same addition amount, added to the emulsion Em-B, chemically sensitized, and used for comparison. Was prepared.

(Preparation of Photographic Material (Sample)) Each of the emulsions obtained above was further added to a sensitizing dye represented by the following formula (ExS
-1, ExS-2 and ExS-3) were added in a molar ratio of 60: 3: 37, and the following components were further added to prepare a coating solution for forming a photosensitive layer.

[0150]

Embedded image

Magenta coupler; 3- {3- [2- (2,4-di-tert-amylphenoxy) butyrylamino] benzoylamino} -1- (2,
4,6-trichlorophenyl) pyrazolone-5-one oil; tricresyl phosphate stabilizer; 4-hydroxy-6-methyl-1,3,3a,
7-tetrazaindene antifoggant; 1- (m-sulfophenyl) -5-mercaptotetrazole monosodium salt Coating aid; sodium dodecylbenzenesulfonate hardener; 1,2-bis (vinylsulfonylacetylamino) ethane Preservative: phenoxyethanol Triacetylcellulose film having an undercoat layer (support) with the above coating solution and a separately prepared coating solution for forming a gelatin protective layer containing polymethyl methacrylate fine particles
Coated on top by simultaneous extrusion method, photographic photosensitive material (sample) 3
0-41 were created.

[Evaluation as Photographic Photosensitive Material] Each sample obtained above was evaluated for photographic properties (fog, relative spectral sensitivity) as follows. (1) The sample obtained above was exposed to red light for sensitometry (1/100 second) and subjected to the following color development processing.

──────────────────────────────────── (Processing method) Processing step Processing time Processing temperature Color development Developing 2 minutes 15 seconds 38 ° C Bleaching 6 minutes 30 seconds 38 ° C Washing 2 minutes 10 seconds 24 ° C Fixing 4 minutes 20 seconds 38 ° C Washing (1) 1 minute 5 seconds 24 ° C Washing (2) 1 minute 0 seconds 24 ° C Stable 1 Min 5 sec 38 ℃ drying 4min 20sec 55 ℃ ────────────────────────────────────

Next, the composition of the processing solution is shown. ──────────────────────────────────── (Color developing solution) Unit g Diethylenetriaminepentaacetic acid 1.0 1 -Hydroxyethylidene-1,1 3.0 diphosphonic acid sodium sulfite 4.0 potassium carbonate 30.0 potassium bromide 1.4 potassium iodide 1.5 mg hydroxylamine sulfate 2.4 4- (N-ethyl-N- β-4.5 hydroxyethylamino) -2-methylaniline sulfate Add water and add 1 liter pH 10.05０．０５ ─────────────

──────────────────────────────────── (Bleaching solution) Unit g Ethylenediaminetetraacetic acid second Iron 100.0 Sodium trihydrate Ethylenediaminetetraacetic acid di 10.0 Sodium salt Ammonium bromide 140.0 Ammonium nitrate 30.0 Ammonia water (27%) 6.5 ml Add water 1.0 liter pH 6.0 ──────────────────────────────────

──────────────────────────────────── (Fixing solution) Unit g Ethylenediaminetetraacetic acid 5.5 Sodium salt Sodium sulfite 7.0 Sodium bisulfite 5.0 Ammonium thiosulfate aqueous solution (70%) 170 ml Add water 1.0 liter pH 6.7─────────────── ─────────────────────

──────────────────────────────────── (Stabilizing solution) Unit g Formalin (37%) 2.0 ml Polyoxyethylene-p-monononyl phenyl ether (average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid di-0.05 sodium salt Water was added to add 1.0 liter, pH 5.0-8.0. ────────────────────────────────

The density of the treated sample was measured with a green filter. Table 5 shows the obtained photographic performance results. The relative spectral sensitivity is represented by the reciprocal of the exposure required to obtain an optical density of (fog value + maximum density) / 2.

[0159]

Table 5 ──────────────────────────────────── Sample Fine particles or fine particles used for emulsion preparation Sensitizer Relative spectral number (addition amount: mol / mol Ag) Fog sensitivity ───────────────────────────────── ─── 30 (comparison) Sodium thiosulfate (S) + chloroauric acid (Au) 0.16 100 31 (comparison) Em-201 (S: 1.2 × 10 ^{-5 /} Au: 2.0 × 10 ^-5 ) 15 110 32 (comparative) I-7 (Se) + chloride Auric acid (Au) 0.26 132 33 (Invention) Em-202 (Se: 1.0 × 10 ⁻⁵ /Au:2.0×10 ⁻⁵ ) 0.20 166 ──────────────────────── 34 (comparison) II-21 (Se) + chloroauric acid (Au) 0.23 138 35 (invention) Em-203 (Se: 8.0 × 10 ⁻⁶ /Au:2.0×10 ⁻⁵ ) 0.19 166 ───────────────────── ─────────────── 36 (comparative) III-10 (Te) + chloroauric acid (Au) 0.31 144 37 (invention) Em-204 (Te: 1.0 × 10 ^-5 /Au:2.0×10 ^-5 ) 0.22 184 ─────────────────────────────────── ─ 38 (comparison) V-32 (Te) + chloroauric acid (Au) 0.28 152 39 (invention) Em-205 (Te: 6.0 × 10 ^{−6 /} Au: 2.2 × 10 ⁻⁵ ) 0.20 185────────────────────────────────────40 (comparison) II-21 (Se) + V-24 (Te) + chloroauric acid (Au) 0.21 140 41 (invention) Em-206 0.18 194 (Se :: 4.0 × 10 -6 / Te: 4.0 × 10 -6 / Au: 1.6 × 10 - ⁵ ) ─────────────────────── ─────────────

As is clear from the results shown in Table 5 above, a sensitization method according to the present invention, in which sensitization was previously performed using selenium or / and tellurium-sensitized silver halide fine grains, was introduced. Silver halide emulsion (samples 33 and 35,
By using (37), (39) and (41), it is possible to obtain a photographic light-sensitive material having less fog and high spectral sensitivity.

[0161]

By using the chemical sensitization method according to the present invention, a silver halide emulsion with less fog and high sensitivity can be obtained. Further, a silver halide emulsion with less deterioration of photographic performance during storage over time can be obtained. Therefore, by using these silver halide emulsions having good performance,
A silver halide photographic material with low fog and high sensitivity can be provided.

Continuation of front page (56) References JP-A-4-342249 (JP, A) JP-A-3-4221 (JP, A) JP-A-3-194538 (JP, A) JP-A-5-2231 (JP) JP-A-3-91736 (JP, A) JP-A-6-11789 (JP, A) JP-A-6-230504 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB G03C 1/09 G03C 1/06 502 G03C 1/07

Claims (5)

(57) [Claims] A chemical sensitization of a silver halide emulsion characterized by adding silver halide fine grains which have been subjected to selenium sensitization and / or tellurium sensitization to a silver halide emulsion of a host for chemical sensitization. Sensibility. 2. The method according to claim 1, wherein said fine silver halide grains are further subjected to gold sensitization. 3. The method according to claim 1, wherein the fine silver halide grains are further subjected to sulfur sensitization. 4. The method according to claim 1, wherein a selenium sensitizer and / or tellurium sensitizer is used, and 50% or more of the selenium sensitizer and / or tellurium sensitizer is reacted with silver halide fine particles. Sensitization method for silver halide emulsions. 5. The method for chemical sensitization of a silver halide emulsion according to claim 1, wherein the silver halide fine particles are dissolved during the chemical sensitization of the silver halide emulsion of the host.