JP2899452B2 - Silver halide photographic emulsion - 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 emulsion, and more particularly to a surface latent image type silver halide photographic emulsion having improved sensitivity by using a tellurium sensitizer and a selenium sensitizer in combination.

[0002]

BACKGROUND OF THE INVENTION Silver halide emulsions used in silver halide photographic light-sensitive materials are usually chemically amplified using various chemical substances in order to obtain desired sensitivity, gradation and the like. Give a feeling. Typical methods include sulfur sensitization, selenium sensitization, tellurium sensitization, sensitization of precious metals such as gold,
Reduction sensitization and a combination thereof. Various sensitization methods 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 which hastened the progress of development and the like, and various improvements of the above-described sensitization method have been required. It has been done.

[0004] 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 great efforts and improvements have already been made. Have been.

On the other hand, selenium sensitization is disclosed in US Pat. Nos. 1,574,944, 1,602,592 and 1,623,499.
No. 3297446, No. 3297447, No. 3320069
No. 3408196, No. 3408197, No. 3442653
No. 3420670, No. 3591385, French Patent No.
No. 2693038, No. 2093209, Japanese Patent Publication No. 52-34491,
Nos. 52-34492, 53-295 and 57-22090, JP-A-5
9-180536, 59-185330, 59-181337, 59
-187338, 59-192241, 60-150046, 60-
No. 151637, No. 61-246738, JP-A-3-4221, Japanese Patent Application No.
1-287380, 1-250950, 1-254441, 2
− 34090, 2−110558, 2−130976, 2−
Nos. 139183 and 2-229300, and UK Patent No. 255846
No. 861984 and H.C. E. FIG. Spencer et al., Journal
al of Photographic Science, Vol. 31, pp. 158-169 (1986), which is known to have a greater sensitizing effect than the above-mentioned sulfur sensitization generally performed in the art. Was.

For the above-mentioned sulfur sensitization and selenium sensitization, a tellurium sensitization method and a tellurium sensitizer are disclosed in US Pat.
623499, 3320069, 3772031, 3531289
No. 3655394, No. 4704349, UK Patent No. 235211
No. 1121496, No. 1295462, No. 1396696, No. 2
No. 160993, generally disclosed in Canadian Patent No. 800958, but detailed and specific descriptions of tellurium sensitizers can be found in British Patent Nos. 1295462 and 1396696 and Canadian Patent No. 800958. And the only Canadian patent
It was only known that the arrival sensitivity could be higher than that of sulfur sensitization.

There is a strong demand for higher sensitivity of silver halide photographic emulsions, and improvement of these sensitization methods has been eagerly desired.

It is an object of the present invention to provide a silver halide photographic emulsion having high sensitivity.

[0009]

The above objects of the present invention are as follows.
This was achieved by a surface latent image type silver halide photographic emulsion characterized by being sensitized with a tellurium sensitizer and a selenium sensitizer.

As the tellurium sensitizers used in the present invention, US Pat. Nos. 1,623,499, 3,320,069 and 3,7
72,031, UK Patent Nos. 235,211 and 1,121,496,
1,295,462, 1,396,696, Canadian Patent 800,958
No., Journal of Chemical Society (J. Chem. Soc. Chem.
Commun.) 635 (1980), ibid 1102 (1979), ibid 6
45 (1979), Journal of Chemical Society Parkin Transaction (J. Chem. Soc.
Perkin Trans. ) The compounds described in 1,2191 (1980) can be used.

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), telluramides (eg, telluroacetamide, N, N-dimethyltellurobenzamide) ), Tellurohydrazide (eg, N ', N'-trimethyltellurobenzhydrazide), telluroester (eg, t-butyl-t)
-Hexyl telluride), phosphine tellurides (e.g. tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride, butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride), other tellurium compounds (e.g. UK) Patent No. 1,295,462 includes negatively charged gelatin containing telluride ions, potassium telluride, potassium tellurocyanate, telluropentathionate sodium salt, allyl tellurocyanate).

However, specific tellurium sensitizers known in the art, such as colloidal tellurium and potassium telluride exemplified in Canadian Patent No. 800958, for example, have a strong property such as stannous chloride. It is difficult to use as a sensitizer with good reproducibility due to its residual and preparation conditions, and slight changes in preparation conditions. Is not preferred for the present invention.

Of the above tellurium compounds, those preferably used in the present invention are those represented by the following general formulas (I) and (II):
Is a compound of

Formula (I)

[0015]

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. Where R
₄ and R ₇ represent an aliphatic group, an aromatic group, a heterocyclic group, a hydrogen atom or a cation, and R ₅ and R ₆ represent an aliphatic group,
Represents an aromatic group, a heterocyclic group or a hydrogen atom, and represents R ₈ , R ₉
And R ₁₀ represent an aliphatic group, and X represents a halogen atom.

Next, the general formula (I) will be described in detail.

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

In the general formula (I), 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, and is particularly a monocyclic or condensed aryl having 6 to 20 carbon atoms. And examples thereof include a phenyl group and a naphthyl group.

In the general formula (I), R ₁ , R ₂ ,
The heterocyclic group represented by R ₃ , R ₄ , R ₅ , R ₆ and R ₇ is a 3- to 10-membered saturated or unsaturated heterocyclic ring containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom. 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, and examples thereof include a pyridyl group, a furyl group, a thienyl group, a thiazolyl group, an imidazolyl group, and a benzimidazolyl group.

In the general formula (I), 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 (I) represents, for example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The 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, urethane group, sulfonylamino group, sulfamoyl group, carbamoyl group, sulfonyl group, sulfinyl group, alkyloxycarbonyl group,
Aryloxycarbonyl group, acyl group, acyloxy group, phosphoric acid amide group, diacylamino group, imide group, alkylthio group, arylthio group, halogen atom, cyano group, sulfo group, carboxy group, hydroxy group, 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 (I), 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.

General formula (II)

[0028]

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. Where R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ and R ₂₀
Represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group or an acyl group, and 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.

Next, the general formula (II) will be described in detail.

In the general formula (II), R ₁₁ , R ₁₃ ,
The aliphatic group represented by R ₁₄ , 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. , A branched or cyclic alkyl group, an alkenyl group, an alkynyl group, and an aralkyl group. Examples of the alkyl group, alkenyl group, alkynyl group, and aralkyl group include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, t-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, and cyclopentyl. Group, cyclohexyl group, allyl group, 2-butenyl group,
Examples include a 3-pentenyl group, a propargyl group, a 3-pentynyl group, a benzyl group, and a phenethyl group.

In the general formula (II), R ₁₁ , R ₁₃ , R ₁₄ ,
The aromatic group represented by R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ and R ₂₀ preferably has 6 to 30 carbon atoms, particularly a monocyclic or condensed ring having 6 to 20 carbon atoms. And examples thereof include a phenyl group and a naphthyl group.

In the general formula (II), R ₁₁ , R ₁₃ , R ₁₄ ,
The heterocyclic group represented by R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ and R ₂₀ 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. Is a 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 group, and examples thereof include a pyridyl group, a furyl group, a thienyl group, a thiazolyl group, an imidazolyl group, and a benzimidazolyl group.

In the general formula (II), 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. And include, for example, an acetyl group, a benzoyl group, a formyl group, a pivaloyl group and a decanoyl group.

Here, 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 (I).

In the general formula (II), 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 (II), 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.

The general formulas (I) and (II) of the present invention are described below.
Specific examples of the compound represented by are shown below, but the present invention is not limited thereto.

[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

Embedded image The compounds represented by the general formulas (I) and (II) of the present invention can be synthesized according to a known method.
For example, the Journal of Chemical Society (J. Chem. Soc. (A) 1969, 2927;
Of Organometallic Chemistry (J. Organ
omet. Chem.) 4, 320 (1965); ibid, 1, 200 (19
63); ibid, 113, C35 (1976); Phosphorus Sulfur 15, 155 (1983);
Hemische Berichte (Chem. Ber.) 109, 2996 (19
76); Journal of Chemical Society Chemical Communication (J. Chem. Soc. Che)
m. Commun.) 635 (1980); ibid, 1102 (1979); ib
id, 645 (1979); ibid, 820 (1987);
Of Chemical Society Parkin Transaction (J. Chem. Soc. Perkin. Trans.) 1, 21
91 (1980); The Chemistry of Organo Selenium and Tellurium Campounds (The C
hemistry of Organo Selenium and Tellurium C
ompounds), Vol. 2, 216-267 (1987).

The tellurium sensitizer used in the present invention may be added by dissolving it in water or an organic solvent (alcohols, esters, amides, etc.) miscible with water. The amount used depends on the silver halide grains to be used and the conditions of chemical ripening, but is generally per mole of silver halide.
10 ^-8 to 10 ^-2 mol, preferably about 10 ^{-7 to} 5 × 10 ^-3 mol is used.

The conditions of the chemical sensitization in the present invention include:
Although there is no particular limitation, the pAg is 6 to 11, preferably 7 to 10, the pH is 3 to 8, preferably 4 to 7, and the temperature is 40 to 95 ° C, preferably 50 to 85 ° C.

As the selenium sensitizer used in the present invention, selenium compounds disclosed in conventionally known patents can be used. That is, usually, an unstable selenium compound and / or a non-unstable selenium compound is added,
It is used by stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain period of time. As unstable selenium compounds, JP-B-44-15748, JP-B-43-13489, and Japanese Patent Application No. 2-13
It is preferable to use the compounds described in Japanese Patent Application No. 0976, Japanese Patent Application No. 2-229300, and the like. Specific examples of unstable selenium sensitizers include isoselenocyanates (eg, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenoamides, and selenocarboxylic acids (eg, , 2-selenopropionic acid, 2-
Selenobutyric acid), selenoesters, diacylselenides (for example, bis (3-chloro-2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphineselenides, and colloidal metal selenium.

The preferred types of unstable selenium compounds have been described above, but these are not limiting. Those skilled in the art will note that an unstable selenium compound as a sensitizer for a photographic emulsion is not very important as long as selenium is unstable, and the structure of the selenium sensitizer molecule is not important. It is generally understood that the moieties carry selenium and have no role other than to make them present in the emulsion in an unstable manner. In the present invention, an unstable selenium compound having such a broad concept is advantageously used.

As the non-labile selenium compound used in the present invention, the compounds described in JP-B-46-4553, JP-B-52-34492 and JP-B-52-34491 can be used. Non-labile selenium compounds include, for example, selenous acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diallyl selenide, diallyl diselenide, dialkyl selenide, dialkyl diselenide, 2-
Selenazolidinedione, 2-selenooxazolidinethione and derivatives thereof are mentioned.

Of these selenium compounds, the following general formulas (III) and (IV) are preferred.

Formula (III)

[0055]

Embedded image In the formula, Z ₁ and Z ₂ may be the same or different from each other, and include an alkyl group (eg, methyl, ethyl, t-butyl, adamaltyl, t-octyl), an alkenyl group (eg, vinyl, propenyl), an aralkyl group (Eg, benzyl, phenethyl), aryl group (eg, phenyl, pentafluorophenyl, 4-chlorophenyl, 3-nitrophenyl, 4-octylsulfamoylphenyl, α-naphthyl), heterocyclic group (eg, pyridyl) , Thienyl, furyl, imidazolyl), -NA ₁ (A
₂₎ - represents the OA ₃ or -SA _4.

Here, A ₁ , A ₂ , A ₃ and A ₄ may be the same or different and each represents an alkyl group, an aralkyl group, an aryl group or a heterocyclic group. Alkyl group, an aralkyl group, ant - as Le group or a heterocyclic group similar example as Z ₁ and the like. However, A ₁ and A ₂
May be a hydrogen atom or an acyl group (eg, acetyl, propanoyl, benzoyl, heptafluorobutanoyl, difluoroacetyl, 4-nitrobenzoyl, α-naphthoyl, 4-trifluoromethylbenzoyl).

In the general formula (III), preferably, Z ₁ represents an alkyl group, an aryl group or —NA ₁ (A ₂ );
₂ represents -NA ₅ (A _6). A ₁ , A ₂ , A ₅ and A ₆ may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group or an acyl group.

In the general formula (III), more preferably N, N
-Dialkylselenourea, N, N, N'-trialkyl-N'-acylselenourea, tetraalkylselenourea, N, N-dialkyl-arylselenoamide, N-
Represents alkyl-N-aryl-arylselenoamide.

Formula (IV)

[0060]

Embedded image In the formula, Z ₃ , Z ₄ and Z ₅ may be the same or different, and may be an aliphatic group, an aromatic group, a heterocyclic group, -OA
₇ , —NA ₈ (A ₉ ), —SA ₁₀ , —SeA ₁₁ , Y or a hydrogen atom.

A ₇ , A ₁₀ and A ₁₁ represent an aliphatic group, an aromatic group, a heterocyclic group, a hydrogen atom or a cation, and A ₈ and A ₉ represent an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom. Y represents a halogen atom.

In the general formula (IV), Z ₃ , Z ₄ ,
The aliphatic group represented by Z ₅ , A ₇ , A ₈ , A ₁₀ and A ₁₁ is a linear, branched or cyclic alkyl group, alkenyl group,
Alkynyl group, aralkyl group (for example, methyl, ethyl, n-propyl, isopropyl, t-butyl, n-butyl, n-octyl, n-decyl, n-hexadecyl,
Cyclopentyl, cyclohexyl, allyl, 2-butenyl, 3-pentenyl, propargyl, 3-pentynyl,
Benzyl, phenethyl).

In the general formula (IV), Z ₃ , Z ₄ ,
The aromatic group represented by Z ₅ , A ₇ , A ₈ , A ₁₀ and A ₁₁ is a monocyclic or condensed aryl group (for example, phenyl, pentafluorophenyl, 4-chlorophenyl, 3-sulfophenyl, α-naphthyl, 4-methylphenyl).

In the general formula (IV), Z ₃ , Z ₄ ,
The heterocyclic group represented by Z ₅ , A ₇ , A ₈ , A ₉ , A ₁₀ and A ₁₁ 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. (For example, pyridyl, thienyl, furyl, thiazolyl, imidazolyl, benzimidazolyl).

In the general formula (IV), cations represented by A ₇ , A ₁₀ and A ₁₁ represent an alkali metal atom or ammonium, and a halogen atom represented by Y is, for example, a fluorine atom, a chlorine atom, a bromine atom Or represents an iodine atom.

In the general formula (IV), preferably, Z ₃ , Z ₄ or Z ₅ represents an aliphatic group, an aromatic group or —OA ₇ ,
A ₇ represents an aliphatic group or an aromatic group.

In formula (IV), more preferably trialkylphosphine selenide, triarylphosphine selenide, trialkylselenophosphate or triarylselenophosphate.

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

[0069]

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[0070]

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[0071]

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[0072]

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[0073]

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[0074]

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[0075]

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[0076]

Embedded image In the present invention, the selenium sensitizer may be added by dissolving it in water or an organic solvent miscible with water (alcohols, esters, amides, etc.). Although it varies depending on the silver halide grains to be used, the conditions of chemical ripening, and the like, generally, about 10 ^-8 to 10 ^-2 mol, preferably about 10 ^-7 to 10 ^-3 mol, per mol of silver halide is used.

The timing of adding the selenium sensitizer may be before or after the timing of adding the tellurium sensitizer, and it suffices if there is a period of coexistence.

Hitherto, among the three chalcogen sensitizers (sulfur, selenium, tellurium), the use of a selenium sensitizer and a sulfur sensitizer in combination has been described in US Pat. No. 3297447, etc. However, as in the present invention, there is no specific knowledge about the use of a tellurium sensitizer and a selenium sensitizer in combination and the action thereof, and the sensitivity was further increased by the combination of the two. It was unforeseeable.

In the present invention, it is preferable to use a gold sensitizer in addition to the tellurium sensitizer and the selenium sensitizer. Specifically, chloroauric acid, potassium chlorooleate, potassium olithiocyanate , Gold sulfide, gold selenide and the like, and about 10 ^-7 to 10 ^-2 mol per mol of silver halide can be used.

In the present invention, a noble metal sensitizer other than gold,
For example, platinum, palladium, iridium and the like can be used in combination.

In the present invention, a sulfur sensitizer may be used in combination. Specifically, thiosulfate (for example,
Hypo), thioureas (eg, diphenylthiourea,
Triethylthiourea, allylthiourea, etc.), rhodanines (for example, rhodanine, N-ethylrhodanine, 5-
Benzylidene-rodanine, 5-benzylidene-N-ethyl-rhodanine), thioamides (for example, thioaceamide, N-phenylthioacetamide), and further, thiohydantoins, 4-oxo-oxazoline-2-thiones, -Known unstable sulfur compounds such as poly-sulfides, mercapto compounds such as cysteine, polythionates, elemental sulfur, etc., and about 10 ^-7 to 10 ^-2 mol per mol of silver halide may be used. it can.

In the present invention, a reduction sensitizer may be used in combination. Specifically, stannous chloride, aminoiminomethanesulfinic acid, a hydrazine derivative, a borane compound (for example, dimethylamine borane), Examples include a silane compound and a polyamine compound.

In the present invention, it is preferable to carry out chemical sensitization in the presence of a silver halide solvent.

Specifically, thiocyanates (eg, potassium thiocyanate), thioether compounds (eg,
U.S. Pat.Nos. 3021215 and 3271157, JP-B-58-305
No. 71, compounds described in JP-A-60-136736, especially 3, 6
Dithia-1,8 octanediol, etc.), tetrasubstituted thiourea compounds (for example, JP-B-59-11892, U.S. Pat.
No. 21863, in particular, tetramethylthiourea), further, a thione compound described in JP-B-60-1134,
Mercapto compounds described in JP-B-63-29727,
Mesoionic compounds described in U.S. Pat.
Selenoether compound described in 782013, JP-A-2-11
No. 8566, for example, a ether compound and a sulfite. In particular, among these, thiocyanate, thioether
Ter 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.

The silver halide emulsion used in the present invention and a silver halide photographic light-sensitive material containing the same will be described below.

The silver halide emulsion used in the present invention is
Silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride are preferred.

The silver halide grains used in the present invention are:
Those having a regular crystal form such as cubic and octahedral, and irregular (irre
gular) or a compound 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 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. Also a particle such as a latent image is formed mainly on the surface (e.g., negative type emulsion).

The silver halide emulsion used in the present invention is:
Tabular grain emulsions having a thickness of 0.5 micron or less, preferably 0.3 micron or less, preferably 0.6 micron or more, and having an average aspect ratio of 3 or more and 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 used in the present invention has a statistical variation coefficient (a value obtained by dividing a standard deviation S by a diameter d in a distribution expressed by a diameter when the projected area is approximated by a circle). Is especially 20% or less, especially
preferable. Further, two or more emulsions may be mixed.

The photographic emulsion used in the present invention is, for example,
・ P.Glafkides, Chimie er Physiqu
e Photographeque) (published by Paul Montell, 1967)
), By GF Duffin
Photographic emulsion chemistry (P
hotographic Emulsion Chemistry (Focal Press, 1966), Vuel Zerikman (VLZ)
elikman) et al., Making and Coating
Photographic emulsion (Making and Coa)
ting Photographic Emulsion) (Focal Press, 1964).

At the time of forming the silver halide grains, for controlling the growth of the grains, a silver halide solvent such as ammonia, rodancali, rodanammonium, or the like may be used.
Thioether compounds (eg, US Pat. No. 3,271,157,
No. 3,574,628, No. 3,704,130, No. 4,297,439
No. 4,276,374) and thione compounds (for example,
53-144319, 53-82408 and 55-77737) and amine compounds (for example, JP-A-54-100717).

In the course of silver halide grain formation or physical ripening, cadmium salts, zinc salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof,
An iron salt or an iron complex salt may coexist.

As a binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, 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; hydroxyethyl cellulose
Cellulose, carboxymethylcellulose, cellulose derivatives such as cellulose sulfates, sodium alginate,
Sugar derivatives such as starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole Various synthetic hydrophilic polymer substances such as a single or a copolymer can be used.

As gelatin, in addition to general-purpose lime-processed gelatin, acid gelatin and the journal of the Japan Society of Scientific Photography (Bull. So
c. Phot. Japan), No. 16, page 30 (1966) may be used, or a hydrolyzate of gelatin may be used.

In the light-sensitive material of the present invention, an inorganic or organic hardener may be contained in any hydrophilic colloid layer constituting the photographic light-sensitive layer or the back layer. For example, chromium salts, aldehyde salts (for example, formaldehyde, glyoxal, glutaraldehyde) and N-methylol-based compounds (for example, dimethylol urea) are mentioned as specific examples. Active halogen compounds (for example, 2,4-dichloro-
6-hydroxy-1,3,5-triazine and its sodium salt) and active vinyl compounds (for example, 1,3-bisvinylsulfonyl-2-propanol, 1,2-bis (vinylsulfonylacetamide) ethane, bis ( Vinyl-based polymers having vinylsulfonylmethyl) ether or bitylsulfonyl groups in the side chain are preferred because they rapidly cure hydrophilic colloids such as gelatin and provide stable photographic properties. N-carbamoylpyridinium salts (for example, (1-morpholinocarbonyl-3-pyridinio) methanesulfonate) and haloamidinium salts (for example, 1- (1-chloro-1-pyridinomethylene) pyrrolidinium-2-naphthalenesulfate) are also cured. Speed is excellent.

The silver halide photographic emulsion used in the present invention may be spectrally sensitized with a methine dye or the like. Dyes to be used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, horopora-cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxanol 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,
Oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc .; nucleus in which alicyclic hydrocarbon ring is fused to these nuclei; and aromatic in these nuclei A nucleus fused with an aromatic hydrocarbon ring, that is, an indolenine nucleus, a pendundrenine nucleus, an indole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a 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 such as 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 the 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, substituted aminostilbenzene compounds having a nitrogen-containing heterocyclic nucleus group (for example, US Pat. Nos. 2,933,390 and 3,635,7
No. 21), formaldehyde condensates of aromatic organic acids (for example, those described in US Pat. No. 3,743,510),
Cadmium salts, azaindene compounds and the like may be included. U.S. Patent Nos. 3,615,613, 3,615,641, 3,6
The combinations described in 17,295 and 3,635,721 are particularly useful.

The silver halide photographic emulsion used in the present technology contains various compounds for the purpose of preventing fogging during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. Can be. That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles,
Mercaptothiazoles, mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles Mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes such as triazaindenes and tetraazaindenes. (Especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes), pentaazaindenes; as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid and benzenesulfonamide Many known compounds can be added

The light-sensitive material of the present invention comprises a coating aid, an antistatic
One or more surfactants may be included for various purposes such as improving slipperiness, emulsifying and dispersing, preventing adhesion and improving photographic properties (eg, accelerating development, increasing contrast, sensitizing).

The light-sensitive material prepared by using the present invention may contain a water-soluble dye in a hydrophilic colloid layer as a filter dye or for various purposes such as prevention of irradiation or halation. Good. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, anthraquinone dyes,
Azo dyes are preferably used, in addition to 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 present invention is applicable to multilayer multicolor photographic materials having at least two different spectral sensitivities on a support.

The multilayer natural color 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 order of arrangement of these layers can be arbitrarily selected as needed. The preferred layer arrangement is from the support side in the order of red-sensitive, green-sensitive and blue-sensitive layers, blue-sensitive layer, green-sensitive layer and red-sensitive layer or in order of blue-sensitive, red-sensitive and green-sensitive layers. 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 may be composed of three layers 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 silver halide or the like may be provided below the high-sensitivity layer, particularly the high-sensitivity blue-sensitive layer, to improve the sensitivity.

In general, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler. You can also match. 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 in the photographic material of the present invention, and specific examples thereof are described in Research Disclosure (RD) Nos. 17643 and VII-C, supra.
G.

As the yellow coupler, for example, US Pat. Nos. 3,933,501, 4,022,620 and 4,326,024
No. 4,401,752, JP-B-58-10739, and British Patent Nos. 1,425,020 and 1,476,760 are preferred.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferred. For example, US Pat. Nos. 4,310,619, 4,351,897, EP 73,636, US Pat. Nos. 3,061,432, and 3,725,067
No., Research Disclosure No. 24220 (1984
June), JP-A-60-33552, Research Disclosure
JA No. 24230 (June 1984), JP-A-60-43659
And those described in U.S. Pat. Nos. 4,500,603 and 4,540,654 are preferred.

Examples of the cyan coupler include phenol-based and naphthol-based couplers.
No. 4,052,212, No. 4,146,396, No. 4,228,233,
Nos. 4,296,200, 2,369,929, 2,801,171
No. 2,772,162, No. 2,895,826, No. 3,772,
No. 002, No. 3,758,308, No. 4,334,011, No. 4,3
27,173, West German Patent Publication No. 3,329,729, European Patent No. 1
21,365A, U.S. Pat.Nos. 3,446,622 and 4,333,999
No. 4,451,559, No. 4,427,767, European Patent
Those described in No. 161,626A are preferred.

A color coupler for correcting unnecessary absorption of a coloring dye is described, for example, in Research Disclosure No. 17643, Section VII-G, US Pat. No. 4,163,670,
JP-B-57-39413, U.S. Pat.No. 4,004,929,
Nos. 4,138,258 and British Patent 1,146,368 are preferred.

A coupler in which the coloring dye has an appropriate diffusibility
Examples include U.S. Pat.No. 4,366,237 and U.K.
2,125,570, European Patent No. 96,570, West German Patent (public)
No. 3,234,533 are preferred.

Typical examples of polymerized dye-forming couplers are described in US Pat. Nos. 3,451,820, 4,080,211 and 4,367,282 and British Patent 2,102,173.

Couplers which release a photographically useful residue upon coupling can also be preferably used in the present invention. The DIR coupler that releases the development inhibitor is the above-mentioned R
D 17643, Patents described in Sections VII to F, JP-A-57-15
Nos. 1944, 57-154234, 60-184248, U.S. Pat.
Those described in 4,248,962 are preferred.

Examples of a cap which releases a nucleating agent or a development accelerator imagewise during development are described in, for example, UK Patent No. 2,099.
No. 7,140, No. 2,131,188, JP-A-59-157638, and No. 5
Those described in No. 9-170840 are preferred.

Other couplers usable in the light-sensitive material of the present invention include, for example, competing couplers described in US Pat. No. 4,130,427, US Pat.
No. 338393, multi-equivalent coupler described in No. 4310618, JP-A-60-185950, DIR redox compound or DIR coupler-release coupler described in JP-A-62-24252,
EP-A-173302A, couplers which release dyes that recolor after disengagement; D. No. 11449, No. 24241, and bleaching accelerator releasing couplers described in JP-A-61-201247, and ligand releasing couplers described in U.S. Pat.

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.

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, 2-ethylhexyl phthalate, decyl phthalate, bis (2,4-di-t-aminophenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1, 1-diethylpropyl) phthalate), esters of phosphoric acid or phosphonic acid (eg, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate) G, tri
2-ethylhexyl phosphate, tridecyl phosphate, tributoxyethyl phosphate and trichloropropyl phosphate, di-2-ethylhexyl phenyl phosphate), benzoic acid esters (for example, -Ethylhexyl benzoate, dodecyl benzoate, 2
-Ethylhexyl-p-hydroxybenzoate), amides (eg, N, N-diethyldodecaneamide,
N, N-diethyllauramide, N-tetradecylpyrrolidone), alcohols or phenols (eg, isostearyl alcohol, 2,4-di-tert-amylphenol), aliphatic carboxylic acids Esters (for example, bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate), aniline derivatives (for example, N, N-dibutyl) -2-butoxy-
5-tert-octylaniline), hydrocarbons (for example,
Paraffin, dodecylbenzene, diisopropylnaphthalene). In addition, as an auxiliary solvent, the boiling point is about
An organic solvent having a temperature of 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used.
Examples include 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. 4,199,363.
West German Patent Application (OLS) Nos. 2,541,274 and 2,5
No. 41,230.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are formed of 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 generally used for the photographic light-sensitive material. Applied to the body. Useful as a flexible support is semi-synthesis or synthesis of cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, etc. Examples thereof include a polymer film, a baryta layer, and paper coated or laminated with an α-olefin polymer (eg, polyethene, 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 a dip coating method, a roller coating method, a curtain coating method, and an extrusion coating method may be used. it can. U.S. Pat.
No. 1294, No. 2761791, No. 3526528 and No. 3
Multiple layers may be applied simultaneously by the application method described in 508947.

The present invention can be applied to various color and black-and-white photographic materials. Color negative film for general or movie use, color reversal film for slide or television, color paper, color positive film and color reversal paper, color diffusion transfer type photosensitive material and A heat-developable color photosensitive material can be mentioned as a typical example. Research Disclosure, No. 1712
3 (July 1978), or by using a black color coupler described in US Pat. No. 4,126,461 and British Patent No. 2,102,136. The present invention can also be applied to black-and-white light-sensitive materials for use in applications. Plate making films such as squirrel films or scanner films, X-ray films for direct / indirect medical or industrial use, negative black-and-white films for photography, black-and-white photographic paper, COM or ordinary microfilms, silver salt diffusion transfer photosensitive materials The present invention can also be applied to a printout type photosensitive material.

When the photographic element of the present invention is applied to a color diffusion transfer photographic method, a peel-apart type or JP-B-46-16356, JP-B-48-33697, and JP-A-50-1
No. 3040 and British Patent No. 1,330,524, an integrated type as disclosed in JP-A-57-119345.
The structure of a film unit of a type that does not require peeling as described in the above item can be adopted.

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

Various exposure means can be used for the light-sensitive material of the present invention. 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-embedded 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 (CRT, etc.) emitted from a phosphor excited by an electron beam or the like, a liquid crystal (LCD) or a lead zirconate titanate doped with lanthanum (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 light-sensitive material of the present invention is preferably an alkaline aqueous solution mainly containing an aromatic primary amine color developing agent. As the color developing agent, aminophenol compounds are also useful, but P-phenylenediamine compounds are preferably used, and typical examples thereof are 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 may be 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, competitive couplers, nucleating agents such as sodium boron hydride, 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 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 hydrmequinone,
Known black-and-white developing agents 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 a bleach-fixing process after the bleaching process may be used. Examples of the bleaching agent include iron (III) and cobalt (III).
), Chromium (IV), copper (II) and other polyvalent metal compounds, peracids, quinones, and nitrone compounds.
Ferricyanides as representative bleaches; dichromates;
Organic complex salts of iron (III) or cobalt (III) such as ethylenediaminetetraacetic acid, diethyleneaminepentaacetic acid,
Nitrilotriacetic acid, 1,3-diamino-2-propano-
Complex salts of aminopolycarboxylic acids such as tetraacetic acid or organic acids such as citric acid, tartaric acid and malic acid; manganate; persulfate; manganate; nitrosophenol, and the like can be used. Of these, iron (III) ethylenediaminetetraacetate, iron (III) diethylenetriaminepentaacetate and persulfate are preferred from the viewpoint of rapid processing and environmental pollution. In addition, iron ethylenediaminetetraacetate (III
Complex salts are particularly useful both in independent bleach solutions and in single bath bleach-fix solutions.

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. Pat. No. 3,893,858, West German Patent 1,290,8.
No. 12, No. 2,059,988, JP-A-53-32736, No. 53-5
No. 7831, No. 37418, No. 53-65532, No. 53-72623
No. 53-95630, No. 53-95631, No. 53-104232
Nos. 53-124424, 53-141623, 53-28426
No. Research Disclosure No. 17129 (1978
Compounds having a mercapto group or a disulfide group described in Japanese Patent Application Laid-Open Nos. 50-140129; JP-B-45-8506; JP-A-52-20832; No. 53-32735, U.S. Pat.No. 3,706,5
No. 61 thiourea derivative; West German Patent No. 1,127,715
And iodides described in JP-A-58-16235; West German Patent No. 9
Polyethylene oxides described in Nos. 66,410 and 2,748,430; Polyamine compounds described in JP-B No. 45-8836;
Other JP-A-49-42434, JP-A-49-59644, JP-A-53-94
927, 54-35727, 55-26506 and 58-1
Compounds described in 63940 and iodine and bromide ions can also 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 preferred are the compounds described in U.S. Pat. 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. Color for shooting
These bleaching accelerators are particularly effective when bleach-fixing a light-sensitive material.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether-based 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 and 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 (LEWest, Phot. Sci. Eng.), Vol. 6, 3
Compounds described on pages 44 to 359 (1965) may be added. In particular, the addition of a chelating agent or an anti-bubble agent 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 (for example, inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, organic phosphonic acid, aminophosphonic acid, phosphonocarboxylic acid), bactericides (for example, benzoisothiazolinone, irithiazolone, Various additives such as 4-thiazoline benzimidazole, halogenated phenol, sulfanilamide, benzotriazole), surfactants, optical brighteners, and hardeners may be used. May be used in combination of two or more.

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

In the color light-sensitive material for photographing, the step (washing-stabilization) usually performed after fixing can be replaced with 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 treatment time of the present invention is usually 20 seconds to 10 minutes, preferably 20 seconds to 5 minutes, though it varies depending on the type of photosensitive material and processing conditions.

The silver halide color light-sensitive material of the present invention 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, indoaniline compounds described in US Pat. No. 3,342,597, Schiff base-type compounds described in Research Disclosure Nos. 14850 and 15159, and aldode compounds described in US Pat. Compounds,
Metal salt complexes described in U.S. Pat.
Including the urethane compounds described in 135628, JP-A-56-6235, JP-A-56-16133, JP-A-56-59232, and JP-A-56-59232.
− 67842, 56−83734, 56−83735, 56−
83736, 56-89735, 56-81837, 56-5
No. 4430, No. 56-106241, No. 56-107236, No. 57-975
The precursors of various salt types described in No. 31 and No. 57-83565 can be mentioned.

The silver halide color light-sensitive material of the present invention comprises:
If necessary, various types of 1
-Phenyl-3-pyrazolidones may be incorporated. Typical compounds are described in JP-A-56-64339, JP-A-57-1444547,
No. 57-211147, No. 58-50532, No. 58-50536, No.
Nos. 58-50533, 58-50534, 58-50535 and 58-115438.

The various processing solutions in the present invention are used at 10 ° C. to 50 ° C. A temperature of 33 ° C to 38 ° C is standard, but higher temperatures can accelerate the processing and shorten the processing time, while lower temperatures can improve the image quality and improve the stability of the processing solution. it can. Further, in order to save silver in the light-sensitive material, a process using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US 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, and the like may be provided in the various treatment baths as necessary.

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

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

Preferred embodiments of the present invention are shown below. (1) A silver halide photographic emulsion sensitized with a tellurium sensitizer and a selenium sensitizer. (2) The silver halide photographic emulsion according to item (1), wherein the tellurium sensitizer represented by the formula (I) is used.

Formula (I)

Wherein R ₁ , R ₂ and R ₃ are an aliphatic group,
Aromatic group, heterocyclic group, OR ₄ , NR ₅ (R ₆ ), S
R ₇ , OSiR ₈ (R ₉ ) (R ₁₀ ), X or a hydrogen atom. Here, R ₄ and R ₁₇ are an aliphatic group, an aromatic group,
X represents a heterocyclic group, a hydrogen atom or a cation; R ₅ and R ₆ represent an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom; R ₈ , R ₁₉ and R ₁₀ represent an aliphatic group; Represents a halogen atom. (3) The silver halide photographic emulsion according to item (1), wherein the tellurium sensitizer represented by the general formula (II) is used.

Formula (II)

In the formula, R ₁₁ represents an aliphatic group, an aromatic group, a heterocyclic group or —NR ₁₃ (R ₁₄ ), and R ₁₂ represents —NR ₁₅ (R
_16), - represents a _{N (R 17) N (R} 18) R 19 or -OR _20. Here, R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉
And R ₂₀ represents 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. (4) The silver halide photographic emulsion as described in (1), wherein a selenium sensitizer represented by the general formula (III) is used.

Formula (III) In the formula, Z ₁ and Z ₂ may be the same or different and include an alkyl group, an alkenyl group, an aralkyl group, and an aryl group.
, A heterocyclic group, -NA ₁ (A ₂ ), -OA ₃ , or-
Represent SA _4.

A ₃ and A ₄ represent an alkyl group, an aralkyl group, an aryl group or a heterocyclic group, and A ₁ and A ₂ represent
Represents a hydrogen atom, an acyl group, an alkyl group, an aralkyl group, an aryl group or a heterocyclic group. (5) The silver halide photographic emulsion according to item (1), wherein a selenium sensitizer represented by the general formula (IV) is used.

Formula (IV) In the formula, Z ₃ , Z ₄ and Z ₅ may be the same or different and each represents an aliphatic group, an aromatic group, a heterocyclic group, —OA ₇ ,
NA ₈ (A ₉ ), —SA ₁₀ , —SeA ₁₁ , Y, or a hydrogen atom.

A ₇ , A ₁₀ and A _{11 each} represent an aliphatic group, an aromatic group, a heterocyclic group, a hydrogen atom or a cation;
A ₈ and A ₉ represent an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, and Y represents a halogen atom. (6) The silver halide photographic emulsion according to item (1), further comprising a sulfur sensitizer. (7) The silver halide photographic emulsion according to the above (1) or (6), further comprising a gold sensitizer.

Specific examples of the present invention will be described below, but the present invention is not limited to the following examples unless the gist of the invention is exceeded.

Example 1 While stirring 0.05 g of potassium bromide and 30 g of gelatin kept at 75 ° C. and 1 l of an aqueous solution kept at pH 2 with nitric acid,
75 ml of silver nitrate aqueous solution (1M) and potassium bromide aqueous solution (1M)
M) at the same time, the silver potential is set to 0 mV with respect to the saturated calomel electrode.
During 4 minutes while maintaining the temperature.

Thereafter, a silver nitrate aqueous solution (1M) 675 was further added.
ml and an aqueous solution of Kalium bromide (1M) were brought to a silver potential of -30.
While maintaining the mV, they were simultaneously added for 36 minutes.

After the completion of the particle formation, desalting and washing with ordinary flocculation were performed, and gelatin and water were added.
Was adjusted to 6.4 and pAg to 8.6.

The obtained silver bromide emulsion had a grain diameter of 0.25 μm.
m, a monodisperse octahedral emulsion having a variation coefficient of grain diameter of 11%.

After the emulsion was subdivided, the temperature was raised to 60 ° C., and a sensitizer was added as shown in Table 1, and the emulsion was chemically ripened for 60 minutes. Thereafter, gelatin, 4-hydroxy-6-methyl 1,3,3a, 7-tetrazaindene, potassium poly-styrenesulfonate and sodium dodecylbenzenesulfonate were added to form a triacetyl cellulose film having an undercoat layer. On a support, gelatin, polymethyl methacrylate particles, 2,4-dichloro-6-hydroxy-s
Co-extrusion with a protective layer containing triazine sodium salt.

The samples were exposed to sensitometry exposure (1 second) through an optical wedge, and then exposed to MA
After developing with an A-1 developer at 20 ° C. for 10 minutes, the mixture was stopped, fixed, washed with water and dried by a conventional method, and the results of density measurement were obtained as shown in Table 1.

The relative sensitivity is represented by the relative value of the reciprocal of the exposure required to obtain an optical density of fog value + 0.2.
Was set to 100.

[0163]

[Table 1] MAA-1 Developer Meter 2.5 g Ascorbic acid 10 g Nabox 35 g Potassium bromide 1 g Add 1 liter of water to 1 liter. As is clear from Table 1, tellurium sensitizer and selenium sensitizer are used alone. Compared to the case of the above, when both were used in combination, a remarkable sensitizing effect was obtained.

This cannot be obtained in combination with a conventional well-known sulfur sensitizer.

Example 2 The same emulsion as in Example 1 was prepared, and then subdivided.
After heating to chloroauric acid (6.4 × 10 ^-5 mol / mol A
g), potassium thiocyanate (2 × 10 ^-3 mol / mol A)
g) and a sensitizer as shown in Table 2 were added and chemically aged for 60 minutes.

Thereafter, the same additives as in Example 1 were added to prepare a coated product, and the same treatment was carried out to obtain the results shown in Table 2.

However, the relative sensitivity was set to 100 for sample 31.

[0168]

[Table 2] As is evident from Table 2, even in the system using the gold sensitizer in combination, the use of the tellurium sensitizer or the selenium sensitizer alone results in a preferable result that the sensitivity is further increased when both are used together. Obtained.

This could not be obtained by combining with a conventionally well-known sulfur sensitizer.

Example 3 20 cc of glacial acetic acid and ammonia (25% by weight) were added to 4 l of an aqueous solution containing 2.8 g of potassium bromide and 120 g of gelatin kept at 60 ° C.
Add 320 cc and stir while stirring silver nitrate aqueous solution (1M) 1.
4 l and a mixed aqueous solution of potassium bromide and potassium iodide (0.
63M + 0.37M) was added simultaneously over 10 minutes while maintaining the silver potential at +40 mV relative to the saturated calomel electrode.

After adding 14 g of potassium bromide and neutralizing with acetic acid, 2.1 l of an aqueous solution of silver nitrate (1M) and an aqueous solution of kalium bromide (1M) were simultaneously added over 80 minutes while keeping the silver potential at -20 mV. did.

The obtained grains have a silver iodide content of about 37 mol% in the core part and an average silver iodide content having a silver bromide shell part of about 37 mol%.
It is a double-structure particle having a core / shell ratio of 15 mol% of 1 / 1.5, a substantially octahedral shape having a (111) plane / (100) plane ratio of 90/10, and a circle equivalent diameter of about 0.8 μm. It is a monodisperse emulsion having a grain diameter with a coefficient of variation of about 16%.

After completion of the addition, the temperature was raised to 35 ° C., desalted and washed with water by a conventional flocculation method, and gelatin and water were added to adjust the pH to 5.9 and the pAg to 8.7. This emulsion was divided into small portions, the temperature was raised to 60 ° C., sensitizers shown in Table 3 were added, and the emulsion was ripened for 40 minutes.

Thereafter, a magenta coupler; 3- {3-
[2- (2,4-di-tert-amylphenoxy) butyrylamino] benzoylamino} -1- (2,4,6-trichlorophenyl) pyrazolin-5-one oil; tricresyl phosphate stabilizer; 4- Hydroxy-6-methyl-1,3,3a,
7-tetrazaindene antifoggant 1- (m-sulfonphenyl) -5-mercaptotetrazole monosodium salt Coating aid; sodium dodecylbenzenesulfonate Hardener; 1,2-bis (vinylsulfonylacetylamino) ethane preservative A phenoxyethanol was added, and the mixture was coated on a triacetyl cellulose film support having an undercoat layer together with a gelatin protective layer containing polymethyl methacrylate fine particles by a coextrusion method.

The samples were exposed to sensitometric exposure (1/100 second) and subjected to the following color development processing.

The density of the treated sample was measured with a green filter. Table 3 shows the obtained photographic performance results. The relative sensitivity was represented by the reciprocal of the exposure required to obtain an optical density of fog value + 0.2.

[0177]

[Table 3] (Processing method) Step Processing time Processing temperature Color development 2 minutes 15 seconds 38 ° C Bleaching 6 minutes 30 seconds 38 ° C Rinse 2 minutes 10 seconds 24 ° C Fixed 4 minutes 20 seconds 38 ° C Rinse (1) 1 minute 05 seconds 24 ℃ Water washing (2) 1 minute 00 seconds 38 ° C Stabilization 1 minute 05 seconds 38 ° C Drying 4 minutes 20 seconds 55 ° C Next, make up the composition of the processing solution. (Color developing solution) (unit: g) diethylenetriaminepentaacetic acid 1.0 1-hydroxyethylidene-1,1-diphosphanoic acid 3.0 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-hydroxyethylamino]-2-methylaniline sulfate 4.5 Add water 1.0 l pH 10.05 (Bleaching solution) (unit g) Sodium ferric ethylenediaminetetraacetate trihydrate 100.0 g Disodium ethylenediaminetetraacetate Salt 10.0 Ammonium bromide 140.0 Ammonium nitrate 30.0 Ammonia water (27%) 6.5 ml Add water 1.0 l pH 6.0 (Fixing solution) (unit g) Ethylenediaminetetraacetic acid disodium salt 0.5 Sodium sulfite 7.0 Sodium bisulfite 5.0 Ammonium thiosulfate aqueous solution ( 70%) Add 170.0 ml water and add 1.0 l pH 6.7 (Stabilizing solution) (Unit g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 Disodium ethylenediaminetetraacetate 0.05 Add water 1.0 l pH 5.0-8.0 Table As is clear, also in this emulsion, a remarkable increase in sensitivity was obtained by using a tellurium sensitizer and a selenium sensitizer in combination, and it could not be obtained by using a conventionally well-known sulfur sensitizer. .

────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Hirotomo Sasaki 210 Nakanuma, Minamiashigara-shi, Kanagawa Fujisha Shin Film Co., Ltd. (56) References JP-A-61-114236 (JP, A) (58) Investigated Field (Int.Cl. ⁶ , DB name) G03C 1/09

Claims (1)

(57) [Claims] A surface latent image type silver halide photographic emulsion sensitized with a tellurium sensitizer and a selenium sensitizer.